Patent Application
20180205056
The present invention relates to a multilayered heat-resistant separator element and a method for manufacturing same.
Microporous membranes made of polyolefin are used for separation membranes, battery separators, capacitors, and the like. Among them, battery separator applications have been focused on according to the progressive development of lithium ion batteries in recent years. A battery separator is a member that functions as a partition wall of an electrolyte and also has ion permeability that is directly linked to a charging and discharging capacity of a battery.
In recent years, for lithium ion batteries and nickel metal hydride batteries suitable for vehicles and mobile terminals, small batteries with a high energy density, a high output, and high durability and safety are required. In such batteries, a battery separator made of a polyolefin microporous membrane and a sheet electrode that are laminated or wound in a battery main body with an electrolyte layer therebetween are arranged inside a main body.
When a temperature inside the battery increases to a polyolefin melting temperature or higher, a polyolefin constituting the separator melts and blocks pores in the separator, ion transfer between electrodes is stopped, and a battery function is shut down. This shutdown operation is an important function for preventing ignition or fuming of a battery, and is an important function of the separator along with ion conductivity. Incidentally, an example of an accident in which this shutdown function was not sufficient, a battery internal temperature exceeded 150° C., and ignition occurred was reported.
Here, in recent years, in order to further increase heat resistance of a battery, the development of a multilayered heat-resistant separator element in which an inorganic particle layer is applied to a separator has progressed. The multilayered heat-resistant separator element is manufactured when a heat-resistant layer material containing inorganic particles and a binder is applied to a substrate film such as a polyolefin microporous membrane and dried.
However, problems specific to a separator element obtained by laminating different materials have been pointed out. In such a multilayered separator element, generally, problems of distortion such as “warpage” or “curling” occur due to a difference in shrinkage rate between the substrate film and the heat-resistant material layer.
In Patent Literatures 1 and 2, methods of preventing curling when a heat-resistant layer containing an inorganic substance as a main component and a substrate made of a resin are laminated are described. In Patent Literature 1, it is described that curling is prevented by regulating the thickness of the substrate film and the heat-resistant layer. In Patent Literature 2, it is described that curling is prevented by providing a low pore area at a specific portion of a multilayered heat-resistant separator element. However, since the substrate of the multilayered separator element described in Patent Literatures 1 and 2 is substantially a polyethylene microporous membrane, multilayered separator elements to which the curling prevention method described in Patent Literatures 1 and 2 can be applied are limited.
As described in Patent Literature 3, the applicant of the present invention has already succeeded in manufacturing a multilayered heat-resistant separator element by applying a coating solution containing an inorganic filler to a polyolefin microporous membrane product to form a heat-resistant layer. However, in the multilayered heat-resistant separator element described in Patent Literature 3, curling prevention was not examined.
As described above, methods of preventing the occurrence of curling in a multilayered heat-resistant separator element in which a heat-resistant layer is provided on a polyolefin substrate film have not yet been sufficiently examined. Here, the inventor of the present invention extensively examined a multilayered heat-resistant separator element in which warpage and curling are reliably prevented using a polyolefin substrate film.
As a result, it is found that, when a specific polyolefin microporous membrane is selected as a substrate and a heat-resistant layer is formed under specific conditions, warpage and curling in a multilayered heat-resistant separator element are prevented significantly.
That is, the present invention is as follows.
A multilayered heat-resistant separator element which is obtained by laminating an inorganic heat-resistant layer on at least one surface of a substrate film including a polyolefin microporous membrane having an elongation of 2% or less when tensioned at 101\1/mm2 at 100° C., and in which the thickness of the substrate film is 10 to 30 μM, the thickness of one inorganic heat-resistant layer is 1 to 5 μm, and a curl height measured by the following method (a) is less than 10 mm,
Curl height measurement method (a): a rectangular sample of 30 cm in the length direction×20 cm in the width direction cut out from a multilayered heat-resistant separator element is left under an atmosphere at 25° C. for 24 hours, and then placed on a horizontal table such that a shrunk surface side faces upward, heights (mm) of four corners of the sample from the table are measured, and an average value (mm) of the four heights (mm) is calculated as a curl height (mm).
The multilayered heat-resistant separator element according to Invention 1, wherein the polyolefin microporous membrane is a polyolefin microporous membrane obtained by microporization a polyolefin according to a dry method including a cold stretching process and a hot stretching process.
The multilayered heat-resistant separator element according to Invention 1 or 2,
wherein the polyolefin microporous membrane is a propylene polymer which has an MFR (JIS K 6758, 230° C., load 21.18 N) of 0.1 to 1.0 g/10 min and a melting point of 150 to 170° C., and optionally contains at least one selected from among ethylene and α-olefins having 4 to 8 carbon atoms.
The multilayered heat-resistant separator element according to any one of Inventions 1 to 3,
wherein the inorganic heat-resistant layer includes alumina and a binder.
A method of manufacturing a multilayered heat-resistant separator element including the following processes:
(Process 1) a process in which a polyolefin microporous membrane having an elongation of 2% or less when tensioned at 10 N/mm2 at 100° C. and having a thickness of 10 to 30 μm is manufactured;
(Process 2) a process in which an inorganic heat-resistant layer agent containing inorganic heat-resistant particles and a binder is applied to at least one surface of a substrate film including the polyolefin microporous membrane obtained in Process 1; and
(Process 3) a process in which the film obtained in Process 2 is dried at a temperature of 80 to 120° C. and a tensile force of 4 to 10 N/mm2, and the inorganic heat-resistant layer agent is dried.
The method of manufacturing a multilayered heat-resistant separator element according to Invention 5,
wherein, in Process 1, a polyolefin is converted into a microporous membrane according to a dry method including a cold stretching process and a hot stretching process.
The method of manufacturing a multilayered heat-resistant separator element according to Inventions 5 or 6,
wherein, in Process 1, according to a dry method including a cold stretching process and a hot stretching process, a propylene polymer which has an MFR (JIS K 6758, 230° C., load 21.18 N) of 0.1 to 1.0 g/10 min and a melting point of 150 to 170° C., and optionally contains at least one selected from among ethylene and α-olefins having 4 to 8 carbon atoms is converted into a microporous membrane.
The method of manufacturing a multilayered heat-resistant separator element according to any one of Inventions 5 to 7,
wherein, in Process 2, an inorganic heat-resistant layer agent including alumina and a binder is used.
Curling in the multilayered heat-resistant separator of the present invention is minimized to a range in which there is no problem in practice. When the multilayered heat-resistant separator element on which Process 3 is completed is placed on a flat table at 25° C. and left on the flat table for 24 hours, even if an end of the separator element is lifted from the surface of the table due to curling, a lifting amount (the height from the surface of the table to the end) is minimized to 10 mm or less in a rectangular sample of 30 cm in the length direction×20 cm in the width direction. The multilayered heat-resistant separator element in which the occurrence of curling is minimized in this way has substantially no problem when a battery separator element is processed and does not deteriorate battery performance.
A multilayered heat-resistant separator element of the present invention is obtained by laminating an inorganic heat-resistant layer on at least one surface of a substrate film made of a polyolefin microporous membrane having an elongation of 2% or less when tensioned at 10 N/mm2 at 100° C. The thickness of the substrate film is 10 to 30 μm, and the thickness of one inorganic heat-resistant layer is 1 to 5 μm. A curl height measured by the following method (a) is less than 10 mm.
Curl height measurement method (a): a rectangular sample of 30 cm in the length direction×20 cm in the width direction cut out from a multilayered heat-resistant separator element is left under an atmosphere at 25° C. for 24 hours, and then placed on a horizontal table such that a shrunk surface side faces upward. Heights (mm) of four corners of the sample from the table are measured. An average value (mm) of the four heights (mm) is calculated as a curl height (mm).
A substrate film used in the present invention is a polyolefin microporous membrane. A polyolefin is a polymer obtained by polymerizing monomers containing mainly olefins. Representative olefins are linear olefins having 2 to 10 carbon atoms. In addition, branched olefins, styrenes, and dienes having 4 to 8 carbon atoms such as 2-methylpropene, 3-methyl-1-butene, and 4-methyl-1-pentene can be used in combination. Representative polyolefins are polymers called polyethylene and polypropylene. Polyethylene is an ethylene homopolymer or polymer obtained by copolymerizing ethylene and a comonomer containing at least one selected from among α-olefins having 3 to 8 carbon atoms. Polypropylene is a propylene homopolymer or polymer obtained by copolymerizing propylene and a comonomer containing at least one selected from among ethylene and α-olefins having 4 to 8 carbon atoms.
As a raw material of the substrate film used in the present invention, a highly crystalline polypropylene having a high melting point is preferable. As a particularly preferable polypropylene, a propylene polymer which has a melt mass flow rate (MFR, measured under conditions according to JIS K6758 (230° C., 21.18 N)) of 0.1 to 1.0 g/10 min and a melting point of 150 to 170° C., and optionally contains at least one selected from among ethylene and α-olefins having 4 to 8 carbon atoms. A content of the above comonomer may be in any range as long as the substrate film satisfies predetermined elongation conditions.
The substrate film used in the present invention satisfies specific elongation conditions. That is, an elongation when a test piece made of the substrate film is tensioned at 10 N/mm2 using a tensile testing machine at 100° C. is in a range of 2% or less. The elongation (%) is obtained by the following formula.
Elongation (%)=[(length (mm) of tensioned test piece)−(length (mm) of initial test piece)]/(length (mm) of initial test piece)×100
Additives such as a crystal nucleating agent and a filler can be blended into a raw material of the microporous membrane of the present invention. The type and the amount of the additive are not limited as long as the above elongation conditions are satisfied, and they are in a range in which the porosity necessary for the substrate of the separator element is not damaged.
The substrate film used in the present invention may be any polyolefin microporous membrane that satisfies the above elongation conditions. As such a substrate film, a polyolefin microporous membrane that is manufactured by a so-called dry method, which is advantageous in terms of cost because no organic solvent is used, is preferable. As such a polyolefin microporous membrane, a microporous membrane having a porosity of 45% or more that is manufactured by a dry method including the following film formation process, heat treatment process, cold stretching process, hot stretching process, and relaxation process is particularly preferable.
In this process, a raw material is extruded and molded to form an original film. A polyolefin raw material is supplied to an extruder, the polyolefin raw material is melt-kneaded at a temperature of a melting point thereof or higher, and a film made of the polyolefin raw material is extruded from a die attached to the tip of the extruder. The extruder used is not limited. As the extruder, for example, any of a single screw extruder, a two-screw extruder, and a tandem extruder can be used. As the die used, any die that is used for forming a film can be used. As the die, for example, various T type dies can be used. The thickness and the shape of the original film are not particularly limited. A ratio (draft ratio) between the die slip clearance and the thickness of the original film is preferably 100 or more and more preferably 150 or more. The thickness of the original film is preferably 10 to 200 μm, and more preferably 15 to 100 μm.
In this process, the original film on which the film formation process is completed is heated. A constant tension is applied to the original film in the length direction at a temperature 5 to 65° C. lower than and preferably 10 to 25° C. lower than a melting point of the polyolefin raw material. A preferable tension is a tension at which the length of the original film becomes more than 1.0 times and 1.1 times or less the original length.
In this process, the original film on which the heat treatment process is completed is stretched at a relatively low temperature. The stretching temperature is −5° C. to 45° C., and preferably 5° C. to 30° C. The stretch ratio is 1.0 to 1.1 in the length direction, preferably 1.00 to 1.08, and more preferably 1.02 or more and less than 1.05. However, the stretch ratio is greater than 1.0 times. The stretching method is not limited. Known methods such as a roll stretching method, and a tenter stretching method can be used. The number of stretching steps can be arbitrarily set. One stretching stage may be performed or two or more stretching stages may be performed through a plurality of rollers. In the cold stretching process, molecules of the polypropylene polymer constituting the original film are oriented. As a result, a stretched film including a lamella part with a dense molecular chain and a region (craze) with a sparse molecular chain between lamellae is obtained.
In this process, the stretched film on which the cold stretching process is completed is stretched at a relatively high temperature. The stretching temperature is a temperature 5 to 65° C. lower than a melting point of the polypropylene polymer, and preferably, a temperature 10 to 45° C. lower than a melting point of the polyolefin raw material. The stretch ratio is 1.5 to 4.5 times, and preferably, 2.0 to 4.0 times in the length direction. The stretching method is not limited. Known methods such as a roll stretching method, and a tenter stretching method can be used. The number of stretching steps can be arbitrarily set. One stretching stage may be performed or two or more stretching stages may be performed through a plurality of rollers. In the hot stretching process, the craze generated in the cold stretching process is elongated and pores are generated.
In this process, in order to prevent the stretched film on which the hot stretching process is completed from shrinking, the film is relaxed. Generally, the relaxation temperature is a temperature slightly higher than a hot stretching temperature and a temperature 0 to 20° C. higher than a hot stretching temperature. The degree of relaxation is adjusted so that the length of the stretched film on which the relaxation process is completed finally becomes 0.7 to 1.0 times the original length. Thus, the substrate film used in the present invention is completed. The thickness of the final substrate film is 15 to 30 μm, and preferably 15 to 25 μm.
The substrate film used in the present invention satisfies specific elongation conditions. That is, an elongation when a test piece made of the substrate film is tensioned at 10 N/mm2 using a tensile testing machine at 100° C. is in a range of 2% or less. The elongation (%) is obtained by the following formula.
Elongation (%)=[(length (mm) of tensioned test piece)−(length (mm) of initial test piece)]/(length (mm) of initial test piece)×100
An inorganic heat-resistant layer is formed on at least one surface of the substrate film. The inorganic heat-resistant layer is formed by applying an inorganic heat-resistant layer agent containing inorganic heat-resistant particles, a binder, and a solvent to the substrate film, and drying and solidifying a coating solution.
As the inorganic heat-resistant particles, an electrochemically stable inorganic substance having a primary particle size of 5 to 100 nm, a melting point of 200° C. or more, and a high insulation ability is used. For example, metal oxides such as alumina, silica, titania, zirconia, magnesia, and barium titanate, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, and clay minerals such as boehmite, talc, kaolin, zeolite, apatite, halloysite, pyrophyllite, montmorillonite, sericite, mica, amesite, bentonite, calcium silicate, and magnesium silicate, are used. A mixture including a plurality of inorganic heat-resistant particles can also be used. Preferable inorganic heat-resistant particles are alumina, silica, titania, and boehmite.
The binder functions as an agent binding the substrate and the inorganic heat-resistant particles. As the binder, various resins such as a polyolefin, a fluorine-containing resin, rubber or an elastomer, celluloses, and a water soluble resin can be used. Preferable binders are polytetrafluoroethylene (PTFE) and polyvinyl fluoride (PVDF).
An amount ratio between the inorganic heat-resistant particles and the binder (inorganic heat-resistant particles:binder, weight ratio) is generally in a range of 40:60 to 98:2, preferably in a range of 50:50 to 95:5, and more preferably in a range of 60:40 to 90:10.
Generally, a solvent is added to the inorganic heat-resistant layer agent. As the solvent, a polar organic solvent such as water or acetone, N-methylpyrrolidone, dimethylacetamide, dimethylformamide, or dimethylsulfoxide can be used.
In addition to the inorganic heat-resistant particles and the binder, additives such as a dispersant, an antimicrobial agent, and a fungicide can be blended into the above inorganic heat-resistant layer agent if necessary.
Raw materials such as the inorganic heat-resistant particles, the binder, the solvent, and the additive described above are mixed and stirred to adjust an inorganic heat-resistant layer agent. The mixing and stirring methods are not limited as long as the inorganic heat-resistant particles are uniformly dispersed in the inorganic heat-resistant layer agent. In general, a homogenizer, a bead mill, and a jet mill are used.
A method of manufacturing a multilayered heat-resistant separator element of the present invention includes the following Processes 1 to 3.
In this process, a polyolefin microporous membrane having an elongation of 2% or less when tensioned at 10 N/mm2 at 100° C. and having a thickness of 10 to 30 μm is manufactured. A polyolefin microporous membrane raw material and a method for manufacturing the same are as described above.
In this process, an inorganic heat-resistant layer agent containing inorganic heat-resistant particles and a binder is applied to at least one surface of a substrate film made of the polyolefin microporous membrane obtained in Process 1. The application device is not limited. Any device that applies a liquid substance in a flat film form can be used, for example, a gravure coater, a micro gravure coater, a die coater, or a knife coater. In Process 2, the inorganic heat-resistant layer agent is applied so that the thickness of the inorganic heat-resistant layer agent provided on one surface of the substrate film is 1 to 5 μm, and preferably 1.5 to 4.0 μm.
In this process, the film obtained in Process 2 is dried at a temperature of 80 to 120° C. and a tensile force of 4 to 10 N/mm2, and the inorganic heat-resistant layer agent is dried. Due to the drying, the inorganic heat-resistant layer agent is solidified and the inorganic heat-resistant layer is formed. When Process 3 is completed, one inorganic heat-resistant layer with a thickness of 1 to 5 μm, and preferably 1.5 to 4 μm is formed. Thus, the multilayered heat-resistant separator element of the present invention is completed.
In this process, the completed multilayered heat-resistant separator element is wound. In general, this process is performed after Process 3. The multilayered heat-resistant separator element of the present invention obtained in Process 3 is wound on a roller, packaged and stored until shipping. In general, a film having a length of several tens of meters to several hundred meters is wound on one roll core.
As a raw material, a propylene polymer having a melt mass flow rate (MFR) measured according to JIS K6758 (230° C., 21.18 N) of 0.5 g/10 min and a melting point of 165° C. was used.
(1) The raw material melt-kneaded in a single screw extruder was extruded from a T die at a draft ratio of 206 to manufacture an original film with a thickness of 17 μm.
(2) Next, the original film was heated at 150° C.
(3) The original film was cold-stretched to 1.03 times at 30° C. in the length direction.
(4) A stretching heater temperature was maintained at 230° C., and the stretched film obtained in Process 3 was hot-stretched to 2.8 times in the length direction.
(5) The obtained stretched film was relaxed so that the length became 0.88 times the original length. Thus, a microporous membrane having a porosity of greater than 45% was obtained. The obtained microporous film was used as a substrate film A in the following examples and comparative examples.
Five belt-like test pieces were cut out from the obtained microporous film (120 mm in the film length (MD) direction)×(10 mm in the film width (TD) direction). Using a tensile testing machine commercially available from Shimadzu Corporation (autograph AGS-X) in a thermostat at 100° C., a tensile force was applied to one test piece. The tension conditions were as follows: initial distance between chucks: 50 mm, tensile rate: 50 mm/min, tensile direction: test piece MD direction, and maximum tensile force: 10 N/mm2 (tensile force per film cross-sectional area). Using the length (MD-max) (mm) of the test piece in the MD direction when the tensile force was 10 N/mm2 and the length (120 mm) of the test piece in the MD direction before tension, an elongation (%) of the test piece was calculated by the following formula.
Elongation (%)=((MD−max)−120)÷120×100
The elongation (%) of the five test pieces was obtained according to the same procedures as above. An average value of elongations (%) of the five test pieces was calculated as an elongation (%) of the substrate film A. The elongation of the substrate film A was 1.7%.
As a raw material, a propylene polymer having a melt mass flow rate (MFR) measured according to JIS K6758 (230° C., 21.18 N) of 1.5 g/10 min and a melting point of 158° C. was used.
(1) The raw material melt-kneaded in a single screw extruder was extruded from a T die at a draft ratio of 205 to manufacture an original film with a thickness of 22 μm.
(2) Next, the original film was heated at 150° C.
(3) The original film was cold-stretched to 1.07 times at 30° C. in the length direction.
(4) A stretching heater temperature was maintained at 175° C., and the obtained stretched film was hot-stretched to 3.2 times in the length direction.
(5) The obtained stretched film was relaxed so that the length became 0.88 times the original length. Thus, a microporous membrane having a porosity of greater than 45% was obtained. The obtained microporous film was used as a substrate film for comparison B in the following comparative examples.
The elongation of the substrate film B was obtained in the same manner as in the substrate film A, and was 2.4%.
Al2O3 (AEROXIDE AluC commercially available from Japan Aerosil) was used as inorganic heat-resistant particles. Polyvinylidene fluoride (Kyner HSV 500 commercially available from Arkema) was used as a binder. First, the inorganic heat-resistant particles (weight concentration of 9%) and the binder (weight concentration of 3%) were added to N-methylpyrrolidone (NMP) serving as a solvent, and stirred using a Disper for 1 hour at a rotational speed of 500 rpm. Further, the obtained slurry was treated once at a processing pressure of 200 MPa using a high pressure treatment device (Nanovater commercially available from Yoshida Kikai Co., Ltd.) and mixed, and an inorganic heat-resistant layer agent C in which the inorganic heat-resistant particles and the binder were uniformly dispersed was obtained.
(Process 1) As described above, the substrate film A was manufactured.
(Process 2) The inorganic heat-resistant layer agent C was applied to one surface of the substrate film A using a gravure coater. The thickness of the applied inorganic heat-resistant layer agent was 4 μm.
A tension of 4.4 N/mm2 was applied to the substrate film to which the inorganic heat-resistant layer agent was applied, the substrate film was transferred into a drying furnace at a temperature of 95° C. and the inorganic heat-resistant layer agent was dried and solidified. Thus, a multilayered heat-resistant separator element according to the method of the present invention was obtained. The occurrence of curling in the multilayered heat-resistant separator element was evaluated by the following method.
Table 1 shows conditions of Processes 1 to 3 and evaluation results of the occurrence of curling.
A rectangular test piece of (30 cm in the length (MD) direction)×(20 cm in the width (TD) direction) was cut out from the multilayered heat-resistant separator element. The test piece was left at an atmosphere of 25° C. for 24 hours. Then, it was visually determined which surface of the test piece shrank or curling occurred. The test piece was placed on a horizontal table such that the shrunk surface faced upward, and four corners of the sample were separated from the table. That is, the test piece seen from the side was curled in a valley shape on the table. The heights (mm) of the four corners from the table were measured. The height (mm) was an integer value rounded off after the decimal point (for example, if the height of one corner from the table was 0.1 mm, 0 mm was set as the height value). Finally, an average value (mm) of the four heights (mm) was calculated as a curl height (mm). When the curl height was 10 mm or more, it was determined as a defected product.
Conditions of Processes 1 to 3 in Example 1 were changed and multilayered heat-resistant separator elements of the present invention were manufactured. Table 1 shows conditions of the processes 1 to 3, and evaluation results of the occurrence of curling.
The conditions of the processes 1 to 3 in Example 1 were changed and multilayered heat-resistant separator elements for comparison were manufactured. Table 1 shows conditions of the processes 1 to 3, and evaluation results of the occurrence of curling.
In Examples 1 to 9 in which the substrate film A was used in Process 1, and drying was performed at a temperature of 80 to 120° C. and a tensile force was 4 to 10 N/mm2 in Process 2, there was substantially no curling, or even if there was curling, it was less than 10 mm, which is not a problem in practice. On the other hand, in Comparative Examples 1 to 9 in which the substrate film B was used in Process 1 or the drying condition in Process 2 was outside the regulation, a curl height of 10 mm or more was observed, which is a problem in practice.
According to the present invention, it is possible to prevent the occurrence of curling in the multilayered heat-resistant separator element. The multilayered heat-resistant separator element of the present invention in which the occurrence of curling is prevented is advantageous in the battery assembling process and battery performance. The multilayered heat-resistant separator element of the present invention can be expected as an excellent battery separator element.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2015-016348 | Jan 2015 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2016/051786 | 1/22/2016 | WO | 00 |
