Power storage device separator and manufacturing method thereof

Abstract

To provide a power storage device separator that can provide a power storage device with excellent cycle stability, and a manufacturing method thereof.SOLUTION: In a power storage device separator with a microporous membrane containing polyethylene as a main component, the percentage of the signal strength after a certain period of time in the observation of spin-spin relaxation time (T2 relaxation time) of all protons in pulse NMR measurement using a solid echo method at 120°C or a CPMG method at 180°C is within a certain range.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present disclosure relates to a separator for an electricity storage device and a method for producing the same. [Background technology]

[0002] Polyolefin microporous membranes exhibit excellent electrical insulation or ion permeability, and are therefore used as separators for power storage devices, such as battery separators, capacitor separators, etc. In recent years, polyolefin microporous membranes have been used particularly as separators for lithium ion secondary batteries, and are being applied not only to small electronic devices such as mobile phones and notebook computers, but also to electric vehicles such as electric cars and small electric motorcycles.

[0003] Patent Document 1 describes a separator for a secondary battery that includes a heat-resistant inorganic layer formed by atomic layer deposition (ALD) on at least one of the first and second surfaces of a porous polymer sheet and on the inner surfaces of the pores. Patent Document 2 describes a two-part adhesive formulation that includes water, a surfactant, and a protected alkylborane complex in a first part and an acrylic monomer and a trialkylborane-substituted initiator in a second part, and describes that the formulation can be applied to a low surface energy substrate without the aid of any surface pretreatment to produce effective adhesion.

[0004] Non-Patent Document 1 describes a technique for improving the wettability of a polypropylene (PP) resin separator by modifying it with polyethylene oxide (PEO) through hyperthermal hydrogen-induced crosslinking (HHIC). Non-Patent Documents 2 and 3 describe a technique for modifying polypropylene (PP) resin using borane, because the tertiary carbon in PP is prone to generating radicals. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2017-84779 [Patent Document 2] Japanese Patent Application Laid-Open No. 2007-523248 [Non-Patent Document]

[0006] [Non-Patent Document 1] Changzhen Man, et.al., 「Enhanced wetting properties of a polypropylene separator for a lithium-ion battery by hyperthermal hydrogen induced cross-linking of poly(ethylene oxide)」, J.Mater.Chem.A, 2014, 2, pp.11980-11986. [Non-Patent Document 2] Mark F. Sonnenschein, et.al., 「Physical and Chemical Probes of the Bond Strength between Trialkylboranes and Amines and Their Utility as Stabilized Free Radical Polymerization Catalysts」, Macromolecules, 2006, 39, pp.2507-2513. [Non-Patent Document 3] Mark F. Sonnenschein, et.al., 「Mechanism of Trialkylborane Promoted Adhesion to Low Surface Energy Plastics」, Macromolecules, 2004, 37, pp.7974-7978. [Non-Patent Document 4] Vincent J. McBrierty, "NMR Solid Polymers (Cambridge Solid State Science Series)", Cambridge University Press, Illustrated Edition, August 21, 2008 [Non-Patent Document 5] PJ Hore, et.al., "Introduction to NMR: Essential Tools, Basics of the Basics (Chemistry Primer Series)", Kagaku Dojin, March 22, 2017 [Non-Patent Document 6] Hideo Akutsu, Kazuo Shimada, Eiichiro Suzuki, and Yoshifumi Nishimura, "NMR Spectroscopy (Spectroscopy Series)", Kodansha, April 23, 2016 Summary of the Invention [Problem to be solved by the invention]

[0007] An object of the present disclosure is to provide a separator for an electricity storage device, which can provide an electricity storage device with excellent cycle stability, and a method for producing the same. [Means for solving the problem]

[0008] As a result of extensive investigations to solve the above-mentioned problems, the inventors of the present application have found that the above-mentioned problems can be solved by a microporous membrane containing polyethylene as a main component (also simply referred to as a "polyethylene microporous membrane") that has a specific thickness, mass-converted strength, air permeability and porosity, and that has a signal intensity ratio within a specific range in observation of the spin-spin relaxation time of all protons in pulse NMR measurement using the solid echo method or the CPMG method. Examples of embodiments of the present disclosure are listed below. [1] A separator for an electricity storage device having a microporous membrane containing polyethylene as a main component, the separator for an electricity storage device having a membrane thickness of 2 to 50 μm, a mass converted strength of 3,000 gf / g to 150,000 gf / g, an air permeability of 10 sec / 100 cc to 500 sec / 100 cc, and a porosity of 25% to 90%, and in observation of the spin-spin relaxation time (T2 relaxation time) of all protons in pulse NMR measurement using a solid echo method at 120°C, the ratio of signal intensity at 0.2 msec after the start of observation is 0.2% to 40% of the signal intensity at the start of observation, and the ratio of signal intensity at 0.8 msec after the start of observation is 0.05% to 10% of the signal intensity at the start of observation. [2] A separator for an electricity storage device having a microporous membrane containing polyethylene as a main component, the separator for an electricity storage device having a membrane thickness of 2 to 50 μm, a mass converted strength of 3,000 gf / g to 150,000 gf / g, an air permeability of 10 sec / 100 cc to 500 sec / 100 cc, and a porosity of 25% to 90%, and in observation of the spin-spin relaxation time (T2 relaxation time) of all protons in pulse NMR measurement using a CPMG method at 180°C, the ratio of signal intensity 40 msec after the start of observation is 5% to 30% of the signal intensity at the start of observation, and the ratio of signal intensity 140 msec after the start of observation is 1.5% to 20% of the signal intensity at the start of observation. [3] 3. The separator for an electricity storage device according to item 1 or 2, wherein the polyethylene present in the microporous membrane is grafted with one or more types of heteroatom-containing functional groups. [4] The one or more heteroatom-containing functional groups may be selected from the following: A type of heteroatom-containing functional group that undergoes self-condensation reactions; A combination of two or more different heteroatom-containing functional groups that undergo a condensation reaction; One or more heteroatom-containing functional groups that form a chelate complex structure via a metal ion; One or more heteroatom-containing functional groups that form any of coordinate bonds, ionic bonds, hydrogen bonds, and covalent bonds with a compound contained in another member in the electricity storage device that is in contact with the surface of the microporous membrane; and One or more heteroatom-containing functional groups having a structure that is stable in one or more stable oxidation or reduction steps 4. The separator for an electricity storage device according to item 3, selected from the group consisting of: [5] 5. The separator for an electricity storage device according to item 4, wherein the one or more heteroatom-containing functional groups have at least one selected from the group consisting of an alkoxysilane group, an alkoxy group, a hydroxyl group, an ester group, a carboxy group, an ether group, and an amine oxide group. [6] A method for producing a separator for an electricity storage device, the method comprising the steps of: (1) a step of extruding a resin composition containing polyethylene and a pore-forming material into a sheet shape using an extruder, and then cooling and solidifying the same to form a sheet-like molded product; (2) stretching the sheet-like molded article to form a stretched sheet; (3) extracting a pore-forming material from the stretched sheet to form a porous sheet; (4) heat treating the porous sheet and stretching and relaxing it in the width direction; Including, The above method further comprises the step of reacting the polyethylene with one or more graft molecules having a functional group for bonding to a molecular chain of the polyethylene and a heteroatom-containing functional group, between steps (1) and (2), between steps (2) and (3), between steps (3) and (4), or after step (4), to graft the polyethylene with the heteroatom-containing functional group. [7] 7. The method according to claim 6, wherein the functional group for bonding to the molecular chain of the polyethylene comprises a vinyl group. [8] The grafting step includes the following steps: immersing the sheet-like molded product, the stretched sheet, or the porous sheet in a solution containing a solvent, the graft molecule, and an alkylborane or an alkylborane complex; providing oxygen in the solution to react the graft molecule with the polyethylene and graft the polyethylene with the heteroatom-containing functional group; 8. The method according to item 6 or 7, comprising: [9] Item 9. The method according to item 8, further comprising extracting and drying the graft molecules and the alkylborane or alkylborane complex from the sheet-like molded body, the stretched sheet, or the porous sheet after the grafting.

[10] The method according to any one of Items 6 to 9, wherein the grafting step is carried out after step (4).

[11] The method according to any one of items 6 to 9, wherein the grafting step is carried out between steps (1) and (2).

[12] The method according to any one of items 6 to 9, wherein the grafting step is carried out between steps (2) and (3).

[13] An electricity storage device comprising: a positive electrode; a negative electrode; and the separator for an electricity storage device according to any one of items 1 to 5 between the positive electrode and the negative electrode. Effect of the Invention

[0009] According to the present disclosure, it is possible to provide a separator for an electricity storage device that can provide an electricity storage device having excellent cycle stability, and a manufacturing method thereof. Note that the above description should not be considered as disclosing all embodiments and all advantages. Further embodiments and advantages thereof will become apparent from the following description and the drawings. [Brief description of the drawings]

[0010] [Figure 1] FIG. 1 is a schematic diagram of a microporous membrane grafted with a type of heteroatom-containing functional group undergoing self-condensation reaction according to the present disclosure. [Diagram 2] FIG. 2 is a schematic diagram of a microporous membrane grafted with two heteroatom-containing functional groups undergoing a condensation reaction according to the present disclosure. [Diagram 3] FIG. 3 is a schematic diagram of a microporous membrane grafted with heteroatom-containing functional groups that form a chelate complex structure according to the present disclosure. [Figure 4] FIG. 4 is a schematic diagram of a microporous membrane grafted with heteroatom-containing functional groups that form bonds with materials in an electrode according to the present disclosure. [Diagram 5] FIG. 5 is a schematic diagram of a microporous membrane grafted with heteroatom-containing functional groups having a stable structure in one or more stable oxidation or reduction steps according to the present disclosure. [Figure 6] Fig. 6(a) shows the results of pulse NMR observation by the CPMG method of the microporous membrane of Example 1. Fig. 6(b) shows the results of pulse NMR observation by the solid echo method of the microporous membrane of Example 1. [Figure 7] Fig. 7(a) shows the results of pulse NMR observation by the CPMG method for the microporous membrane of Example 2. Fig. 7(b) shows the results of pulse NMR observation by the solid echo method for the microporous membrane of Example 2. [Figure 8] Fig. 8(a) shows the results of pulse NMR observation by the CPMG method for the microporous membrane of Example 3. Fig. 8(b) shows the results of pulse NMR observation by the solid echo method for the microporous membrane of Example 3. [Figure 9] Fig. 9(a) shows the results of pulse NMR observation by the CPMG method of the microporous membrane of Example 4. Fig. 9(b) shows the results of pulse NMR observation by the solid echo method of the microporous membrane of Example 4. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] Hereinafter, the present disclosure will be described in detail for the purpose of illustrating the embodiments, but the present disclosure is not limited to the embodiments. In the present specification, the upper limit and the lower limit of each numerical range can be arbitrarily combined.

[0012] <Separator for power storage device> Graft structure The separator for an electric storage device of the present disclosure has a microporous membrane containing polyethylene as a main component. The polyethylene present in the microporous membrane is preferably grafted with one or more heteroatom-containing functional groups. "Grafted" refers to a structure in which a heteroatom-containing functional group is bonded to a molecular chain of polyethylene as a pendant group. By grafting polyethylene with a heteroatom-containing functional group, it is possible to provide a microporous membrane having various properties such as thermal stability, electrical properties, and adhesion to electrodes.

[0013] The heteroatom is an atom other than carbon and hydrogen. The heteroatom is preferably a typical nonmetallic atom, such as a halogen atom, an oxygen atom, a sulfur atom, a nitrogen atom, a phosphorus atom, and a silicon atom. The halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The polymer high-order structure of the separator mainly composed of polyethylene has low electrostatic polarity and low affinity with the electrolyte having high intramolecular polarity. It has been found that by providing a functional group having a heteroatom in an appropriate structure of the polymer high-order structure, a partial polar structure can be imparted to the polymer high-order structure, which tends to facilitate swelling and retention of the electrolyte. As a result, even if the separator is compressed and deformed, the electrolyte swells, the volume recovery in the compression direction is good, and the uniform pore size structure of the separator can be maintained for a long period of time. Therefore, Li ion conduction can be uniformly achieved, which leads to suppression of dendrite growth, and the safety of the battery can be ensured.

[0014] Preferred examples of the heteroatom-containing functional group include a type of heteroatom-containing functional group that undergoes a self-condensation reaction; a combination of two or more different heteroatom-containing functional groups that undergo a condensation reaction; one or more types of heteroatom-containing functional groups that form a chelate complex structure via a metal ion; one or more types of heteroatom-containing functional groups that form any of coordinate bonds, ionic bonds, hydrogen bonds, and covalent bonds with a compound contained in another member in the electricity storage device that is in contact with the surface of the microporous membrane; and one or more types of heteroatom-containing functional groups that have a stable structure in one or more stable oxidation or reduction steps.

[0015] A heteroatom-containing functional group that undergoes a self-condensation reaction (also referred to as a "self-condensation functional group") refers to a functional group that can react with the same type of functional group, with a portion of the functional group being detached and the remaining portion being able to form a new bond. It is preferable that a crosslinked structure is formed between the molecular chains of polyethylene by the self-condensation reaction. By forming a crosslinked structure between the molecular chains of polyethylene, the melt viscosity of the microporous film is increased, improving the safety of the battery when it heats up. The crosslinked structure may be formed between molecular chains of polyethylene present inside or on the surface of the same microporous film.

[0016] Self-condensation may occur spontaneously in the environment within the electrical storage device or may be triggered by external stimuli, including heat and light, such as ultraviolet light.

[0017] The self-condensing functional group includes a functional group having both electrophilic and nucleophilic properties, such as a carbonyl group having a hydrogen atom at the α-position, such as an acetyl group, and an aldehyde group; and an alkoxysilane group, etc. The self-condensing functional group is preferably an alkoxysilane group, such as a methoxysilane group, and an ethoxysilane group, and more preferably a trimethoxysilane group.

[0018] FIG. 1 is a schematic diagram of a PE polymer high-order structure (10) of a microporous membrane grafted with a kind of heteroatom-containing functional group (20) undergoing a self-condensation reaction according to the present disclosure. In FIG. 1, the molecular chains of polyethylene present in the microporous membrane are grafted with a functional group having a trimethoxysilane group (-Si(OMe)3). The trimethoxysilane group undergoes a dehydration condensation reaction by heating as an external stimulus to form a crosslinked structure (30) between the molecular chains of polyethylene. In FIG. 1, n and m are each an integer of 0 to 3, and n+m is 3. As shown in FIG. 1, the trimethoxysilane group grafted to the PE polymer high-order structure in the microporous membrane may form a crosslinked structure in a battery by the stimulus of an electrolyte and / or an electrolyte solution. Although not shown, a crosslinked structure may be formed between molecular chains of polyethylene present inside or on the surface of the same microporous membrane.

[0019] A combination of two or more different heteroatom-containing functional groups (also referred to as "condensation functional groups") that undergo a condensation reaction refers to a functional group in which two or more different functional groups react with each other, some of which are detached, and the other parts can form new bonds. It is preferable that a crosslinked structure is formed in the molecular chains of polyethylene by the self-condensation reaction. By forming a crosslinked structure between the molecular chains of polyethylene, the melt viscosity of the microporous film is increased, improving the safety of the battery when it heats up.

[0020] Self-condensation may occur spontaneously in the environment within the electrical storage device or may be triggered by external stimuli, including heat and light, such as ultraviolet light.

[0021] The combination of condensed functional groups includes a combination of a functional group having properties as an electrophile and a functional group having properties as a nucleophile. The functional group having properties as an electrophile includes a carbonyl group, such as a carboxy group, an ester group, a ketone group, and an aldehyde group. The functional group having properties as a nucleophile includes a hydroxyl group, an alkoxy group, and an amine group. The combination of condensed functional groups is preferably a combination of an alkoxy group or a hydroxyl group and a carboxy group or an ester group, more preferably a combination of a hydroxyl group and an ester group, and even more preferably a combination of a hydroxyl group and a methyl ester group.

[0022] Figure 2 is a schematic diagram of a PE polymer higher-order structure (10) of a microporous membrane grafted with two types of heteroatom-containing functional groups (20) that undergo a condensation reaction according to the present disclosure. In Figure 2, the molecular chains of polyethylene present in the microporous membrane are grafted with a functional group having a carboxy group and a functional group having a methyl ester group. The functional group having a carboxy group and the functional group having a methyl ester group undergo a condensation reaction by eliminating methanol when heated as an external stimulus, forming a crosslinked structure (30) between the molecular chains of polyethylene.

[0023] A heteroatom-containing functional group that forms a chelate complex structure via a metal ion (also referred to as a "chelate complex-forming functional group") is a functional group that can coordinate to a metal ion. The ability to form a chelate complex structure is preferable because it traps metal ions generated in the energy storage element and improves the cycle characteristics of the energy storage element.

[0024] Depending on the number of coordination sites of the metal ion, the chelate complex-forming functional group may be coordinated to one metal ion alone or in combination with a plurality of chelate complex-forming functional groups. When a plurality of chelate complex-forming functional groups are coordinated to one metal ion, the plurality of chelate complex-forming functional groups may be present in the same microporous membrane.

[0025] The metal ion may be a metal ion having one or more coordination sites (M n+ , n=1-3), such as lithium ion (Li + ), cobalt ion (Co 2+ , Co 3+ ), nickel ion (Ni 2+ ), iron ion (Fe 3+ ), and manganese ions (Mn 2+ ) and the like. The metal ion is lithium ion (Li + ), the ionic resistance at the interface of the microporous membrane tends to be reduced, and the cycle characteristics and output characteristics of the electricity storage element tend to be improved.

[0026] Examples of the chelate complex-forming functional group include functional groups capable of providing an unshared electron pair capable of coordinating with a metal ion, such as an amino group, an amine group, an ether group, a hydroxyl group, a carboxyl group, and a thiol group, etc. Examples of the chelate complex-forming functional group include preferably a functional group having an ether group, more preferably an alkylene glycol group, and further preferably a methoxyethylene glycol group.

[0027] FIG. 3 is a schematic diagram of a PE polymer higher-order structure (10) of a microporous membrane grafted with a heteroatom-containing functional group (20) forming a chelate complex structure (40) according to the present disclosure. In the upper diagram of FIG. 3, the molecular chains of polyethylene present in the microporous membrane are grafted with a functional group (20) having a methoxyethylene glycol group. In FIG. 3, two ether oxygens of one methoxyethylene glycol group are bonded to a metal ion (M n+ ) is coordinated bidentately to the metal ion (M n+ ) in a bidentate coordination relationship. As shown in the lower diagram of FIG. 3, the other methoxyethylene glycol groups may form a chelate complex structure (40) in the battery so as to form a crosslinked structure upon stimulation with an electrolyte and / or an electrolyte solution. Although not shown, a crosslinked structure may also be formed between molecular chains of polyethylene present inside or on the surface of the same microporous membrane.

[0028] A heteroatom-containing functional group (also referred to as a "bond-forming functional group") that forms any of coordinate bonds, ionic bonds, hydrogen bonds, and covalent bonds with a compound contained in another component in the electricity storage device that is in contact with the surface of the microporous membrane is preferred because it can improve adhesion with the electrode and contribute to improving the stability of the electricity storage element. The bond is preferably an ionic bond formed by a carboxyl group. Other components in the electricity storage device that are in contact with the surface of the microporous membrane include a positive electrode and a negative electrode.

[0029] The compounds contained in the positive electrode include a positive electrode active material, a binder, etc. The positive electrode active material includes a material capable of absorbing and releasing metal ions, a carbon material, a metal oxide, a metal sulfide, a metal nitride, etc. Metal oxides, for example, lithium transition metal oxides, are included.

[0030] The compounds contained in the negative electrode include a negative electrode active material, a binder, etc. The negative electrode active material includes a material capable of absorbing and releasing metal ions, such as a carbon material, a metal oxide, a metal sulfide, a metal nitride, etc.

[0031] The compound to which the bond-forming functional group is bonded is preferably a compound contained in the positive electrode and / or the negative electrode, and more preferably, is a compound contained in the positive electrode active material and / or the negative electrode active material, such as a metal oxide (MO), via ionic bonds or coordination. x ) to form a bond. The bond-forming functional group is preferably a carboxyl group or the like.

[0032] FIG. 4 is a schematic diagram of a PE polymer higher-order structure (10) of a microporous membrane grafted with heteroatom-containing functional groups (20) that form bonds with materials in an electrode according to the present disclosure. In FIG. 4, the molecular chains of polyethylene present in the microporous membrane are grafted with functional groups having methyl ester groups. The methyl ester groups are converted to carboxy groups by a small amount of hydrofluoric acid (HF) in the electrolyte, and the carboxy groups are converted to carboxy groups by the metal oxide (MO) in the electrode. x ) (50) is ionically bonded to (30).

[0033] FIG. 5 is a schematic diagram of a PE polymer high-order structure (10) of a microporous membrane grafted with a heteroatom-containing functional group (20) having a stable structure in one or more stable oxidation or reduction steps according to the present disclosure. A heteroatom-containing functional group having a stable structure in one or more stable oxidation or reduction steps means that the compound can exist stably without decomposition in a structure with a changed oxidation number in an electrochemical oxidation and reduction environment in an electricity storage device. In other words, even if electrochemical oxidation and reduction are repeated, the structure of the heteroatom-containing functional group does not decompose, and a reproducible reversible oxidation and reduction waveform can be observed in cyclic voltammetry (CV) measurement. The term "one or more steps" of oxidation / reduction means that there are one or more oxidation and reduction states. For example, in the case of a 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) group, it takes two oxidation and reduction states, a reduction state with a valence of -1 and an oxidation state with a valence of +1, so it is a "two-step" oxidation / reduction.

[0034] Preferred examples of heteroatom-containing functional groups having a stable structure in one or more stable oxidation or reduction steps include nitronyl nitroxide, 4-nitrophenyl nitronyl nitroxide, phenothiazine, dihydrophenazine, and catechol.

[0035] The amount of grafting is preferably about 10 mol% or less, more preferably 2 mol% or less, and even more preferably 1.8 mol% or less, based on the total molar amount of the polyethylene units. A separator that is excessively grafted in excess of 10 mol% tends to significantly change the polymer high-order structure due to various chemical reactions that proceed within the battery. The amount of grafting is preferably 0.01 mol% or more, more preferably 0.03 mol% or more, and even more preferably 0.1 mol% or more, based on the total molar amount of the polyethylene units. If the amount of grafting is 0.01 mol% or more, it is easy to obtain the effect due to the influence on the polymer high-order structure. As will be described later, if the entire polymer high-order structure is difficult to unravel, swelling of the electrolyte is inhibited. The desired range varies depending on the graft type, and in the electrolyte, when the compressive force due to the internal pressure of the battery is released, the separator is likely to swell with the electrolyte, and it is desirable for the volume recovery rate to be high in the compression direction, so it is more important to adjust the mobility of the entire polymer structure of the separator by grafting. In the crystalline polymer, a polymer high-order structure is constructed as a crystalline component, a non-crystalline component, and an intermediate component. In the high-order structure, the crystalline component is made of a plurality of molecular chains, so the crystalline component becomes an entanglement point, and the non-crystalline component also becomes an entanglement point having a structure in which the molecular chains are entangled. Such a polymer high-order structure having a complex entanglement structure can cause swelling upon immersion with low molecules (solvent, plasticizer, electrolyte, etc.). This phenomenon is governed by the thermodynamic behavior when the entire high-order structure expands due to low molecules. For example, in a high-temperature region, the polymer high-order structure has strong molecular motion, so the entire entanglement is easily loosened and the swelling phenomenon is easily promoted. On the other hand, in the present disclosure, we have focused on the construction of a polymer high-order structure that is easily swollen by an electrolyte not only in a high-temperature region (α2 crystal relaxation temperature region of polyethylene measured by viscoelasticity measurement: around 100 to 120 ° C.) but also in a battery operating temperature region. When the polymer structure of the separator has a limited range of mobility, the electrolyte can easily penetrate the polymer structure, and a separator having a polymer higher-order structure that exhibits a high volume recovery rate even when the separator is compressed can be obtained. In the present disclosure, the mobility is quantified using a pulsed NMR method.The inventors have demonstrated that a separator with a more appropriate mobility structure can exhibit good cycle performance by maintaining uniformity in the pore size of the separator as a whole and uniformity in the electrolyte even during long-term cycles, while at the same time suppressing the formation of dendrites caused by uneven conduction of Li-ions, thereby ensuring the safety of the battery during long-term use.

[0036] It is known that the mobility of polyethylene in a separator can be quantified by observing the spin-spin relaxation time (T2 relaxation time) of all protons in the separator. Specifically, the mobility of polyethylene is divided into three components: low mobility component, high mobility component, and intermediate component. The inventors of the present application conducted repeated experiments and found that a separator having a high volume recovery rate when compressed in an electrolyte can be obtained by adjusting the ratio of signal intensity at a specific time after the start of observation to within a specific range based on the signal intensity at the start of observation using the solid echo method and the CPMG (Carr-Purcell-Meiboom-Gill) method (JEOL JNM-MU25A pulse NMR device, DOS / V Windows version operation manual reference, pages: 2-16 to 17). In general, the physical properties such as mechanical strength and heat resistance of polyethylene molded products have been explained by the crystal structure composed of crystalline and non-crystalline parts of polyethylene. These tests involve applying an external force to polyethylene to cause it to deform or break, or observing the relaxation phenomenon when heated at a temperature range much wider than the temperature range in which it is normally used. In other words, the performance of the crystal structure in the state and temperature in which the molded product is actually used cannot be directly observed, and accurate analysis is not possible in principle. On the other hand, polyethylene molded products can also be analyzed by X-ray structural analysis. However, while X-ray structural analysis can directly observe the crystal structure, it has the disadvantage that it cannot obtain information on molecular mobility. In response to this, the inventors have experimentally found an appropriate polymer high-order structure of polyethylene using a pulse NMR method that can directly observe the mobility of the entire polymer structure, focusing on the fact that the volume recovery phenomenon caused by the swelling of the separator when compressed, which is caused by the interaction between the crystal structure of polyethylene and the electrolyte, can depict the thermodynamic energy information of the entire polymer high-order structure without significantly deforming the shape of the separator.

[0037] In the case of the solid echo method, the ratio of the signal intensity 0.2 msec after the start of observation is preferably 0.2% to 40%, more preferably 0.5% to 30%, and even more preferably 2.0% to 25% based on the signal intensity at the start of observation. Also, the ratio of the signal intensity 0.8 msec after the start of observation is preferably 0.05% to 10%, more preferably 0.1% to 8.0%, and even more preferably 0.2 to 4.0% based on the signal intensity at the start of observation. In the case of the CPMG method, the ratio of the signal intensity 40 msec after the start of observation is preferably 5% to 30%, more preferably 8% to 28%, and even more preferably 10 to 25% based on the signal intensity at the start of observation. Also, the ratio of the signal intensity 140 msec after the start of observation is preferably 1.5% to 20%, more preferably 2.0% to 18%, and even more preferably 2.5 to 15% based on the signal intensity at the start of observation. By using such a method, an appropriate modification amount can be determined from the viewpoint of improving the battery cycle performance, regardless of the type of grafted chemical species to be modified. The separator of the present disclosure can cause various chemical reactions (crosslinking reaction, metal complex formation reaction, redox reaction) in the battery, and slightly changes the overall mobility of the polymer higher-order structure observed by pulse NMR before and after the chemical reaction, but satisfies the above-mentioned signal intensity ratio before and after the chemical reaction from the viewpoint of effect expression.

[0038] <polyethylene> In the present disclosure, the microporous membrane contains polyethylene as a main component. In the present specification, "containing as a main component" means that the target resin is contained in an amount of 50% by mass or more based on the total mass of the resin components constituting the microporous membrane. The polyethylene contained in the microporous membrane may be, for example, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, 99% by mass or more, or 100% by mass based on the total mass of the resin components constituting the microporous membrane.

[0039] In the present disclosure, the microporous membrane may contain other resins, for example, polyolefin resins other than polyethylene, so long as it contains polyethylene as a main component. The polyolefin resin may be a polymer containing a monomer having 3 to 10 carbon atoms as a repeating structure. Examples of the monomer having 3 to 10 carbon atoms include propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, and 1-octene. The polyolefin may be a homopolymer, a copolymer, or a multi-stage polymerization polymer, and is preferably a homopolymer. The polyolefin is preferably at least one selected from the group consisting of polypropylene and polybutadiene. The polyolefin resin may be used alone or in a mixture of two or more kinds. From the viewpoint of improving the heat resistance of the microporous membrane, the polyolefin other than polyethylene may be a mixture of polyethylene and polypropylene.

[0040] The polyethylene is low-density polyethylene (density 0.925 g / cm 3 less than 0.925g / cm), linear low density polyethylene, medium density polyethylene (density 0.925g / cm 3 More than 0.942g / cm 3 less than 0.942g / cm 3 More than 0.970g / cm 3 less than 0.970g / cm3), and ultra-high molecular weight polyethylene (density 0.970g / cm3 3 The polyethylene is preferably an ultra-high molecular weight polyethylene, since it can provide a separator with a low melting point and high strength. The density of the polyethylene is measured according to "D) Density gradient tube method" described in JIS K7112 (1999).

[0041] From the viewpoint of exhibiting rapid fuse characteristics, the lower limit of the amount of polyethylene contained in the microporous membrane, based on the total mass of the resin components constituting the microporous membrane, may be preferably 50% by mass or more, for example 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, 99% by mass or more, or 100% by mass. The upper limit of the amount of polyethylene contained in the microporous membrane, based on the total mass of the resin components constituting the microporous membrane, may be preferably 99% by mass or less, for example 90% by mass or less, 80% by mass or less, or 70% by mass or less.

[0042] Examples of polypropylene include isotactic polypropylene, syndiotactic polypropylene, atactic polypropylene, etc. Examples of copolymers of ethylene and propylene include ethylene-propylene random copolymers, ethylene-propylene rubber, etc.

[0043] From the viewpoint of improving the heat resistance of the microporous membrane, the lower limit of the amount of polypropylene contained in the microporous membrane may be preferably 1 mass% or more, 2 mass% or more, 3 mass% or more, 4 mass% or more, or 5 mass% or more based on the total mass of the resin components constituting the microporous membrane. The lower limit of the amount of polypropylene contained in the microporous membrane may be preferably 40 mass% or less, for example 35 mass% or less, 30 mass% or less, 25 mass% or less, 20 mass% or less, 15 mass% or less, or 10 mass% or less based on the total mass of the resin components constituting the microporous membrane.

[0044] Additives The microporous membrane may contain any additive. Examples of additives include polymers other than polyolefins; inorganic fillers; phenol-based, phosphorus-based, sulfur-based antioxidants; metal soaps such as calcium stearate and zinc stearate; ultraviolet absorbers; light stabilizers; antistatic agents; antifogging agents; and coloring pigments. From the viewpoint of shutdown performance, the amount of these additives may be preferably 20 parts by mass or less, for example 10 parts by mass or less, and more preferably 5 parts by mass or less, based on 100 parts by mass of the resin component constituting the microporous membrane.

[0045] <Functional Layer> The separator for an electric storage device may have one or more functional layers on one or both sides of the microporous membrane in addition to the microporous membrane. Examples of the functional layer include a heat-resistant layer containing a heat-resistant resin such as inorganic particles or a crosslinkable polymer, and an adhesive layer containing an adhesive polymer. Methods for laminating the functional layer on the microporous membrane include a method of coating the functional layer on the microporous membrane with a coater such as a gravure coater or a die coater, and a method of laminating by co-extrusion.

[0046] <Microporous membrane thickness> The thickness of the microporous membrane is preferably 0.1 μm or more and 100 μm or less, more preferably 1 μm or more and 50 μm or less, and even more preferably 3 μm or more and 25 μm or less. The thickness of the microporous membrane is preferably 0.1 μm or more from the viewpoint of mechanical strength, and is preferably 100 μm or less from the viewpoint of increasing the capacity of the electricity storage device. The thickness of the microporous membrane can be adjusted by controlling the die lip distance, the stretch ratio in the stretching step, etc.

[0047] <Porosity of Microporous Film> The porosity of the microporous membrane is preferably 25% or more and 95% or less, more preferably 30% or more and 65% or less, and even more preferably 35% or more and 60% or less. From the viewpoint of improving ion conductivity, the porosity is preferably 25% or more, and from the viewpoint of voltage resistance characteristics, it is preferably 95% or less. The porosity of the microporous membrane can be adjusted by controlling the mixing ratio of the polyethylene resin composition and the plasticizer, the stretching temperature, the stretching ratio, the heat setting temperature, the stretching ratio during heat setting, the relaxation rate during heat setting, or a combination of these.

[0048] <Air permeability of microporous membrane> The air permeability of the microporous membrane is preferably 10 sec / 100cc or more, more preferably 50 sec / 100cc or more, and preferably 1000 sec / 100cc or less, more preferably 500 sec / 100cc or less, and even more preferably 300 sec / 100cc or less. An air permeability of 10 sec / 100cc or more is preferable from the viewpoint of suppressing self-discharge of the electricity storage device. An air permeability of 1000 sec / 100cc or less is preferable from the viewpoint of obtaining good charge / discharge characteristics. The air permeability can be adjusted by changing the stretching temperature, the stretching ratio, etc.

[0049] <<Method for producing a microporous membrane>> The method for producing a separator for an electricity storage device according to the present disclosure includes the following steps: (1) a step of extruding a resin composition containing polyethylene and a pore-forming material into a sheet shape using an extruder, and then cooling and solidifying the same to form a sheet-like molded product; (2) stretching the sheet-like molded article to form a stretched sheet; (3) extracting a pore-forming material from the stretched sheet to form a porous sheet; (4) heat treating the porous sheet and stretching and relaxing it in the width direction; Includes. The method further includes the step of reacting the polyethylene with one or more graft molecules having a functional group for bonding to the molecular chain of the polyethylene and a heteroatom-containing functional group, between steps (1) and (2), between steps (2) and (3), between steps (3) and (4), or after step (4), to graft the polyethylene with the heteroatom-containing functional group.

[0050] Grafting Step The method for producing a separator for an electricity storage device according to the present disclosure further includes a step of reacting polyethylene with one or more molecules having a functional group for bonding to a molecular chain of the polyethylene and a heteroatom-containing functional group, thereby grafting the polyethylene with the heteroatom-containing functional group. The grafting step can be carried out between steps (1) and (2), between steps (2) and (3), between steps (3) and (4), or after step (4).

[0051] In the method for producing a separator for an electric storage device according to the present disclosure, a higher concentration of grafting (amount of modification) can be obtained by modifying polyethylene in the grafting step, as compared with a method using a modified polyethylene that has been grafted in advance as a raw material. In addition, even modified polyethylene that is generally difficult to produce can be easily modified. Therefore, the production method is simple and low-cost, and has excellent production efficiency.

[0052] In the grafting step, polyethylene is reacted with one or more molecules having a functional group for bonding to a polyethylene molecular chain and a heteroatom-containing functional group (hereinafter also referred to as "graft molecule"). As the heteroatom-containing functional group in the graft molecule, the heteroatom-containing functional group explained in the above section "Graft Structure" can be used.

[0053] The functional group to be bonded to the polyethylene molecular chain is preferably a functional group having a carbon-carbon unsaturated double bond, more preferably an α-olefin (terminal carbon-carbon unsaturated double bond). The functional group to be bonded to the polyethylene molecular chain is more preferably a vinyl group. Graft molecules having a vinyl group are preferred because they are inexpensive and easy to use.

[0054] The grafting step may include immersing the sheet-like molded product obtained in step (1), the stretched sheet obtained in step (2), the porous sheet obtained in step (3), or the heat-treated porous sheet obtained in step (4) in a solution containing a solvent, graft molecules, and an alkylborane or an alkylborane complex; and providing oxygen in the solution to react the graft molecules with the polyethylene and graft the polyethylene with a heteroatom-containing functional group.

[0055] The alkylborane or alkylborane complex is preferably a borane compound having a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. The alkylborane or alkylborane complex is preferably a trialkylborane having an alkyl group having 1 to 3 carbon atoms, and more preferably a triethylborane.

[0056] The solvent used in the grafting step is one that can dissolve the graft molecule and the alkylborane or alkylborane complex. The solvent is preferably an ether compound, a halogen compound, or a heterocyclic compound, and the ether compound may be diethyl ether or methyl butyl ether. The halogen compound may be a chloromethane solvent such as chloromethane, dichloromethane, or chloroform. The heterocyclic compound may be THF, furan, pyran, pyrrole, thiophene, pyridine, or NMP.

[0057] An example of a method for providing oxygen to a solution is bubbling gaseous oxygen into the solution. The oxygen concentration in the solution is preferably 2% to 100%, and more preferably 10% to 90%. Experiments have shown that air bubbling also exhibits good efficiency. The temperature of the solution is preferably -30 to 80°C, and more preferably 0 to 70°C.

[0058] By providing oxygen to a solution containing the graft molecule and an alkylborane or an alkylborane complex, it is preferable to cause a reaction as shown in the following chemical reaction formula to proceed, although the present disclosure is not limited to this reaction.

[0059] [ka]

[0060] In the above chemical reaction formula, first, triethylborane reacts with oxygen present in the solvent (Sol) to generate peroxyl radicals and ethyl radicals. Next, the ethyl radicals abstract hydrogen atoms from the polyethylene, and the resulting polyethylene radicals attack the α-olefin of the graft molecule to form bonds.

[0061] After the grafting, the method may further comprise extracting the graft molecules and the trialkylborane or trialkylborane complex from the sheet-like molded body, the stretched sheet, or the porous sheet, and drying the extracted molecules.

[0062] The solvent used for extracting the grafted molecules and the trialkylborane or trialkylborane complex is a dehydrated solvent such as THF, hexane, pentane, benzene, toluene, dichloromethane, 1,2-dichloroethane, ethyl acetate, acetonitrile, DMSO, or DMP.

[0063] <Sheet forming process> In the sheet forming process, a resin composition containing polyethylene and a pore forming material is extruded into a sheet by an extruder, cooled and solidified, and a sheet-shaped molded product is formed. As the polyethylene, the resins described in the above section on "Polyethylene" can be used. As the pore forming material, a plasticizer, an inorganic material, and a combination thereof can be used.

[0064] As the plasticizer, it is preferable to use a non-volatile solvent capable of forming a uniform solution at or above the melting point of polyethylene. Examples of such non-volatile solvents include hydrocarbons such as liquid paraffin and paraffin wax; esters such as dioctyl phthalate and dibutyl phthalate; and higher alcohols such as oleyl alcohol and stearyl alcohol. The plasticizer can be used alone or in combination of two or more. As the plasticizer, liquid paraffin is preferable. Liquid paraffin is highly compatible with polyethylene, and even when the sheet-shaped molded body is stretched, interfacial peeling between the resin and the plasticizer is unlikely to occur, resulting in more uniform stretching.

[0065] The ratio of polyethylene and plasticizer is within a range that allows them to be melt-kneaded uniformly and molded into a sheet. For example, the amount of plasticizer in the resin composition is preferably 20 to 90% by mass, more preferably 30 to 80% by mass, based on the total mass of the resin composition. When the mass fraction of the plasticizer is 90% by mass or less, moldability is improved when the melt is molded into a sheet. When the amount of plasticizer is 20% by mass or more, scission of polyethylene molecular chains is unlikely to occur even when the resin composition is stretched at a high ratio, and a more uniform and fine pore structure is easily formed, resulting in increased strength.

[0066] Examples of inorganic materials include oxide ceramics such as alumina, silica (silicon oxide), titania, zirconia, magnesia, ceria, yttria, zinc oxide, and iron oxide; nitride ceramics such as silicon nitride, titanium nitride, and boron nitride; ceramics such as silicon carbide, calcium carbonate, aluminum sulfate, aluminum hydroxide, potassium titanate, talc, kaolin clay, kaolinite, halloysite, pyrophyllite, montmorillonite, sericite, mica, amesite, bentonite, asbestos, zeolite, calcium silicate, magnesium silicate, diatomaceous earth, and silica sand; and glass fibers. The inorganic materials can be used alone or in combination of two or more. As inorganic materials, silica, alumina, and titania are preferred from the viewpoint of electrochemical stability, and silica is more preferred from the viewpoint of ease of extraction from the sheet-shaped molded body.

[0067] The amount of inorganic material in the resin composition is, based on the total mass of the resin composition, preferably 5 mass % or more, more preferably 10 mass % or more, from the viewpoint of obtaining good insulating properties, and is preferably 99 mass % or less, more preferably 95 mass % or less, from the viewpoint of ensuring high strength.

[0068] The resin composition may contain additives other than polyethylene and a pore-forming material. The additives described in the above section on additives can be used. From the viewpoint of shutdown performance, etc., the amount of additives in the resin composition is such that the amount of additives in the microporous membrane is preferably 20 parts by mass or less, for example 10 parts by mass or less, and more preferably 5 parts by mass or less, based on 100 parts by mass of the resin component constituting the microporous membrane.

[0069] As the extruder, any extruder such as a single screw extruder or a twin screw extruder can be used. The melt-kneaded material is extruded into a sheet by the extruder. As a method for extruding into a sheet, for example, a method for extruding the melt-kneaded material into a sheet through a T-die or the like can be mentioned. The die lip interval of the T-die may be preferably 200 μm or more and 3,000 μm or less, for example 500 μm or more and 2,500 μm or less. When the die lip interval is 200 μm or more, the occurrence of smears and the like is reduced, and the influence on the film quality such as streaks or defects is small, and the risk of film breakage in the subsequent stretching process can be reduced. On the other hand, when the die lip interval is 3,000 μm or less, the cooling speed is fast, and cooling unevenness can be prevented, and the thickness stability of the sheet can be maintained.

[0070] The molten kneaded material extruded into a sheet is cooled and solidified to obtain a sheet-shaped molded product. Examples of the cooling and solidifying method include a method in which the sheet-shaped molten kneaded material is brought into contact with a thermal conductor and cooled to a temperature sufficiently lower than the crystallization temperature of the resin component to solidify it. Examples of the thermal conductor include metal, water, and air. As the thermal conductor, metal is preferable because of its high thermal conductivity efficiency, and from the viewpoint of production efficiency, it is more preferable to use a metal roll. When the extruded sheet-shaped molten kneaded material is brought into contact with a metal roll, it is more preferable to sandwich it between at least a pair of rolls, because this further increases the thermal conductivity efficiency, and the sheet is oriented to increase the film strength and tends to improve the surface smoothness of the sheet.

[0071] The sheet-shaped molded body may be optionally rolled. The rolling can be performed, for example, by a pressing method using a double belt press or the like. By rolling the sheet-shaped molded body, the orientation of the surface layer portion in particular can be increased. The rolling area ratio is preferably more than 1 time and not more than 3 times, more preferably more than 1 time and not more than 2 times. When the rolling ratio exceeds 1 time, the surface orientation increases, and the membrane strength of the finally obtained porous membrane tends to increase. On the other hand, when the rolling ratio is 3 times or less, the orientation difference between the surface layer portion and the center inside is small, and a uniform porous structure tends to be formed in the thickness direction of the membrane.

[0072] <Stretching process> In the stretching step, the sheet-like molded body is stretched to form a stretched sheet. The stretching may be either uniaxial stretching or biaxial stretching. From the viewpoint of increasing the strength of the obtained microporous membrane, the stretching is preferably biaxial stretching. When the sheet-like molded body is stretched in the biaxial direction at a high ratio, the molecules are oriented in the plane direction, the obtained microporous membrane is less likely to tear, and a microporous membrane having high pin puncture strength is obtained. Examples of the biaxial stretching method include simultaneous biaxial stretching, sequential biaxial stretching, multi-stage stretching, and multiple stretching. From the viewpoints of improving pin puncture strength, uniformity of stretching, and shutdown property, simultaneous biaxial stretching is preferred. From the viewpoint of easy control of plane orientation, sequential biaxial stretching is preferred.

[0073] Simultaneous biaxial stretching refers to a stretching method in which stretching in MD (machine direction of continuous microporous membrane molding) and stretching in TD (direction crossing the MD of the microporous membrane at an angle of 90°) are performed simultaneously, and the stretching ratios in each direction may be different. Sequential biaxial stretching refers to a stretching method in which stretching in MD and TD is performed independently, and while stretching is performed in MD or TD, the other direction is unconstrained or fixed at a fixed length.

[0074] In the case of biaxial stretching, the areal ratio is preferably 20 times or more and 250 times or less, more preferably 20 times or more and 100 times or less, and even more preferably 25 times or more and 70 times or less. When the areal ratio is 20 times or more, it is preferable in terms of the strength of the microporous membrane. When the areal ratio is 200 times or less, it is preferable in terms of productivity, since it reduces membrane breakage in the stretching process. The stretching ratio in each direction is preferably 4 times or more and 10 times or less in MD and 4 times or more and 10 times or less in TD, more preferably 5 times or more and 8 times or less in MD and 5 times or more and 8 times or less in TD. The stretching ratio is the value obtained by dividing the dimension of the microporous membrane after the stretching operation by the dimension of the microporous membrane before the stretching operation. The areal ratio is the value obtained by multiplying the stretching ratio in MD and the stretching ratio in TD.

[0075] <Porous process> In the porosity forming step, the pore forming material is extracted from the stretched sheet to form a porous sheet. For example, the extraction method may be a method in which the sheet is immersed in an extraction solvent to extract the pore forming material, and then dried. The extraction method may be either a batch method or a continuous method. In order to suppress the shrinkage of the sheet, it is preferable to restrain the end of the sheet during the series of immersion and drying steps. In addition, it is preferable to adjust the remaining amount of the pore forming material in the obtained porous sheet to less than 1 mass % based on the total mass of the porous sheet.

[0076] The extraction solvent is preferably a poor solvent for polyethylene and a good solvent for the pore-forming material, and has a boiling point lower than the melting point of polyethylene. Examples of such extraction solvents include hydrocarbons such as n-hexane and cyclohexane; halogenated hydrocarbons such as methylene chloride and 1,1,1-trichloroethane; non-chlorine halogenated solvents such as hydrofluoroethers and hydrofluorocarbons; alcohols such as ethanol and isopropanol; ethers such as diethyl ether and tetrahydrofuran; and ketones such as acetone and methyl ethyl ketone. These extraction solvents may be recovered and reused by operations such as distillation. When an inorganic material is used as the pore-forming material, an alkaline aqueous solution such as sodium hydroxide and potassium hydroxide can be used as the extraction solvent.

[0077] <Heat treatment process> In the heat treatment step, the porous sheet is heat treated, and stretched and relaxed in the width direction. The heat treatment step heat fixes the porous sheet, and the shrinkage of the sheet can be suppressed. The heat treatment includes a stretching operation for adjusting the physical properties and a relaxation operation for reducing the stretching stress. The relaxation operation may be performed after the stretching operation, or the stretching operation may be performed after the relaxation operation. The heat treatment can be performed using a tenter or a roll stretching machine.

[0078] The temperature of the heat treatment including the stretching or relaxation operation is preferably within the range of 100°C to 170°C from the viewpoint of the crystal structure in which the grafted chemical species is easily modified. The temperatures of the stretching and relaxation operations are preferably within the above range from the viewpoint of the balance between the reduction in the thermal shrinkage rate and the porosity. The lower limit of the heat treatment temperature is more preferably 110°C or more, even more preferably 115°C or more, and the upper limit is more preferably 160°C or less, even more preferably 150°C or less, and even more preferably 140°C or less.

[0079] The stretching operation is an operation of stretching the microporous membrane in MD and / or TD. The stretching operation may be performed in both MD and TD, or only in one of MD and TD. The stretching ratio is the value obtained by dividing the dimension of the microporous membrane after the stretching operation by the dimension of the microporous membrane before the stretching operation. From the viewpoint of obtaining a microporous membrane with high strength and high porosity, the stretching ratio is preferably 1.1 times or more, more preferably 1.2 times or more, in MD and / or TD of the microporous membrane, respectively.

[0080] The relaxation operation is a shrinking operation of the microporous membrane in MD and / or TD. The relaxation operation may be performed in both MD and TD, or only one of MD and TD. The relaxation rate is the value obtained by dividing the dimension of the microporous membrane after the relaxation operation by the dimension of the microporous membrane before the relaxation operation. When both MD and TD are relaxed, the relaxation rate means the value obtained by multiplying the relaxation rate of MD and the relaxation rate of TD. The relaxation rate is preferably 1.0 or less, more preferably 0.97 or less, and even more preferably 0.95 or less.

[0081] The stretching and relaxation operations are preferably performed in TD. The temperature in the stretching and relaxation operations is preferably lower than the melting point of polyethylene, and more preferably in the range of 1° C. to 25° C. lower than the melting point of polyethylene. The temperature in the stretching and relaxation operations within the above range is preferred from the viewpoint of the balance between reduced thermal shrinkage and porosity of the microporous membrane.

[0082] Post-processing The microporous membrane may be subjected to optional post-treatments such as hydrophilization with a surfactant or crosslinking with ionizing radiation.

[0083] <Electricity storage device> The separator for an electric storage device of the present disclosure can be used as a separator for an electric storage device. The electric storage device of the present disclosure includes a positive electrode, a negative electrode, and the separator for an electric storage device of the present disclosure between the positive electrode and the negative electrode. Examples of the electric storage device include a battery, a capacitor, and preferably a lithium ion secondary battery.

[0084] The electric storage device contains an electrolytic solution, and the positive electrode, the negative electrode, and the separator for the electric storage device are impregnated with the electrolytic solution. The electrolytic solution may contain water, and the water contained in the system after the battery is produced may be water contained in the electrolytic solution, or water carried over from a member such as an electrode or a separator. The electrolytic solution may contain a non-aqueous solvent. Examples of the solvent contained in the non-aqueous solvent of the present disclosure include alcohols such as methanol and ethanol; aprotic solvents, and the like. Among them, aprotic solvents are preferable as the non-aqueous solvent.

[0085] Examples of aprotic solvents include cyclic carbonates, fluoroethylene carbonates, lactones, organic compounds having sulfur atoms, chain fluorinated carbonates, cyclic ethers, mononitriles, alkoxy group-substituted nitriles, dinitriles, cyclic nitriles, short-chain fatty acid esters, chain ethers, fluorinated ethers, ketones, and compounds in which some or all of the H atoms of the above aprotic solvents have been substituted with halogen atoms.

[0086] Examples of cyclic carbonates include ethylene carbonate, propylene carbonate, 1,2-butylene carbonate, trans-2,3-butylene carbonate, cis-2,3-butylene carbonate, 1,2-pentylene carbonate, trans-2,3-pentylene carbonate, cis-2,3-pentylene carbonate, vinylene carbonate, 4,5-dimethylvinylene carbonate, and vinylethylene carbonate.

[0087] Examples of fluoroethylene carbonate include 4-fluoro-1,3-dioxolan-2-one, 4,4-difluoro-1,3-dioxolan-2-one, cis-4,5-difluoro-1,3-dioxolan-2-one, trans-4,5-difluoro-1,3-dioxolan-2-one, 4,4,5-trifluoro-1,3-dioxolan-2-one, 4,4,5,5-tetrafluoro-1,3-dioxolan-2-one, and 4,4,5-trifluoro-5-methyl-1,3-dioxolan-2-one.

[0088] Examples of lactones include γ-butyrolactone, α-methyl-γ-butyrolactone, γ-valerolactone, γ-caprolactone, δ-valerolactone, δ-caprolactone, and ε-caprolactone.

[0089] Examples of organic compounds having a sulfur atom include ethylene sulfite, propylene sulfite, butylene sulfite, pentene sulfite, sulfolane, 3-sulfolene, 3-methylsulfolane, 1,3-propane sultone, 1,4-butane sultone, 1-propene 1,3-sultone, dimethyl sulfoxide, tetramethylene sulfoxide, and ethylene glycol sulfite.

[0090] Examples of the chain carbonate include ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, methyl propyl carbonate, methyl isopropyl carbonate, dipropyl carbonate, methyl butyl carbonate, dibutyl carbonate, and ethyl propyl carbonate.

[0091] Examples of cyclic ethers include tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, and 1,3-dioxane.

[0092] Examples of mononitriles include acetonitrile, propionitrile, butyronitrile, valeronitrile, benzonitrile, and acrylonitrile.

[0093] Examples of alkoxy-substituted nitriles include methoxyacetonitrile and 3-methoxypropionitrile.

[0094] Examples of dinitriles include malononitrile, succinonitrile, methylsuccinonitrile, glutaronitrile, 2-methylglutaronitrile, adiponitrile, 1,4-dicyanoheptane, 1,5-dicyanopentane, 1,6-dicyanohexane, 1,7-dicyanoheptane, 2,6-dicyanoheptane, 1,8-dicyanooctane, 2,7-dicyanooctane, 1,9-dicyanonane, 2,8-dicyanononane, 1,10-dicyanodecane, 1,6-dicyanodecane, 2,4-dimethylglutaronitrile, and ethylene glycol bis(propionitrile) ether.

[0095] Examples of cyclic nitriles include benzonitrile.

[0096] Examples of short-chain fatty acid esters include methyl acetate, methyl propionate, methyl isobutyrate, methyl butyrate, methyl isovalerate, methyl valerate, methyl pivalate, methyl hydroangelate, methyl caproate, ethyl acetate, ethyl propionate, ethyl isobutyrate, ethyl butyrate, ethyl isovalerate, ethyl valerate, ethyl pivalate, ethyl hydroangelate, ethyl caproate, propyl acetate, propyl propionate, propyl isobutyrate, propyl butyrate, propyl isovalerate, propyl valerate, propyl pivalate, propyl hydroangelate, propyl caproate, isopropyl acetate, isopropyl propionate, isopropyl isobutyrate, isopropyl butyrate, isopropyl isovalerate, isopropyl valerate, and isopropyl pivalate. , isopropyl hydroangelate, isopropyl caproate, butyl acetate, butyl propionate, butyl isobutyrate, butyl butyrate, butyl isovalerate, butyl valerate, butyl pivalate, butyl hydroangelate, butyl caproate, isobutyl acetate, isobutyl propionate, isobutyl isobutyrate, isobutyl butyrate, isobutyl isovalerate, isobutyl valerate, isobutyl pivalate, isobutyl hydroangelate, isobutyl caproate, tert-butyl acetate, tert-butyl propionate, tert-butyl isobutyrate, tert-butyl butyrate, tert-butyl isovalerate, tert-butyl valerate, tert-butyl pivalate, tert-butyl hydroangelate, and tert-butyl caproate.

[0097] Examples of the chain ether include dimethoxyethane, diethyl ether, 1,3-dioxolane, diglyme, triglyme, and tetraglyme. Examples of the fluorinated ether include those represented by the general formula Rf aa -OR bb (In the formula, Rf aa is an alkyl group containing a fluorine atom, and R bbis an organic group which may contain a fluorine atom). Examples of the ketone include acetone, methyl ethyl ketone, and methyl isobutyl ketone.

[0098] Examples of the above-mentioned aprotic solvent compounds in which some or all of the H atoms have been substituted with halogen atoms include compounds in which the halogen atoms are fluorine.

[0099] Here, examples of fluorinated chain carbonates include methyl trifluoroethyl carbonate, trifluorodimethyl carbonate, trifluorodiethyl carbonate, trifluoroethylmethyl carbonate, methyl 2,2-difluoroethyl carbonate, methyl 2,2,2-trifluoroethyl carbonate, and methyl 2,2,3,3-tetrafluoropropyl carbonate. The above-mentioned fluorinated chain carbonates are represented by the following general formula: R cc -OC(O)OR dd {where, R cc and R dd is CH3, CH2CH3, CH2CH2CH3, CH(CH3)2, and the formula CH2Rf ee (In the formula, Rf ee is an alkyl group having 1 to 3 carbon atoms in which a hydrogen atom is substituted with at least one fluorine atom), and R cc and / or R dd contains at least one fluorine atom. It can be expressed as:

[0100] Examples of fluorinated short-chain fatty acid esters include fluorinated short-chain fatty acid esters such as 2,2-difluoroethyl acetate, 2,2,2-trifluoroethyl acetate, and 2,2,3,3-tetrafluoropropyl acetate. Fluorinated short-chain fatty acid esters are represented by the following general formula: R ff -C(O)OR gg {where, Rff is CH3, CH2CH3, CH2CH2CH3, CH(CH3)2, CF3CF2H, CFH2, CF2H, CF2Rf hh , CFHRf hh , and CH2Rf ii and R is at least one selected from the group consisting of gg is CH3, CH2CH3, CH2CH2CH3, CH(CH3)2, and CH2Rf ii Rf is at least one selected from the group consisting of hh is an alkyl group having 1 to 3 carbon atoms in which a hydrogen atom may be substituted with at least one fluorine atom, and Rf ii is an alkyl group having 1 to 3 carbon atoms in which a hydrogen atom is substituted with at least one fluorine atom, and R ff and / or R gg contains at least one fluorine atom, and R ff If is CF2H, R gg can be expressed as {is not CH3}. EXAMPLES

[0101] Hereinafter, the embodiments of the present disclosure will be specifically described with reference to examples and comparative examples, but the present disclosure is not limited to these examples and comparative examples.

[0102] Measurement and evaluation methods <Microporous membrane thickness (μm)> A 10 cm x 10 cm square sample was cut from the microporous membrane, and 9 points (3 points x 3 points) were selected in a grid pattern to measure the membrane thickness using a micro thickness gauge (Type KBM, Toyo Seiki Seisakusho Co., Ltd.) at room temperature of 23 ± 2° C. The average value of the measurements at the 9 points was calculated as the membrane thickness (μm) of the microporous membrane.

[0103] <Mass conversion strength (gf / g)> A 10 cm x 10 cm square sample was cut from the microporous membrane, its weight (g) was measured, and the puncture strength (gf) at the center was then measured and the mass converted strength (gf / g) was calculated using the following formula. Mass conversion strength (gf / g) = Puncture strength (gf) / weight (g) The puncture strength was determined by conducting a puncture test on the sample film using a handy compression tester "KES-G5" (manufactured by Kato Tech, trademark) under conditions of a needle tip curvature radius of 0.5 mm and a puncture speed of 2 mm / sec.

[0104] <Porosity of microporous membrane (%)> A 10 cm x 10 cm square sample was cut from the microporous membrane and its volume (cm 3 ) and mass (g) were calculated. Using these values, the density of the microporous membrane was calculated to be 0.95 (g / cm 3 ) and the porosity was calculated using the following formula. Porosity (%) = (1-mass / volume / 0.95) x 100

[0105] <Air permeability of microporous membrane (sec / 100cc)> The air permeability was measured in accordance with JIS P-8117 using a Gurley air permeability meter G-B2 (trademark, inner cylinder mass: 567g) manufactured by Toyo Seiki Seisakusho Co., Ltd., at 645 mm 2 (circle with a diameter of 28.6 mm) was measured, and the time (seconds) it took for 100 cc of air to pass through was measured as air permeability (seconds / 100 cc).

[0106] <Volume recovery rate (%) before and after compression in electrolyte> A 10 cm x 10 cm square sample was cut from the microporous membrane, impregnated with the nonaqueous electrolyte described in item c of <Preparation of evaluation battery> below, and compressed at 10 MPa for 3 minutes in a hot press machine heated to 60°C. The pressure was then released and the membrane was left for 10 minutes, after which the electrolyte was washed off with ethanol and then acetone, and air-dried. The thickness of the microporous membrane obtained by the above procedure was measured according to the method described in <Thickness of microporous membrane (μm)> above. The average value of measurements taken at 25 random points within the sample was used. Volume recovery rate (%) before and after compression in electrolyte = 100 × (thickness after compression in electrolyte swollen state / thickness before compression in electrolyte swollen state)

[0107] <Pulsed NMR> The spin-spin relaxation time (T2 relaxation time) of all protons in the microporous membrane was observed under the following conditions using a pulsed NMR measurement device (Minispec MQ20 ​​manufactured by Bruker Japan). (1) Conditions for the solid echo method Nuclide: 1H Measurement: T2 Measurement temperature: 120℃ (measured 5 minutes after reaching the set temperature) Number of times accumulated: 256 Repeat time: 5.0sec The maximum observed intensity at the start of the measurement (several μsec immediately after the pulse was turned off) was taken as the standard (100%), and the ratio of the signal intensity at 0.2 msec and 0.8 msec from the start of the measurement for each Example and Comparative Example was observed. When the detected signal intensity was 2.0% or less, the average value of ±0.1 msec before and after was used. (2) Conditions of the CPMG Act Nuclide: 1H Measurement: T2 Measurement temperature: 180℃ (measured 5 minutes after reaching the set temperature) Number of times accumulated: 256 Pulse Sensitivity: 0.1 msec Number of echoes: 800 Repeat time: 5.0sec In the CPMG method, the signal intensity ratios at 40 msec and 140 msec from the start of measurement in each example and comparative example were observed in the same manner as in the solid echo method. Pulse NMR can be measured on the separator before being incorporated into the battery and on the separator after being incorporated into the battery. The separator after being incorporated into the battery may be in a state after the chemical reaction of the graft has progressed. When measuring the separator after being incorporated into the battery, the separator removed from the battery is washed multiple times with ethanol and acetone, the electrolyte and electrolyte are thoroughly washed away, and the measurement is performed after vacuum drying. In addition, in the case of a separator in which an inorganic substance-containing coating layer, a resin binder-containing coating layer, a resin composition-containing coating layer, etc. are combined, washing is performed with a solvent, and the measurement is performed after the microporous membrane mainly composed of PE is separated from the layer structure. For the measurement of pulse NMR, Non-Patent Documents 4 to 6 can be referred to.

[0108] <Weight average molecular weight (Mw), number average molecular weight (Mn)> A calibration curve was created by measuring standard polystyrene under the following conditions using a Waters ALC / GPC 150C (trademark). Chromatograms were also measured for the following polymers under the same conditions, and the weight-average molecular weight and number-average molecular weight of each polymer were calculated based on the calibration curve by the following method. Column: Tosoh GMH6-HT (trademark) x 2 + GMH6-HTL (trademark) x 2 Mobile phase: o-dichlorobenzene Detector: Differential refractometer Flow rate: 1.0ml / min Column temperature: 140℃ Sample concentration: 0.1wt% (Weight average molecular weight and number average molecular weight of polyethylene and polypropylene) Each molecular weight component in the obtained calibration curve was multiplied by 0.43 (Q factor of polyethylene / Q factor of polystyrene = 17.7 / 41.3) or 0.64 (Q factor of polypropylene / Q factor of polystyrene = 26.4 / 41.3) to obtain a molecular weight distribution curve converted into polyethylene or polypropylene, and the weight average molecular weight and number average molecular weight were calculated.

[0109] <Viscosity average molecular weight (Mv)> The intrinsic viscosity [η] at 135°C in decalin solvent was determined based on ASTM-D4020. The Mv of polyethylene was calculated using the following formula. [η]=6.77×10 -4 Mv 0.67 The Mv of polypropylene was calculated using the following formula. [η]=1.10×10 -4 Mv 0.80

[0110] <Preparation of Evaluation Battery> a. Preparation of the positive electrode A slurry was prepared by dispersing 92.2 mass% of lithium cobalt composite oxide LiCoO2 as the positive electrode active material, 2.3 mass% each of flake graphite and acetylene black as the conductive material, and 3.2 mass% of polyvinylidene fluoride (PVDF) as the binder in N-methylpyrrolidone (NMP). This slurry was applied to one side of a 20 μm thick aluminum foil that serves as a positive electrode current collector using a die coater, dried at 130 ° C for 3 minutes, and then compression molded using a roll press machine. At this time, the amount of active material applied to the positive electrode was 250 g / m 2 , the bulk density of the active material is 3.00 g / cm 3 It was adjusted to be.

[0111] b. Preparation of the negative electrode A slurry was prepared by dispersing 81.9% by mass of artificial graphite as the negative electrode active material, 15% by mass of silicon particles manufactured by Elkem (Silgrain e-Si408), and 1.4% by mass of ammonium salt of carboxymethylcellulose and 1.7% by mass of styrene-butadiene copolymer latex as the binder in purified water. This slurry was applied to one side of a 12 μm-thick copper foil serving as a negative electrode current collector using a die coater, dried at 120° C. for 3 minutes, and then compression molded using a roll press. At this time, the amount of active material applied to the negative electrode was 106 g / m 2 , the bulk density of the active material is 1.35 g / cm 3 It was adjusted to be.

[0112] c. Preparation of non-aqueous electrolyte The solution was prepared by dissolving LiPF6 as a solute in a mixed solvent of ethylene carbonate:ethyl methyl carbonate = 1:2 (volume ratio) to a concentration of 1.0 mol / L.

[0113] d. Battery assembly The separator obtained in the examples and comparative examples was cut into a circle with a diameter of 18 mm, and the positive and negative electrodes were cut into a circle with a diameter of 16 mm. The positive and negative electrodes were stacked in a set of 28 opposing positive electrodes, separators, and negative electrodes so that the active material surfaces of the positive and negative electrodes faced each other, and then stored in a stainless steel metal container with a lid. The container and the lid were insulated, and the container was in contact with the copper foil of the negative electrode, and the lid was in contact with the aluminum foil of the positive electrode. The nonaqueous electrolyte obtained in c. above was poured into this container and sealed. After leaving it at room temperature for one day, the battery was charged at a current value of 3 mA (0.5 C) in an atmosphere of 25°C up to a battery voltage of 4.2 V, and the current value was started to be reduced from 3 mA so as to maintain 4.2 V after reaching that voltage, for a total of 6 hours, in the manner that the first charge after the preparation of the battery was performed. Then, the battery was discharged at a current value of 3 mA (0.5 C) down to a battery voltage of 3.0 V.

[0114] <Battery characteristic retention rate (%) at 1000th cycle> The cycle characteristics were evaluated using the battery assembled according to the above a to d. The obtained battery was charged and discharged 1000 times in an atmosphere of 40°C. The battery was charged at a current value of 6.0mA (1.0C) up to a battery voltage of 4.2V, and after reaching the voltage, the current value was reduced from 6.0mA so as to maintain 4.2V, for a total of 3 hours. The battery was discharged at a current value of 6.0mA (1.0C) down to a battery voltage of 3.0V. The capacity retention rate was calculated from the discharge capacity at the 1000th cycle and the discharge capacity at the 1st cycle. A battery with a high capacity retention rate was evaluated as having good cycle characteristics.

[0115] <Nail penetration test pass rate after 1000 cycles (%)> The battery that had been charged and discharged 1000 times was placed on an iron plate in a temperature-controllable explosion-proof booth. The temperature in the explosion-proof booth was set to 40°C, and an iron nail with a diameter of 3.0 mm was inserted into the center of the battery at a speed of 2 mm / sec, and the nail was maintained in the penetrated state. The temperature of a thermocouple installed inside the nail so that the temperature inside the battery could be measured after the nail penetrated was measured, and the presence or absence of ignition was evaluated. The evaluation was repeated using newly prepared batteries in the same manner, and the number of samples that did not ignite (no ignition) was calculated as a percentage using the following formula. The evaluation was performed by preparing 100 batteries using each separator. Evaluation result (%) = (100 x number of samples that did not ignite / total number of samples)

[0116] Example 1 [Film production example] (Sheet molding process) As the raw polyethylene, a homopolymer polyethylene (ultra-high molecular weight polyethylene) with a weight-average molecular weight of 1,900,000 and a viscosity-average molecular weight of 2,300,000 was used. 1% by mass of pentaerythrityl-tetrakis-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] as an antioxidant was added to the polyethylene, and the mixture was dry-blended using a tumbler blender to obtain a mixture. The mixture obtained was fed to a twin-screw extruder by a feeder under a nitrogen atmosphere. Liquid paraffin (dynamic viscosity at 37.78°C: 7.59 x 10 -5 m 2 / s) was injected into the extruder cylinder by a plunger pump. The mixture and liquid paraffin were melt-kneaded in the extruder, and the feeder and pump were adjusted so that the ratio of liquid paraffin in the extruded polyethylene composition was 70 mass% (i.e., the polymer concentration was 26 mass%). The melt-kneading conditions were a set temperature of 230°C, a screw rotation speed of 240 rpm, and a discharge rate of 18 kg / h. The molten mixture was then extruded and cast through a T-die onto a cooling roll whose surface temperature was controlled to 20°C, to obtain a gel sheet (sheet-shaped molded product) having a thickness of 1750 μm.

[0117] (Stretching process) Next, the gel sheet was introduced into a simultaneous biaxial tenter stretching machine and biaxially stretched to obtain a stretched product (stretched sheet). The stretching conditions were set as follows: MD magnification 7.0 times, TD magnification 7.14 times (i.e., 7 × 7.14 times = 49.98 times ≒ 50 times), and biaxial stretching temperature 115 °C.

[0118] (Porous body formation process) Next, the stretched gel sheet was introduced into a dichloromethane tank and thoroughly immersed in dichloromethane to extract and remove the liquid paraffin, and then the dichloromethane was dried and removed to obtain a porous body (porous sheet).

[0119] (Heat treatment process) Next, the porous material was introduced into a TD tenter for heat setting (HS), and HS was performed at a heat setting temperature of 129°C and a stretch ratio of 2.0 times in the TD direction, and then a relaxation operation was performed in the TD direction at a stretch ratio of 0.9 times (i.e., based on the state before the heat treatment process, the material was stretched 2.0 times in the TD direction, and then relaxed to 1.8 times).

[0120] (Grafting step) The membrane obtained in the above heat treatment step was introduced into a THF solution tank containing trimethoxyvinylsilane (10 Wt%) and triethylborane (1 mol / l), and a grafting reaction was carried out while bubbling air from the bottom of the tank. Next, the unreacted trimethoxyvinylsilane and the catalyst triethylborane were washed with THF, and then the THF was dried and removed to obtain a heteroatom-containing functional group grafted membrane. The ends of the obtained microporous membrane were then cut and wound into a mother roll with a width of 1,100 mm and a length of 5,000 m.

[0121] Examples 2 to 14 Except for changing the conditions as shown in Tables 1 and 2, the same procedure as in Example 1 was carried out to obtain a separator for an electricity storage device.

[0122] Comparative Examples 1 to 4 A separator for an electricity storage device was obtained in the same manner as in Example 1, except that the conditions were changed as shown in Table 3. In Comparative Examples 1 and 2, the oxygen concentration was "0%" and borane was "none," so that a heteroatom-containing functional group was not grafted onto the surface of the separator for an electricity storage device.

[0123] [Table 1]

[0124] [Table 2]

[0125] [Table 3]

[0126] Example 15 [Film production example] (Sheet molding process) As the raw polyethylene, a homopolymer polyethylene (ultra-high molecular weight polyethylene) with a weight-average molecular weight of 2,100,000 and a viscosity-average molecular weight of 2,370,000 was used. 1% by mass of pentaerythrityl-tetrakis-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] as an antioxidant was added to the polyethylene, and the mixture was dry-blended using a tumbler blender to obtain a mixture. The mixture obtained was fed to a twin-screw extruder by a feeder under a nitrogen atmosphere. Liquid paraffin (dynamic viscosity at 37.78°C 7.59×10 -5 m 2 / s) was injected into the extruder cylinder by a plunger pump. The mixture and liquid paraffin were melt-kneaded in the extruder, and the feeder and pump were adjusted so that the ratio of liquid paraffin in the extruded polyethylene composition was 70 mass% (i.e., the polymer concentration was 25 mass%). The melt-kneading conditions were a set temperature of 230°C, a screw rotation speed of 240 rpm, and a discharge rate of 18 kg / h. The molten mixture was then extruded and cast through a T-die onto a cooling roll whose surface temperature was controlled to 20°C, to obtain a gel sheet (sheet-shaped molded product) having a thickness of 1800 μm.

[0127] (Stretching process) Next, the gel sheet was introduced into a simultaneous biaxial tenter stretching machine and biaxially stretched to obtain a stretched product (stretched sheet). The stretching conditions were set as follows: MD magnification 7.0 times, TD magnification 6.9 times (i.e., 7 × 6.9 times = 48.3 times), and biaxial stretching temperature 115 °C.

[0128] (Porous body formation process) Next, the stretched gel sheet was introduced into a dichloromethane tank and thoroughly immersed in dichloromethane to extract and remove the liquid paraffin, and then the dichloromethane was dried and removed to obtain a porous body (porous sheet).

[0129] (Heat treatment process) Next, the porous material was introduced into a TD tenter for heat setting (HS), and HS was performed at a heat setting temperature of 129°C and a stretch ratio of 2.0 times in the TD direction, and then a relaxation operation was performed in the TD direction at a stretch ratio of 0.9 times (i.e., based on the state before the heat treatment process, the material was stretched 2.0 times in the TD direction, and then relaxed to 1.8 times).

[0130] (Grafting step) The membrane obtained in the above heat treatment step was introduced into a THF solution tank containing trimethoxysilane (8 Wt%) and triethylborane (1 mol / l), and a grafting reaction was carried out while bubbling air from the bottom of the tank. Next, the unreacted trimethoxyvinylsilane and the catalyst triethylborane were washed with THF, and then the THF was dried and removed to obtain a heteroatom-containing functional group grafted membrane. The ends of the obtained microporous membrane were then cut and wound up into a mother roll with a width of 1,100 mm and a length of 5,000 m.

[0131] Examples 16 to 36 Except for changing the conditions as shown in Tables 4 to 6, the same procedure as in Example 15 was carried out to obtain a separator for an electricity storage device.

[0132] Comparative Examples 5 and 6 Except for changing the conditions as shown in Table 6, the same procedure as in Example 15 was carried out to obtain a separator for an electricity storage device.

[0133] [Table 4]

[0134] [Table 5]

[0135] [Table 6] [Industrial Applicability]

[0136] The separator for an electricity storage device according to the present disclosure can be used, for example, as a separator for an electricity storage device, such as a battery or a capacitor, preferably a lithium ion secondary battery. [Explanation of symbols]

[0137] 10. Higher-order structure of PE polymer in microporous membrane 20 Heteroatom-containing functional groups 30 Crosslinked structure 40 Chelate Complex Structure 50 electrodes

Claims

1. A method for producing a separator for an electricity storage device, the method comprising the steps of: (1) a step of extruding a resin composition containing polyethylene and a pore-forming material into a sheet shape using an extruder, and then cooling and solidifying the same to form a sheet-like molded product; (2) stretching the sheet-like molded body to form a stretched sheet; (3) extracting a hole-forming material from the stretched sheet to form a hole-forming sheet; (4) heat treating the porous sheet to stretch and relax it in the width direction; Including, The method further comprises the step of reacting the polyethylene with one or more graft molecules having a functional group for bonding to a molecular chain of the polyethylene and a heteroatom-containing functional group, between steps (1) and (2), between steps (2) and (3), between steps (3) and (4), or after step (4), to graft the polyethylene with the heteroatom-containing functional group; The grafting step includes the steps of: Immersing the sheet-like molded body, the stretched sheet, or the porous sheet in a solution containing a solvent, the graft molecule, and an alkylborane or an alkylborane complex; providing oxygen in the solution to react the graft molecule with the polyethylene and graft the polyethylene with the heteroatom-containing functional group; Including, The separator for an electricity storage device produced by the above method is such that, in observation of the spin-spin relaxation time (T2 relaxation time) of all protons in pulsed NMR measurement using a solid echo method at 120°C, the ratio of the signal intensity 0.2 msec after the start of observation is 0.2% to 40% of the signal intensity at the start of observation, and the ratio of the signal intensity 0.8 msec after the start of observation is 0.05% to 10% of the signal intensity at the start of observation.

2. A method for producing a separator for an electricity storage device, the method comprising: (1) a step of extruding a resin composition containing polyethylene and a pore-forming material into a sheet shape using an extruder, and then cooling and solidifying the same to form a sheet-like molded product; (2) stretching the sheet-like molded body to form a stretched sheet; (3) extracting a hole-forming material from the stretched sheet to form a hole-forming sheet; (4) heat treating the porous sheet to stretch and relax it in the width direction; Including, The method further comprises the step of reacting the polyethylene with one or more graft molecules having a functional group for bonding to a molecular chain of the polyethylene and a heteroatom-containing functional group, between steps (1) and (2), between steps (2) and (3), between steps (3) and (4), or after step (4), to graft the polyethylene with the heteroatom-containing functional group; The grafting step includes the steps of: Immersing the sheet-like molded body, the stretched sheet, or the porous sheet in a solution containing a solvent, the graft molecule, and an alkylborane or an alkylborane complex; providing oxygen in the solution to react the graft molecule with the polyethylene and graft the polyethylene with the heteroatom-containing functional group; Including, In the power storage device separator produced by the above method, in pulse NMR measurement of the spin-spin relaxation time (T2 relaxation time) of all protons using a CPMG method at 180°C, the ratio of the signal intensity 40 msec after the start of observation is 5% to 30% of the signal intensity at the start of observation, and the ratio of the signal intensity 140 msec after the start of observation is 1.5% to 20% of the signal intensity at the start of observation.

3. 3. The method of claim 1 or 2, wherein the functional group for bonding to the polyethylene molecular chain comprises a vinyl group.

4. The method according to any one of claims 1 to 3, further comprising extracting and drying the graft molecules and the alkylborane or alkylborane complex from the sheet-like molded body, the stretched sheet, or the porous sheet after the grafting.

5. The method according to any one of claims 1 to 4, wherein the grafting step is carried out after step (4).

6. The method according to any one of claims 1 to 4, wherein the grafting step is carried out between steps (1) and (2).

7. The method according to any one of claims 1 to 4, wherein the grafting step is carried out between steps (2) and (3).

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