CN110911617A - High-toughness polyolefin lithium ion battery diaphragm and preparation method thereof - Google Patents
High-toughness polyolefin lithium ion battery diaphragm and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
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Abstract
The invention discloses a high-toughness polyolefin lithium ion battery diaphragm and a preparation method thereof, and belongs to the technical field of battery diaphragms. The high-toughness polyolefin lithium ion battery diaphragm is prepared by taking polyethylene, an elastomer material and inorganic rigid particles as raw materials and performing melt extrusion, biaxial stretching and extraction; the preparation method of the diaphragm comprises the following steps: step one, preparing modified particles from an elastomer material and inorganic rigid particle slurry by a spray drying method; step two, mixing the obtained modified particles with polyethylene to obtain a uniform mixed material; and step three, adding the mixed material and the pore-forming agent into a double-screw extruder for melting, plasticizing and mixing, and then extruding and biaxially stretching to obtain the isotropic high-toughness polyolefin lithium ion battery diaphragm. By adopting the technical scheme of the invention, the elongation at break of the diaphragm in each direction can be effectively improved on the basis of ensuring the mechanical strength of the diaphragm, and the safety performance of the lithium ion battery is greatly improved.
Description
Technical Field
The invention belongs to the technical field of battery diaphragms, and particularly relates to a high-toughness polyolefin lithium ion battery diaphragm and a preparation method thereof.
Background
The lithium ion battery is one of main energy sources of future new energy sources, and has the characteristics of high energy density, long service life, environment-friendly composition materials and the like, so that the lithium ion battery is widely applied to the fields of electronic equipment, aerospace, energy storage, power automobiles and the like. The diaphragm is one of the key inner layer components in each structure of the lithium ion battery, and has the main functions of separating the positive electrode from the negative electrode of the battery, preventing the two electrodes from contacting and short-circuiting, and enabling electrolyte ions to pass through, so that the performance of the diaphragm determines the characteristics of the interface structure, internal resistance, battery capacity, cycle, safety performance and the like of the battery, and especially plays a vital role in the safety performance of the lithium ion battery.
Because the use environment involves high temperature, organic solvent, mechanical compression and stretching, the lithium ion battery separator has extremely high requirements on the use performance, and must have excellent dimensional stability, chemical stability, compression resistance, puncture resistance, high tensile strength and the like. At present, the mainstream diaphragm is mainly a dry diaphragm made of polypropylene and a wet diaphragm made of polyethylene, particularly the wet diaphragm has high tensile strength due to micropores obtained by biaxial stretching, but the diaphragm has the defects of low breaking elongation, small deformation after puncture and the like due to the fact that molecular chains of the diaphragm are stretched and oriented at a high degree, and therefore the diaphragm is easy to directly damage. How to improve the breaking elongation of the lithium ion battery wet-process diaphragm in all directions and improve the puncture strength and puncture deformation rate of the lithium ion battery wet-process diaphragm is an important research direction for improving the safety of the lithium ion battery diaphragm.
Through retrieval, researchers research that the performance of the diaphragm is improved by adopting a composite or modified mode. For example, CN102751460 proposes to improve the heat resistance and mechanical properties of a polyolefin separator and a polyphenylene sulfide microporous membrane by dry compounding, and CN201810652773 proposes to perform swelling modification on a polypropylene separator by using low molecular weight oligomer or organic small molecular substance, thereby improving the mechanical properties of the separator. However, the method has complex and complicated process and high cost, and the performance of the polyolefin diaphragm body is not improved in a composite mode, so that the effect of improving the safety performance of the battery in the final use is very limited.
For another example, the chinese patent application No. 2011101017839 discloses a post-crosslinked rubber, polyolefin composite material nano-microporous membrane and a method for manufacturing the same, the microporous membrane of the application at least comprises a nano-microporous membrane a layer with a chemical gel content of more than 20%, and the microstructure thereof is designed to be that rubber material after post-crosslinking treatment is uniformly dispersed in a polyolefin nano-microfiber matrix to form the rubber, plastic composite material nano-microporous membrane. According to the application, a certain amount of rubber is added into the polyolefin diaphragm, and then irradiation crosslinking treatment is carried out, so that the elasticity and the safety performance of the obtained diaphragm can be improved to a certain extent, but the mechanical strength of the diaphragm prepared by the method cannot be effectively guaranteed, and the heat resistance of the diaphragm is reduced to a certain extent due to the addition of the rubber material, so that the safety performance of a prepared product for a battery is not obviously improved.
Disclosure of Invention
1. Problems to be solved
The invention aims to overcome the defects of low elongation at break and relatively poor safety performance of the existing lithium ion wet-process diaphragm, and provides a high-toughness polyolefin lithium ion battery diaphragm and a preparation method thereof. By adopting the technical scheme of the invention, the elongation at break of the diaphragm in each direction can be effectively improved on the basis of ensuring the mechanical strength of the diaphragm, and the safety performance of the lithium ion battery is greatly improved.
2. Technical scheme
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the high-toughness polyolefin lithium ion battery diaphragm is prepared by taking polyethylene, an elastomer material and inorganic rigid particles as raw materials and performing melt extrusion, biaxial stretching and extraction.
Furthermore, the elastomer material is one or more of nitrile rubber, styrene butadiene rubber, butyl rubber and ethylene propylene diene monomer, and the inorganic rigid particles are one or more of nano montmorillonite, hectorite, sepiolite, mica, talc, kaolin, calcium carbonate and ceramic.
Furthermore, the elastomer material is preferably ethylene propylene diene monomer, and the inorganic rigid particles are preferably ceramic.
Furthermore, the molecular weight of the polyethylene is 30-250 ten thousand.
The preparation method of the high-toughness polyolefin lithium ion battery diaphragm comprises the following steps:
step one, preparation of modified particles
Preparing modified particles from an elastomer material and inorganic rigid particle slurry by a spray drying method;
step two, mixing the obtained modified particles with polyethylene to obtain a uniform mixed material;
and step three, adding the mixed material and the pore-forming agent into a double-screw extruder for melting, plasticizing and mixing, and then extruding and biaxially stretching to obtain the isotropic high-toughness polyolefin lithium ion battery diaphragm.
Furthermore, the concentration of the inorganic rigid particle slurry obtained in the step one is 0.5-10%, the mass ratio of the elastomer material to the inorganic rigid particle slurry is (0.5-1.5): 1, and the obtained modified particles are of a core-shell structure with the elastomer coating the inorganic rigid particles.
Furthermore, the addition amount of the modified particles in the second step is 1-10% of the total weight of the obtained mixed material.
Furthermore, the addition amount of the mixed material in the third step is 25-60% of the total weight of the melt extrusion raw materials.
Furthermore, the temperature of the twin-screw melting and mixing in the third step is 160-220 ℃, and the residence time is 5-30 min; the ratio of the biaxial stretching is 5-10 times, and the stretching temperature is 90-130 ℃.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the high-toughness polyolefin lithium ion battery diaphragm, the elastomer material and the inorganic rigid particles are added into the polyethylene raw material to modify the polyethylene raw material, so that the diaphragm has high mechanical strength and high toughness, the breaking elongation of the diaphragm in each direction is effectively improved, the puncture deformation capability of the diaphragm is effectively improved, and the safety performance of a lithium ion battery is ensured.
(2) According to the high-toughness polyolefin lithium ion battery diaphragm, the composite addition of the elastomer material and the inorganic rigid particles can effectively improve the temperature deformation resistance of the diaphragm in the use process, the heat-resistant shrinkage performance of the diaphragm is more excellent, the addition of the inorganic rigid ions can also effectively improve the affinity of polyolefin and electrolyte, so that the liquid absorption rate of the diaphragm is obviously improved, and the improvement of the electrical property of the lithium ion battery is facilitated.
(3) According to the preparation method of the high-toughness polyolefin lithium ion battery diaphragm, the inorganic rigid particles are modified by rubber, then the polyethylene is subjected to melt extrusion toughening treatment by using the modified particles, the modified particles form cross-linking points to improve the strength, and the inorganic rigid particles generate a silver streak effect in the stretching process to improve the elongation, so that the toughness and puncture resistance of the obtained polyolefin lithium ion battery diaphragm can be effectively improved, the diaphragm can be ensured to have higher mechanical strength, and meanwhile, the permeability and porosity of the diaphragm can be kept basically unchanged.
(4) The preparation method of the high-toughness polyolefin lithium ion battery diaphragm comprises the steps of firstly preparing modified particles with a similar core-shell structure from an elastomer material and inorganic rigid particle slurry by a spray drying method, and then carrying out melt extrusion modification on polyethylene, wherein the modified particles with a special structure play a part in crosslinking, so that the diaphragm has stronger temperature deformation resistance (energy absorption) in the using process, and the diaphragm has more excellent heat-resistant shrinkage performance.
(5) According to the preparation method of the high-toughness polyolefin lithium ion battery diaphragm, the types, the addition amounts, the stretching process parameters and the like of the elastomer material and the inorganic rigid particles are optimally designed, so that the strength, the toughness, the safety performance and the like of the obtained diaphragm can be optimally matched, and meanwhile, the whole preparation process is similar to the existing preparation equipment and process route of the polyethylene diaphragm, so that the preparation method has the capacity of batch production and is easy to realize industrialization.
Drawings
FIG. 1 is a tensile test curve of the separator obtained in example 1;
fig. 2 is a puncture test curve of the separator obtained in example 1.
Detailed Description
Polyethylene (wet process) diaphragms are used as the current mainstream diaphragms, in order to enable the diaphragms to have certain mechanical strength, a large tensile ratio is used for orienting polyethylene molecular chains, and according to a Young modulus equation delta ═ E.epsilon (wherein delta is stress borne by a material, E is the modulus of the material, and epsilon is deformation of the material), when the modulus is not changed, the deformation of the material and the stress (and the strength) are in an inverse proportion relation, so that the toughness, namely the elongation at break of the polyethylene diaphragm is poor while the polyethylene diaphragm has high mechanical strength, the best level in the industry at present can be about 150%, and the puncture deformation resistance of the polyolefin diaphragm is a great influence factor influencing the service performance and the safety performance of a battery. Therefore, improving the toughness and the puncture deformation resistance of the polyolefin separator is of great significance for the application of the lithium ion battery, but the existing method can improve the breaking elongation of the polyolefin separator, but inevitably leads to the reduction of the strength of the separator, so that the improvement effect of the toughness of the separator is greatly limited.
Based on the problems, the elastomer material and the inorganic rigid ions are mixed and modified in a modification mode to obtain modified particles with a special core-shell structure, and then the polyethylene diaphragm is toughened and modified in a mixed co-extrusion mode, so that the toughness of the diaphragm is effectively improved, the elongation at break of the diaphragm in each direction is improved, and the puncture deformation capability of the diaphragm is improved. Namely, the obtained high-toughness diaphragm can have better deformation capacity when meeting the piercing of burrs or metal foreign matters in the battery winding process and the using process, the burrs or the metal foreign matters are coated, the risk of direct short circuit of the anode and the cathode is reduced, and the safety performance of the lithium ion battery is greatly improved.
Specifically, the modified particles play a part in crosslinking action in the modified diaphragm, so that the acting force among molecular chains is stronger, the diaphragm can have higher strength when being stretched, and meanwhile, due to the existence of the inorganic rigid particles, a plurality of hollow-hole-like silver-line structures can be preferentially formed in the region where the inorganic rigid particles exist in the stretching process of the diaphragm, and the silver-line-like structures can absorb energy in the stretching process, so that the toughness of the diaphragm is greatly enhanced, and the diaphragm has higher strength and higher elongation at break. Meanwhile, the elastomer particles with special structures play a part in crosslinking, so that the diaphragm has stronger temperature deformation resistance (energy absorption) in the use process, and the heat-resistant shrinkage performance of the diaphragm is more excellent. In addition, the polyethylene has a large polarity difference with the electrolyte, so that the affinity to the electrolyte is poor, the polyethylene has better affinity with the electrolyte after being modified by adding inorganic rigid ions, and the liquid absorption rate is obviously improved, so that the electrical property of the lithium ion battery can be further improved. In addition, the ultrahigh molecular weight polyethylene is modified by the modified particles, and then the ultrahigh molecular weight polyethylene is subjected to biaxial tension, so that the elongation at break and the puncture resistance of the diaphragm can be improved, and the permeability and the porosity of the diaphragm can be effectively kept unchanged.
The elastomer is one or more of nitrile rubber, styrene butadiene rubber, butyl rubber and ethylene propylene diene monomer, the nano inorganic rigid particles are one or more of nano montmorillonite, hectorite, sepiolite, mica, talcum, kaolin, calcium carbonate and ceramic (preferably aluminum oxide ceramic), and the effect is best when the elastomer is the ethylene propylene diene monomer and the inorganic rigid particles are ceramic particles. It should be noted that the mass ratio of the elastomer material to the inorganic rigid particles and the addition ratio of the modified particles are critical to the performance of the obtained separator, and the inventors optimize the ratio through a large number of experiments, so as to ensure that the mechanical strength, toughness, heat shrinkage resistance and electrical performance of the obtained separator are optimally matched.
Example 1:
the preparation method of the super-tough polyolefin lithium ion battery diaphragm comprises the following steps:
step one, carrying out spray drying on an elastomer material and inorganic rigid particle slurry (the concentration of the inorganic rigid particle slurry is 3%) according to the weight part of 1:1 to prepare modified particle composite powder with a special structure; the elastomer of this example is ethylene propylene diene monomer, and the nano inorganic rigid particles are alumina ceramics.
Step two, uniformly mixing the modified particle composite powder and the ultra-high molecular weight polyethylene through mechanical stirring to obtain a mixed material, wherein the addition amount of the modified particle composite powder is 5% of the total weight of the mixed material;
and step three, adding the uniformly stirred mixed material into a double-screw extruder, shearing and blending the mixed material with paraffin oil to form a uniform melt, and performing biaxial tension to obtain the polyethylene microporous membrane with high toughness, wherein the weight of the mixed material is 25% of the total weight of the melt extrusion raw materials. The temperature of the twin-screw melting and mixing is 160 ℃, and the residence time is 30 min; the ratio of biaxial stretching was 5 times, and the stretching temperature was 130 ℃.
Example 2:
the preparation method of the super-tough polyolefin lithium ion battery diaphragm comprises the following steps:
step one, carrying out spray drying on an elastomer material and inorganic rigid particle slurry (the concentration of the inorganic rigid particle slurry is 0.5 percent) according to the weight part of 0.5:1 to prepare modified particle composite powder with a special structure; the elastomer of the embodiment is nitrile rubber, and the nano inorganic rigid particles are nano montmorillonite.
Step two, uniformly mixing the modified particle composite powder and the ultra-high molecular weight polyethylene through mechanical stirring to obtain a mixed material, wherein the addition amount of the modified particle composite powder is 1% of the total weight of the mixed material;
and step three, adding the uniformly stirred mixed material into a double-screw extruder, shearing and blending the mixed material with paraffin oil to form a uniform melt, and performing biaxial tension to obtain the polyethylene microporous membrane with high toughness, wherein the weight of the mixed material is 60% of the total weight of the melt extrusion raw materials. The temperature of the twin-screw melting and mixing is 220 ℃, and the residence time is 5 min; the ratio of the biaxial stretching is 10 times, and the stretching temperature is 90 ℃.
Example 3:
the preparation method of the super-tough polyolefin lithium ion battery diaphragm comprises the following steps:
step one, carrying out spray drying on an elastomer material and inorganic rigid particle slurry (the concentration of the inorganic rigid particle slurry is 10%) according to the weight part of 1.5:1 to prepare modified particle composite powder with a special structure; the elastomer of this example is a combination of styrene-butadiene rubber and butyl rubber, and the nano inorganic rigid particles are a combination of hectorite, calcium carbonate and alumina ceramic.
Step two, uniformly mixing the modified particle composite powder and the ultra-high molecular weight polyethylene through mechanical stirring to obtain a mixed material, wherein the addition amount of the modified particle composite powder is 10% of the total weight of the mixed material;
and step three, adding the uniformly stirred mixed material into a double-screw extruder, shearing and blending the mixed material with paraffin oil to form a uniform melt, and performing biaxial tension to obtain the polyethylene microporous membrane with high toughness, wherein the weight of the mixed material is 35% of the total weight of the melt extrusion raw materials. The temperature of the double-screw melting and mixing is 185 ℃, and the retention time is 15 min; the ratio of the biaxial stretching is 7 times, and the stretching temperature is 100 ℃.
Example 4:
the preparation method of the super-tough polyolefin lithium ion battery diaphragm comprises the following steps:
step one, carrying out spray drying on an elastomer material and inorganic rigid particle slurry (the concentration of the inorganic rigid particle slurry is 7.5%) according to the weight part of 0.4:1 to prepare modified particle composite powder with a special structure; the elastomer of this example is butyl rubber and the nano inorganic rigid particles are mica.
Step two, uniformly mixing the modified particle composite powder and the ultra-high molecular weight polyethylene through mechanical stirring to obtain a mixed material, wherein the addition amount of the modified particle composite powder is 3% of the total weight of the mixed material;
and step three, adding the uniformly stirred mixed material into a double-screw extruder, shearing and blending the mixed material with paraffin oil to form a uniform melt, and performing biaxial tension to obtain the polyethylene microporous membrane with high toughness, wherein the weight of the mixed material is 50% of the total weight of the melt extrusion raw materials. The temperature of the twin-screw melting and mixing is 210 ℃, and the residence time is 18 min; the ratio of biaxial stretching was 7 times, and the stretching temperature was 125 ℃.
Example 5:
the preparation method of the super-tough polyolefin lithium ion battery diaphragm comprises the following steps:
step one, carrying out spray drying on an elastomer material and inorganic rigid particle slurry (the concentration of the inorganic rigid particle slurry is 2%) according to the weight part of 0.7:1 to prepare modified particle composite powder with a special structure; the elastomer of this example is a combination of nitrile rubber, butyl rubber, and ethylene propylene diene monomer, and the nano inorganic rigid particles are a combination of talc, calcium carbonate, and ceramic.
Step two, uniformly mixing the modified particle composite powder and the ultra-high molecular weight polyethylene through mechanical stirring to obtain a mixed material, wherein the addition amount of the modified particle composite powder is 7% of the total weight of the mixed material;
and step three, adding the uniformly stirred mixed material into a double-screw extruder, shearing and blending the mixed material with paraffin oil to form a uniform melt, and performing biaxial tension to obtain the polyethylene microporous membrane with high toughness, wherein the weight of the mixed material is 45% of the total weight of the melt extrusion raw materials. The temperature of the twin-screw melting and mixing is 195 ℃, and the residence time is 27 min; the ratio of biaxial stretching was 6 times, and the stretching temperature was 116 ℃.
Example 6:
the preparation method of the super-tough polyolefin lithium ion battery diaphragm comprises the following steps:
step one, carrying out spray drying on an elastomer material and inorganic rigid particle slurry (the concentration of the inorganic rigid particle slurry is 4.5%) according to the weight part of 1:1 to prepare modified particle composite powder with a special structure; the elastomer of this embodiment is styrene-butadiene rubber, and the nano inorganic rigid particles are ceramic.
Step two, uniformly mixing the modified particle composite powder and the ultra-high molecular weight polyethylene through mechanical stirring to obtain a mixed material, wherein the addition amount of the modified particle composite powder is 4% of the total weight of the mixed material;
and step three, adding the uniformly stirred mixed material into a double-screw extruder, shearing and blending the mixed material with paraffin oil to form a uniform melt, and performing biaxial tension to obtain the polyethylene microporous membrane with high toughness, wherein the weight of the mixed material is 28% of the total weight of the melt extrusion raw materials. The temperature of the twin-screw melting and mixing is 160 ℃, and the residence time is 20 min; the ratio of biaxial stretching was 10 times, and the stretching temperature was 93 ℃.
Claims (9)
1. A high-toughness polyolefin lithium ion battery diaphragm is characterized in that: the diaphragm is prepared by taking polyethylene, elastomer material and inorganic rigid particles as raw materials and carrying out melt extrusion, biaxial stretching and extraction.
2. The high-toughness polyolefin lithium ion battery separator according to claim 1, characterized in that: the elastomer material is one or more of nitrile rubber, styrene butadiene rubber, butyl rubber and ethylene propylene diene monomer, and the inorganic rigid particles are one or more of nano montmorillonite, hectorite, sepiolite, mica, talc, kaolin, calcium carbonate and ceramic.
3. The high-toughness polyolefin lithium ion battery separator according to claim 2, characterized in that: the elastomer material is preferably ethylene propylene diene monomer, and the inorganic rigid particles are preferably ceramic.
4. The high-toughness polyolefin lithium ion battery separator according to any one of claims 1 to 3, wherein: the molecular weight of the polyethylene is 30-250 ten thousand.
5. The preparation method of the high-toughness polyolefin lithium ion battery separator as claimed in any one of claims 1 to 4, characterized by comprising the following steps:
step one, preparation of modified particles
Preparing modified particles from an elastomer material and inorganic rigid particle slurry by a spray drying method;
step two, mixing the obtained modified particles with polyethylene to obtain a uniform mixed material;
and step three, adding the mixed material and the pore-forming agent into a double-screw extruder for melting, plasticizing and mixing, and then extruding and biaxially stretching to obtain the isotropic high-toughness polyolefin lithium ion battery diaphragm.
6. The preparation method of the high-toughness polyolefin lithium ion battery separator according to claim 5, characterized by comprising the following steps: in the first step, the mass ratio of the elastomer material to the inorganic rigid particle slurry is (0.5-1.5): 1, and the obtained modified particles are in a core-shell structure with the elastomer coating the inorganic rigid particles.
7. The preparation method of the high-toughness polyolefin lithium ion battery separator according to claim 5, characterized by comprising the following steps: and in the second step, the addition amount of the modified particles accounts for 1-10% of the total weight of the obtained mixed material.
8. The method for preparing the high-toughness polyolefin lithium ion battery separator according to any one of claims 5 to 7, wherein the method comprises the following steps: the addition amount of the mixed material in the third step is 25-60% of the total weight of the melt extrusion raw materials.
9. The method for preparing the high-toughness polyolefin lithium ion battery separator according to any one of claims 5 to 7, wherein the method comprises the following steps: the temperature of the twin-screw melting and mixing in the third step is 160-220 ℃, and the retention time is 5-30 min; the ratio of the biaxial stretching is 5-10 times, and the stretching temperature is 90-130 ℃.
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| CN112490582A (en) * | 2020-10-30 | 2021-03-12 | 河北金力新能源科技股份有限公司 | High-mechanical-strength high-toughness diaphragm and preparation method thereof |
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| CN115286857A (en) * | 2022-08-15 | 2022-11-04 | 武汉纺织大学 | Processing method for recycling lithium battery diaphragm material based on polypropylene modification |
| CN115286857B (en) * | 2022-08-15 | 2023-07-14 | 武汉纺织大学 | Polypropylene modification-based lithium battery diaphragm material recycling processing method |
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