CN113013552B - Battery diaphragm and preparation method thereof - Google Patents
Battery diaphragm and preparation method thereof Download PDFInfo
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- CN113013552B CN113013552B CN202110290244.8A CN202110290244A CN113013552B CN 113013552 B CN113013552 B CN 113013552B CN 202110290244 A CN202110290244 A CN 202110290244A CN 113013552 B CN113013552 B CN 113013552B
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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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- 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 present invention provides a battery separator comprising: a porous film formed of a polyolefin resin and inorganic nanoparticles. The battery diaphragm provided by the invention is composed of polyolefin resin and inorganic nanoparticles. The invention provides a preparation method of the battery diaphragm in the technical scheme, which comprises the following steps: mixing polyolefin resin, inorganic nano particles and a plasticizer, then carrying out mixing extrusion and tape casting by a double-screw extruder to form a casting sheet, and then carrying out biaxial tension, extraction drying and heat setting to prepare the battery diaphragm. The battery diaphragm provided by the invention can effectively improve the thermal stability of the diaphragm and provides high safety for a lithium battery.
Description
Technical Field
The invention belongs to the technical field of porous membrane materials, and particularly relates to a battery diaphragm and a preparation method thereof.
Background
Lithium ion batteries are currently the most widely used energy storage power sources, and the safety of the lithium ion batteries is always concerned by the industry. The thermal runaway inside the battery is a main factor which causes the burning and even explosion of the battery and influences the safety of the battery. Among the four key materials of the lithium battery, the diaphragm has the lowest thermal stability and is a key material for the inherent thermal safety of the battery, and the closed pore temperature and the rupture temperature are two key parameters for ensuring the safety performance of the diaphragm. Generally, battery manufacturers desire lower closed cell temperatures and higher rupture temperatures for separators, i.e., the greater the safety temperature window the better.
Due to the low melting point of polyethylene, the polyethylene microporous membrane generally has a lower closed-cell temperature, and closed cells can be realized at a lower temperature to block the transmission of lithium ions and prevent further release of energy. However, the polyethylene microporous membrane has a low membrane rupture temperature (155 ℃), and with further increase of the internal temperature of the battery, the polyethylene battery separator can be fused, so that the risk of short circuit caused by contact between the positive electrode and the negative electrode of the battery is caused.
To achieve both low closed cell and high rupture temperatures, two approaches are generally used: firstly, a polyethylene microporous membrane and a polypropylene microporous membrane are compounded, the high membrane rupture temperature (165 ℃) of polypropylene and the low closed pore temperature of polyethylene are utilized, so that the expansion of a safety window is realized, however, the thickness of a diaphragm can be additionally increased by two layers or three layers of composite membranes, and the battery diaphragm is not beneficial to the lightening and thinning; and secondly, the polyethylene, the polypropylene, the polymethylpentene and other high-thermal stability polymers are blended and extruded and then stretched to form a film, so that the polyethylene composite film is prepared, and the large safety window of low closed pore temperature and high film breaking temperature is also met, however, the air permeability of the diaphragm and the affinity of electrolyte are influenced by the addition of the high-thermal stability polymers.
Disclosure of Invention
In view of the above, the present invention provides a battery separator and a method for manufacturing the same, and the battery separator provided by the invention has a high film breaking temperature.
The present invention provides a battery separator comprising: a porous film formed of a polyolefin resin and inorganic nanoparticles.
Preferably, the inorganic nanoparticles are hydrophobically modified inorganic oxides.
Preferably, the mass content of the inorganic nanoparticles in the battery diaphragm is 5-20%.
Preferably, the polyolefin resin is selected from one or more of polyethylene, polypropylene and poly-4-methyl-1-pentene.
Preferably, the polyolefin resin has a weight average molecular weight of 30 to 150 ten thousand.
The invention provides a preparation method of a battery diaphragm in the technical scheme, which comprises the following steps:
mixing and extruding polyolefin resin, inorganic nano particles and a plasticizer to obtain an extrudate;
casting and solidifying the extrudate to obtain a cast sheet;
and stretching the casting sheet, extracting, drying and heat setting to obtain the battery diaphragm.
Preferably, the total mass of the polyolefin resin and the inorganic nanoparticles in the extrudate is 20 to 40% by mass.
Preferably, the plasticizer is selected from paraffin oil and/or decalin.
Preferably, the casting temperature in the casting curing process is 20-80 ℃.
Preferably, the stretching surface magnification is 30 to 120 times.
The battery diaphragm provided by the invention is a microporous membrane formed by mixing polyolefin resin and inorganic nanoparticles, and in order to improve the film breaking temperature of the battery diaphragm and improve the dispersibility of the inorganic nanoparticles in a plasticizer, the inorganic nanoparticles modified by hydrophobic groups are selected; the porous membrane containing the inorganic nano-particles modified by the hydrophobic polymer chains has a membrane rupture temperature of up to 180 ℃, and meanwhile, the inorganic nano-particles can be uniformly dispersed in the battery diaphragm; according to the invention, the membrane breaking temperature of the membrane is increased by adding inorganic nano particles, and the problem of 'powder falling' of the membrane is solved; the wettability of the diaphragm electrolyte is improved by adding the inorganic nano particles.
Drawings
Fig. 1 is a scanning electron microscope image and an EDS elemental distribution diagram of a silicon element of a battery separator prepared in example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other examples, which may be modified or appreciated by those of ordinary skill in the art based on the examples given herein, are intended to be within the scope of the present invention. It should be understood that the embodiments of the present invention are only for illustrating the technical effects of the present invention, and are not intended to limit the scope of the present invention. In the examples, the methods used were all conventional methods unless otherwise specified.
The present invention provides a battery separator comprising: a porous film formed of a polyolefin resin and inorganic nanoparticles.
In the present invention, the polyolefin resin is preferably one or more selected from the group consisting of polyethylene, polypropylene and poly-4-methyl-1-pentene, more preferably polyethylene; the polyolefin resin preferably has a weight average molecular weight of 30 to 150 ten thousand, more preferably 60 to 100 ten thousand.
In the present invention, the polyolefin resin is preferably contained in the battery separator in an amount of 80 to 95% by mass, more preferably 85 to 95% by mass, even more preferably 88 to 92% by mass, and most preferably 90% by mass.
In the present invention, the inorganic nanoparticles are preferably an inorganic oxide subjected to hydrophobic treatment, more preferably an inorganic oxide subjected to hydrophobic polymer treatment, and the inorganic oxide is preferably a silicon oxide and/or an aluminum oxide.
The present invention is not particularly limited in the source of the inorganic nanoparticles and the inorganic oxide subjected to hydrophobic treatment or hydrophobic polymer treatment, and may be commercially available.
In the invention, the mass content of the inorganic nanoparticles in the battery separator is preferably 5-20%, more preferably 5-15%, more preferably 8-12%, and most preferably 10%.
In the invention, the porosity of the battery separator is preferably 40-45%, more preferably 41-44%, and most preferably 42-43%.
The invention provides a preparation method of a battery diaphragm in the technical scheme, which comprises the following steps:
mixing and extruding polyolefin resin, inorganic nano particles and a plasticizer to obtain an extrudate;
casting and solidifying the extrudate to obtain a cast sheet;
and stretching the cast sheet, and then extracting, drying and heat-setting to obtain the battery diaphragm.
In the present invention, the total mass of the polyolefin resin and the inorganic nanoparticles is preferably 20 to 40% by mass, more preferably 25 to 35% by mass, and most preferably 30% by mass in the extrudate.
In the present invention, the mass ratio of the polyolefin resin and the inorganic nanoparticles is preferably 1 Kg: (50-200) g, more preferably 1 Kg: (50-150) g, most preferably 1 Kg: 100 g.
In the present invention, the plasticizer is preferably paraffin oil and/or decalin, and more preferably paraffin oil.
In the present invention, the mass content of the plasticizer in the extrusion species is preferably 60 to 80%, more preferably 65 to 75%, and most preferably 70%.
In the present invention, the method of mixing the polyolefin resin, the inorganic nanoparticles, and the plasticizer preferably includes:
mixing inorganic nano particles and a plasticizer, carrying out ultrasonic treatment, and then adding polyolefin resin for mixing.
In the present invention, the time of the ultrasonic treatment is preferably 0.5 to 1.5 hours, more preferably 0.8 to 1.2 hours, and most preferably 1 hour.
In the invention, the extrusion is preferably mixing extrusion of a double-screw extruder; the extrusion temperature is preferably 200-240 ℃, more preferably 210-230 ℃, and most preferably 220 ℃; the screw rotating speed in the extrusion process is preferably 50-70 rpm, more preferably 55-65 rpm, and most preferably 60 rpm.
In the present invention, the casting solidification is preferably cooled and solidified by a casting roll; the temperature of the casting roller in the casting process is preferably 20-80 ℃, more preferably 30-70 ℃, more preferably 40-60 ℃ and most preferably 50 ℃.
In the present invention, the stretching is preferably at least in a uniaxial direction, and more preferably in a biaxial direction. In the present invention, the stretching area magnification of the stretching is preferably 30 to 120 times, more preferably 50 to 100 times, more preferably 60 to 90 times, more preferably 70 to 80 times, and most preferably 75 times. In the invention, the stretching temperature is preferably 80-120 ℃, more preferably 90-110 ℃, and most preferably 100 ℃.
In the present invention, the extraction drying enables removal of the plasticizer. In the present invention, the method of extraction drying preferably comprises:
and putting the stretched product into a solvent for ultrasonic extraction.
In the present invention, the solvent is preferably n-hexane.
In the invention, the heat setting is preferably carried out in a clamp of a double-drawing machine, and the heat setting process is preferably stretched by 1.2-1.4 times, more preferably 1.3 times along the transverse direction; the heat setting temperature is preferably 110-130 ℃, more preferably 115-125 ℃, and most preferably 120 ℃.
The battery diaphragm provided by the invention is a microporous membrane formed by mixing polyolefin resin and inorganic nanoparticles, and in order to improve the film breaking temperature of the battery diaphragm and improve the dispersibility of the inorganic nanoparticles in a plasticizer, the inorganic nanoparticles modified by hydrophobic groups are selected; the film breaking temperature of the microporous film containing the inorganic nano-particles modified by the hydrophobic polymer chains reaches up to 180 ℃, and meanwhile, the inorganic nano-particles can be uniformly dispersed in the battery diaphragm; according to the invention, the membrane breaking temperature of the membrane is increased by adding inorganic nano particles, and the problem of 'powder falling' of the membrane is solved; the wettability of the diaphragm electrolyte is improved by adding the inorganic nano particles. The battery diaphragm provided by the invention has the rupture temperature of up to 180 ℃.
The polydimethylsiloxane modified silica used in the following examples of the invention is HB139 type nano silica provided by hubei huichi nano materials ltd; the polyethylene is 4116 type ultrahigh molecular weight polyethylene provided by tacona.
Example 1
Firstly, adding 50g of polydimethylsiloxane modified silicon dioxide into 3kg of paraffin oil, and then carrying out ultrasonic treatment on the silicon dioxide to facilitate the dispersion of the silicon dioxide, wherein the ultrasonic time is about 1 h; then, 1kg of 60 ten thousand ultrahigh molecular weight polyethylene was added to paraffin oil containing silica and mixed uniformly to obtain a mixture.
Melting and mixing the obtained mixture by using a double-screw extruder, wherein the temperature of the extruder is set to be 220 ℃, and the rotating speed of screws is 60 rpm; then, the molten mixed material is extruded by a die head and extruded to a casting roller with the surface temperature controlled at 25 ℃ to obtain a polyolefin casting sheet with oil; then, the obtained cast sheet was cut into a square of 9cm by 9cm, placed in a jig of a biaxial stretcher, and subjected to asynchronous biaxial stretching in sequence by 8 times in the longitudinal direction and 8 times in the transverse direction at a stretching temperature of 100 ℃.
Then, fixing the membrane after double-drawing on a frame, putting the membrane into n-hexane for ultrasonic extraction to remove paraffin oil, and then drying; and then placing the dried membrane in a clamp of a double-drawing machine again for heat setting, stretching the membrane by 1.3 times in the transverse direction, and then recovering the membrane to 1.1 times of the initial length, wherein the heat setting temperature is 120 ℃, thus obtaining the battery diaphragm.
SEM (scanning electron microscope) detection and EDS (electron distribution spectroscopy) element distribution analysis of silicon elements are carried out on the battery diaphragm prepared in the embodiment 1, the detection result is shown in figure 1, as can be seen from figure 1, the surface appearance of the diaphragm is basically the same as that of a conventional wet diaphragm, the diaphragm is composed of fibers and micropores among the fibers, and meanwhile, silicon dioxide can be uniformly dispersed on the surface of the diaphragm.
The battery diaphragm prepared in the embodiment 1 of the invention is tested for the closed pore temperature and the rupture temperature by a resistance method, and the specific test process is as follows: impregnating a battery diaphragm with electrolyte (a mixture of ethylene carbonate and propylene carbonate with a mass ratio of 1: 1), clamping the battery diaphragm between two nickel foils, connecting the nickel foils with a resistance testing device, putting the whole device into an oven for heating or heating by using a thermal resistor, wherein the heating rate is 2 ℃/min, continuously measuring the temperature and the resistance at the same time, obtaining a resistance-temperature curve, and defining the resistance to be increased to 10 DEG 3 The temperature at ohm is the closed pore temperature, defining the resistance to drop to 10 again 3 The temperature at ohm is the film breaking temperature.
The battery separator prepared in example 1 of the present invention was tested for air permeability using a Gurley air permeability tester (model: Gurley 4110N); the porosity of the battery prepared in example 1 of the present invention was measured by a weighing method; the battery separator prepared in example 1 of the present invention was tested for the electrolyte contact angle using a contact angle meter (Dongguan sandin, model: SDC-350).
The performance test results of the battery separator prepared in example 1 of the present invention are shown in table 1.
Example 2
A battery separator was prepared according to the method of example 1, except that 50g of the polydimethylsiloxane-modified silica in example 1 was replaced with 100 g.
The battery separator prepared in example 2 of the present invention was measured for its performance according to the method of example 1, and the results are shown in table 1.
Comparative example 1
Adding 50g of silicon dioxide modified by dimethyldichlorosilane (HB 612 type silicon dioxide provided by Hubei Huichi nanometer materials Co., Ltd.) into 3kg of paraffin oil, and then carrying out ultrasonic treatment on the paraffin oil to facilitate the dispersion of the silicon dioxide, wherein the ultrasonic time is about 1 h; then, 1kg of 60 ten thousand ultrahigh molecular weight polyethylene was added to paraffin oil containing silica and mixed uniformly to obtain a mixture.
Melting and mixing the obtained mixture by using a double-screw extruder, wherein the temperature of the extruder is set to be 220 ℃, and the rotating speed of screws is 60 rpm; subsequently, the molten kneaded material was extruded through a die and extruded onto a casting roll whose surface temperature was controlled at 25 ℃ to obtain an oil-impregnated polyolefin cast sheet. Then, the obtained cast sheet was cut into a square of 9cm by 9cm, placed in a jig of a biaxial stretcher, and subjected to asynchronous biaxial stretching in the longitudinal direction by 8 times and in the transverse direction by 8 times in sequence at a stretching temperature of 100 ℃.
Then, fixing the membrane after double-drawing on a frame, putting the membrane into n-hexane for ultrasonic extraction to remove paraffin oil, and then drying; and then placing the dried film in a clamp of a double-drawing machine again for heat setting, stretching the film by 1.3 times along the transverse direction, and then recovering the film to 1.1 times of the initial length, wherein the heat setting temperature is 120 ℃. The resulting battery separator.
The performance of the battery separator prepared in comparative example 1 of the present invention was measured according to the method of example 1, and the results are shown in table 1.
Comparative example 2
A battery separator was prepared according to the method of comparative example 1, except that the dimethyldichlorosilane-modified silica in comparative example 1 was replaced with hexamethyldisilazane-modified silica (type HB151 silica supplied by hubeihui nano materials ltd).
The battery separator prepared in comparative example 2 of the present invention was tested for performance according to the method of example 1, and the results are shown in table 1.
Comparative example 3
A battery separator was prepared according to the method of example 1, except that silica was not added, as in example 1.
The battery separator prepared in comparative example 3 of the present invention was tested for performance according to the method of example 1, and the results are shown in table 1.
Table 1 results of performance test of battery separators prepared in examples of the present invention and comparative examples
From the above examples, it is known that the addition of the inorganic nanoparticles modified by the hydrophobic polymer chains can not only increase the membrane rupture temperature of the battery separator, but also improve the gas permeability of the separator and the affinity of the electrolyte.
The battery diaphragm provided by the invention is a microporous membrane formed by mixing polyolefin resin and inorganic nanoparticles, and in order to improve the film breaking temperature of the battery diaphragm and improve the dispersibility of the inorganic nanoparticles in a plasticizer, the inorganic nanoparticles modified by hydrophobic groups are selected; the film breaking temperature of the microporous film containing the inorganic nano-particles modified by the hydrophobic polymer chains reaches up to 180 ℃, and meanwhile, the inorganic nano-particles can be uniformly dispersed in the battery diaphragm; according to the invention, the membrane breaking temperature of the membrane is increased by adding inorganic nano particles, and the problem of 'powder falling' of the membrane is solved; the wettability of the diaphragm electrolyte is improved by adding the inorganic nano particles.
While only the preferred embodiments of the present invention have been described, it should be understood that various modifications and adaptations thereof may occur to one skilled in the art without departing from the spirit of the present invention and should be considered as within the scope of the present invention.
Claims (1)
1. A method of making a battery separator, comprising:
firstly, 100g of silicon dioxide modified by polydimethylsiloxane is added into 3kg of paraffin oil, and then ultrasonic treatment is carried out on the silicon dioxide to facilitate the dispersion of the silicon dioxide, wherein the ultrasonic time is about 1 h; then adding 1kg of 60 ten thousand ultrahigh molecular weight polyethylene into paraffin oil containing silicon dioxide, and uniformly mixing to obtain a mixture;
melting and mixing the obtained mixture by using a double-screw extruder, wherein the temperature of the extruder is set to be 220 ℃, and the rotating speed of screws is 60 rpm; then, the molten mixed material is extruded by a die head and extruded to a casting roller with the surface temperature controlled at 25 ℃ to obtain a polyolefin casting sheet with oil; then, cutting the obtained cast sheet into squares with the size of 9cm by 9cm, putting the squares into a clamp of a biaxial stretcher, and sequentially carrying out asynchronous biaxial stretching along the longitudinal 8 times and the transverse 8 times at the stretching temperature of 100 ℃;
then, fixing the membrane after double-drawing on a frame, putting the membrane into n-hexane for ultrasonic extraction to remove paraffin oil, and then drying; and then placing the dried membrane in a clamp of a double-drawing machine again for heat setting, stretching the membrane by 1.3 times along the transverse direction, and then recovering the membrane to 1.1 times of the initial length, wherein the heat setting temperature is 120 ℃, thus obtaining the battery diaphragm.
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| CN114221090B (en) * | 2021-12-10 | 2024-04-26 | 蜂巢能源科技股份有限公司 | Diaphragm and preparation method and application thereof |
| CN114744363B (en) * | 2022-03-29 | 2024-05-28 | 中材锂膜(宁乡)有限公司 | Lithium ion battery diaphragm slurry, preparation method thereof and diaphragm |
| CN114937851A (en) * | 2022-06-08 | 2022-08-23 | 中国科学技术大学先进技术研究院 | Diaphragm for lithium ion battery, preparation method of diaphragm and lithium ion battery |
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| JP4806159B2 (en) * | 2003-12-01 | 2011-11-02 | 三菱樹脂株式会社 | Porous film |
| KR100750009B1 (en) * | 2003-12-24 | 2007-08-16 | 아사히 가세이 케미칼즈 가부시키가이샤 | Microporous membrane made from polyolefin |
| JP2009242779A (en) * | 2008-03-13 | 2009-10-22 | Asahi Kasei E-Materials Corp | Polyolefin fine porous membrane and separator for storage battery |
| US8470898B2 (en) * | 2011-05-31 | 2013-06-25 | GM Global Technology Operations LLC | Methods of making lithium ion battery separators |
| US8993646B2 (en) * | 2011-11-18 | 2015-03-31 | GM Global Technology Operations LLC | Making a lithium ion battery separator |
| CN104157816A (en) * | 2014-08-25 | 2014-11-19 | 深圳市星源材质科技股份有限公司 | Inorganic nano particle hybridized polyolefin microporous membrane and preparation method thereof |
| CN108336276A (en) * | 2017-12-12 | 2018-07-27 | 合肥国轩高科动力能源有限公司 | Preparation method of high-stability hydrophobic ceramic coated lithium ion battery diaphragm |
| CN110854339B (en) * | 2018-08-20 | 2022-07-12 | 安徽美芯新材料有限公司 | In-situ composite ceramic diaphragm with core-shell structure and preparation method and application thereof |
| CN109461866A (en) * | 2018-08-30 | 2019-03-12 | 上海顶皓新材料科技有限公司 | A kind of low moisture lithium ion battery ceramic coating membrane and preparation method thereof |
| CN109980162B (en) * | 2019-03-01 | 2022-01-25 | 广东工业大学 | Polyphosphazene coated ceramic particles and application thereof in lithium ion battery diaphragm |
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