Flame retardant group-containing polymer, separator of non-aqueous electrolyte battery comprising the same, and non-aqueous electrolyte battery

Abstract

The present invention relates to a flame-retardant group-containing polymer, a non-aqueous electrolyte cell separator comprising the same, and a non-aqueous electrolyte cell.

Description

Technology Field

[0001] The present invention relates to a flame-retardant group-containing polymer, a non-aqueous electrolyte cell separator comprising the same, and a non-aqueous electrolyte cell. Background Technology

[0003] Recently, non-aqueous electrolyte batteries, particularly lithium-ion secondary batteries, which have high voltage and high energy density, are attracting attention as power sources for mobile terminals such as laptop computers or mobile phones, or for hybrid and electric vehicles. Since non-aqueous electrolyte batteries, such as lithium-ion secondary batteries, have high capacity and high energy density, a large current flows when there is an internal or external short circuit in the battery, and there are problems such as the battery overheating due to the Joule heat generated at that time, and the expansion of the battery or degradation of performance due to gas generation accompanying the decomposition of the electrolyte.

[0004] In current lithium-ion secondary batteries, to solve this problem, a separator containing a porous substrate having fine holes, such as polypropylene or polyethylene film, is interposed between the positive and negative electrodes. When the temperature of these separators containing porous substrates rises due to heat generated during a short circuit, the separator melts and the fine holes become blocked, thereby preventing the movement of ions and preventing current from flowing, which suppresses the runaway of the battery.

[0005] Today, as the applications of lithium-ion secondary batteries expand, there is a demand for batteries with higher heat resistance, particularly improved heat resistance in the event of an internal short circuit. In particular, when an internal short circuit occurs in a battery, the temperature at the short-circuited area can reach 600°C or higher due to localized heat generation. Consequently, in conventional separators containing porous substrates with fine pores, such as polyolefin films, the separator at the short-circuited area may shrink or melt due to the heat generated during the short circuit, thereby exposing the battery to risks such as smoke, ignition, and explosion.

[0006] As a technology to increase the reliability of the battery by preventing short circuits caused by thermal shrinkage or thermal melting of such separators, a multilayer separator is proposed having a heat-resistant porous layer on one side or both sides (front and back) of a porous substrate having fine holes, such as a polyolefin-based film.

[0007] In such separators, the heat-resistant porous layer utilizes a polymer containing cyanoethyl groups or flame-retardant groups as a dispersant to evenly disperse the inorganic material. The dispersant must have an appropriate level of dispersion ability to sufficiently ensure the stability of the battery separator, and if the dispersion ability is poor, the inorganic material is not evenly dispersed, making it difficult to sufficiently ensure the thermal stability of the separator.

[0008] Therefore, research is needed on separators that possess excellent adhesion and dispersion capabilities, while also ensuring superior safety in the event of accidents such as smoke generation, ignition, or explosion. The problem to be solved

[0010] The present specification aims to provide a non-aqueous electrolyte battery separator and a non-aqueous electrolyte battery that not only firmly adheres an inorganic filler when forming a heat-resistant porous layer of the separator but also effectively disperses it to further improve the heat resistance of the separator, while also having excellent flame retardancy to ensure safety in the event of accidents such as smoke generation, ignition, or explosion. means of solving the problem

[0012] The present specification provides a flame-retardant group-containing polymer comprising a first repeating unit represented by the following chemical formula 1, a second repeating unit represented by the following chemical formula 2, and a third repeating unit represented by the following chemical formula 3.

[0013] [Chemical Formula 1]

[0014]

[0015] In the above chemical formula 1, R1 is hydrogen or an alkyl having 1 to 8 carbon atoms, and

[0016] [Chemical Formula 2]

[0017]

[0018] In the above chemical formula 2, R21 is an acetate (CH3COO-) group, and

[0019] [Chemical Formula 3]

[0020]

[0021] In the above chemical formula 3, R31 is -(C=O)O-, R32 is a phosphorus-based flame retardant group, and R33 is an electron withdrawing group.

[0023] According to one embodiment of the invention, the R32 may include one or more flame-retardant groups selected from the group consisting of the following chemical formulas.

[0024] , , , , ,

[0025] In the above chemical formula, R1 and R2 are each independently hydrogen, a monovalent metal cation, an ammonium ion, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or an alkylaryl group having 7 to 10 carbon atoms.

[0027] And the above R33 is -CN, -NO2, -CO-R34, -CON-R34, or -COO-R34, where R34 is hydrogen or an alkyl having 1 to 5 carbon atoms.

[0029] At this time, it may be more preferable that R1 and R2 are each independently hydrogen, ammonium ions, alkyl groups having 1 to 5 carbon atoms, or phenyl groups.

[0031] In the above flame-retardant group-containing polymer, the ratio of the number of repetitions of the first repeating unit to the total number of repetitions of the first to third repeating units, that is, the ratio of repeating units derived from alkene-based monomers, may be about 0.1 to about 0.5, the lower limit value may be about 0.1 or more, or about 0.15 or more, and the upper limit value may be about 0.5 or less, or about 0.45 or less.

[0033] And, the ratio of the number of repeating units of the second repeating unit to the total number of repeating units of the first to third repeating units in the flame-retardant group-containing polymer, that is, the ratio of repeating units derived from vinyl acetate-based monomers, may be about 0.3 to about 0.8, the lower limit value may be about 0.3 or more, or about 0.4 or more, or about 0.45 or more, and the upper limit value may be about 0.8 or less, or about 0.75 or less.

[0035] And, the ratio of the number of repetitions of the third repeating unit to the total number of repetitions of the first to third repeating units in the polymer containing the flame-retardant group, that is, the ratio of the repeating unit into which the flame-retardant group is introduced, may be about 0.01 to about 0.3, the lower limit value may be about 0.01 or more, or greater than about 0.02, or about 0.03 or more, or about 0.04 or more, and the upper limit value may be 0.3 or less, or less than about 0.3, or about 0.25 or less.

[0037] According to another embodiment of the invention, the weight average molecular weight value of the flame-retardant group-containing polymer may be 100,000 to 500,000 g / mol, the lower limit may be about 100,000 g / mol or more, or about 150,000 g / mol or more, and the upper limit may be about 500,000 g / mol or less, or about 400,000 g / mol or less, or about 350,000 g / mol or less.

[0039] Meanwhile, according to another aspect of the invention, a dispersant composition for a non-aqueous electrolyte cell separator is provided, comprising a polymer containing flame-retardant groups.

[0041] The above-mentioned dispersant composition for a non-aqueous electrolyte battery separator may further include an inorganic filler.

[0043] At this time, the inorganic filler may include one or more selected from the group consisting of inorganic oxides, inorganic nitrides, sparingly soluble ionic crystal microparticles, covalent crystals, clay, materials derived from mineral resources, lithium titanium phosphate, and combinations thereof.

[0045] Meanwhile, according to another aspect of the invention, a separator for a non-aqueous electrolyte battery is provided, comprising a porous substrate and a heat-resistant porous layer formed on at least one surface of the porous substrate, wherein the heat-resistant porous layer comprises a dispersant composition for a non-aqueous electrolyte battery separator according to claim 8.

[0047] At this time, the porous substrate may be composed of one or more resins selected from the group consisting of polyolefin resin, polyester resin, polyacetal resin, polyamide resin, polycarbonate resin, polyimide resin, polyetheretherketone resin, polyethersulfone resin, and combinations thereof.

[0049] Meanwhile, according to another aspect of the invention, a non-aqueous electrolyte battery is provided, comprising a positive electrode, a negative electrode, a separator for the non-aqueous electrolyte battery, and an electrolyte.

[0051] In the present invention, terms such as first, second, etc. are used to describe various components, and these terms are used solely for the purpose of distinguishing one component from another.

[0052] Furthermore, the terms used herein are used merely to describe exemplary embodiments and are not intended to limit the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this specification, terms such as “comprising,” “comprising,” or “having” are intended to specify the existence of the implemented features, numbers, steps, components, or combinations thereof, and should be understood as not precluding the existence or addition of one or more other features, numbers, steps, components, or combinations thereof.

[0053] Furthermore, in the present invention, when each layer or element is described as being formed "on" or "above" each layer or element, it means that each layer or element is formed directly on each layer or element, or that another layer or element may be additionally formed between each layer, on an object, or on a substrate.

[0054] The present invention is capable of various modifications and may take various forms, and specific embodiments are illustrated and described in detail below. However, this is not intended to limit the invention to the specific disclosed forms, and it should be understood that the invention includes all modifications, equivalents, and substitutions that fall within the spirit and scope of the invention.

[0056] A polymer, a composition, a non-aqueous electrolyte battery separator using the same, and a non-aqueous electrolyte battery according to specific embodiments of the invention will be described in more detail below.

[0058] polymer

[0059] According to one embodiment of the present invention, a flame-retardant group-containing polymer is provided, comprising a first repeating unit represented by the following chemical formula 1, a second repeating unit represented by the following chemical formula 2, and a third repeating unit represented by the following chemical formula 3.

[0060] [Chemical Formula 1]

[0061]

[0062] In the above chemical formula 1, R1 is hydrogen or an alkyl having 1 to 8 carbon atoms, and

[0063] [Chemical Formula 2]

[0064]

[0065] In the above chemical formula 2, R21 is an acetate (CH3COO-) group, and

[0066] [Chemical Formula 3]

[0067]

[0068] In the above chemical formula 3, R31 is -(C=O)O-, R32 is a phosphorus-based flame retardant group, and R33 is an electron withdrawing group.

[0070] In the above, the term "phosphorus-based flame retardant group" refers to a phosphorus atom-containing functional group that is included in a compound used as a phosphorus-based flame retardant and imparts flame retardancy, and more specifically, means a phosphate group, a phosphonate group, a phosphinate group, a phosphine oxide group, or a phosphazene group.

[0072] The inventors of the present invention have completed the present invention by confirming through experiments that, in a polymer containing flame-retardant groups used as a dispersant for inorganic fillers within a heat-resistant porous layer of a non-aqueous electrolyte battery separator, flame-retardant groups are introduced into the polymer side chains, and additionally, by controlling the ratio of each repeating unit constituting the polymer, namely the ethylene series, vinyl acetate series, and the degree of introduction of flame-retardant groups, the bonding properties of the inorganic filler can be improved and the dispersibility increased, thereby improving the heat resistance of the separator and simultaneously imparting flame retardancy to the separator.

[0074] It is well known that in non-aqueous electrolyte cell separators, polymers containing cyanoethyl groups or polymers containing flame-retardant groups serve as binders to firmly adhere inorganic fillers, but methods to impart properties such as flame retardancy by introducing functional groups to the side chains of such polymers are not specifically known.

[0076] A flame-retardant group-containing polymer according to one aspect of the present invention can not only serve as a binder for firmly adhering an inorganic filler when forming a heat-resistant porous layer of a separator, but also serve as a dispersant capable of effectively dispersing the inorganic filler, and by also possessing flame retardancy, it is possible to realize a separator having significantly improved adhesion, heat resistance, and flame retardancy compared to prior art.

[0078] According to one aspect of the present invention, a flame-retardant group-containing polymer is provided, comprising a first repeating unit represented by the following chemical formula 1, a second repeating unit represented by the following chemical formula 2, and a third repeating unit represented by the following chemical formula 3.

[0079] [Chemical Formula 1]

[0080]

[0081] In the above chemical formula 1, R1 is hydrogen or an alkyl having 1 to 8 carbon atoms, and

[0082] [Chemical Formula 2]

[0083]

[0084] In the above chemical formula 2, R21 is an acetate (CH3COO-) group, and

[0085] [Chemical Formula 3]

[0086]

[0087] In the above chemical formula 3, R31 is -(C=O)O-, R32 is a phosphorus-based flame retardant group, and R33 is an electron withdrawing group.

[0089] In such flame-retardant group-containing polymers, the repeating unit represented by Chemical Formula 1 above can be seen as a repeating unit derived from alpha-olefins such as ethylene, propylene, butene, i.e., alkene series monomers, and these monomers can be specifically represented by Chemical Formula 1-1 below.

[0090] [Chemical Formula 1-1]

[0091]

[0092] In the above chemical formula 1-1, R1 is as defined in the above chemical formula 1.

[0094] And, the repeating unit represented by the above chemical formula 2 can be viewed as ii) a repeating unit derived from a vinyl acetate series monomer, and such a monomer can be specifically represented by the following chemical formula 2-1.

[0095] [Chemical Formula 2-1]

[0096]

[0097] In the above chemical formula 2-1, R21 is as defined in the above chemical formula 2.

[0099] Copolymers in which vinyl acetate or vinyl alcohol-based repeating units are introduced into ethylene repeating units, or copolymers in which cyanoethyl groups are additionally introduced thereto, are commonly used for bonding and dispersion of substrate components and inorganic fillers in non-aqueous electrolyte cell separators. In particular, the carbonyl groups of vinyl acetate can improve the dispersibility of inorganic fillers through interaction with the inorganic fillers.

[0101] And, the repeating unit represented by the above chemical formula 3 can be seen as derived from a vinyl-acetate-based monomer into which a flame-retardant group has been introduced, and such a monomer can specifically be represented by the following chemical formula 3-1 or 3-2.

[0102] [Chemical Formula 3-1]

[0103]

[0104] [Chemical Formula 3-2]

[0105]

[0106] In the above chemical formulas 3-1 and 3-2, R31, R32, and R33 are as defined in the above chemical formula 3. Additionally, the flame-retardant group represented by R32 may be in a form that is introduced into the monomer used for polymerization from the beginning, as in chemical formula 3-1, or it may be introduced to the adjacent carbon of CN through an addition reaction, etc., after polymerization is carried out using the monomer of chemical formula 3-2.

[0108] The flame-retardant group may be one or more selected from the group consisting of phosphate, phosphonate, phosphinate, phosphine oxide, and phosphazene.

[0110] According to one embodiment of the invention, the R32 may include one or more flame-retardant groups selected from the group consisting of the following chemical formulas.

[0111] , , , , ,

[0112] In the above chemical formula, R1 and R2 are each independently hydrogen, a monovalent metal cation, an ammonium ion, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or an alkylaryl group having 7 to 10 carbon atoms.

[0113] At this time, it may be more preferable that R1 and R2 are each independently hydrogen, ammonium ions, alkyl groups having 1 to 5 carbon atoms, or phenyl groups.

[0114] In addition, one or more flame-retardant groups selected from the group consisting of the above-described chemical formulas may be connected to the repeating unit of the chemical formula 3 by an alkylene having 1 to 5 carbon atoms or an alkynylene group having 1 to 5 carbon atoms, and in this case, one or more flame-retardant groups may be introduced within a single repeating unit.

[0117] These phosphorus-based flame retardant groups can reduce the possibility of fire caused by electrical defects during the charging and discharging of secondary batteries.

[0118] Specifically, these phosphorus-based flame retardant groups can promote the formation of char through mechanisms such as ester exchange reaction, dehydration reaction, dehydrogenation reaction, and carbonization reaction when a fire occurs, and this char can prevent fire by physically blocking heat transfer and oxygen access caused by the fire.

[0119] In addition, phosphorus-based flame retardant groups form phosphate radicals through thermal decomposition, and these phosphate radicals capture substances such as hydrogen or hydroxyl radicals, effectively blocking the propagation of oxidation or combustion reactions, thereby preventing the fire from growing larger.

[0121] In this regard, within the flame-retardant group-containing polymer, the ratio of the number of repeating units of the first repeating unit to the total number of repeating units of the first to third repeating units, that is, the ratio of repeating units derived from alkene-based monomers, may be about 0.1 to about 0.5, the lower limit value may be about 0.1 or more, or about 0.15 or more, and the upper limit value may be about 0.5 or less, or about 0.45 or less.

[0122] If the ratio of the number of repeating units of the first repeating unit, that is, the ratio of repeating units derived from alkene monomers, is too low, the adhesion between the separator and the inorganic porous material is weak, which may cause problems such as thermal shrinkage of the separator.

[0124] And, the ratio of the number of repeating units of the second repeating unit to the total number of repeating units of the first to third repeating units in the flame-retardant group-containing polymer, that is, the ratio of repeating units derived from vinyl acetate-based monomers, may be about 0.3 to about 0.8, the lower limit value may be about 0.3 or more, or about 0.4 or more, or about 0.45 or more, and the upper limit value may be about 0.8 or less, or about 0.75 or less.

[0125] If the ratio of the number of repeating units of the second repeating unit, that is, the ratio of repeating units derived from vinyl acetate-based monomers, is too low, the dispersion of the inorganic porous material attached to the separator is not well achieved, which may lead to thermal expansion problems at local points on the separator.

[0127] And, the ratio of the number of repetitions of the third repeating unit to the total number of repetitions of the first to third repeating units in the polymer containing the flame-retardant group, that is, the ratio of the repeating unit into which the flame-retardant group is introduced, may be about 0.01 to about 0.3, the lower limit value may be about 0.01 or more, or greater than about 0.02, or about 0.03 or more, or about 0.04 or more, and the upper limit value may be 0.3 or less, or less than about 0.3, or about 0.25 or less.

[0128] If the ratio of the number of repetitions in the second repetition unit, that is, the ratio of repetition units to which the flame-retardant group has been introduced, is too low, a problem may arise in which the fire occurrence rate increases when phenomena such as thermal shrinkage of the separator occur.

[0130] These flame-retardant group-containing polymers can be produced by copolymerizing i) alpha-olefins, i.e., alkene-series monomers, such as ethylene, propylene, butene, ii) vinyl acetate-series monomers, and iii) vinyl acetate-series monomers into which flame-retardant groups have been introduced.

[0131] iii) In the case of vinyl acetate-based monomers with introduced flame-retardant groups, a monomer in which flame-retardant groups are introduced to the side chains from the beginning may be used, or a vinyl acetate-based monomer without introduced flame-retardant groups may be used to proceed with polymerization, and then flame-retardant groups may be introduced through a separate addition reaction.

[0132] However, in terms of the stability of the polymerization reaction, it may be desirable to proceed with polymerization using a vinyl acetate-based monomer without a flame-retardant group, and then introduce a flame-retardant group next to the electron-withdrawing group through a separate addition reaction.

[0134] For polymerization, a solution polymerization method can be used in which each monomer is added to a solvent to prepare a monomer mixture for polymerization, and the polymerization reaction is carried out in the presence of an initiator.

[0135] At this time, solvents that do not affect the polymerization reaction of monomers, such as alcohol-based solvents like water, methanol, ethanol, isopropanol, butanol, and isobutanol; ketone-based solvents like dimethyl ketone, diethyl ketone, methyl ethyl ketone, and methyl isobutyl ketone; and aromatic-based solvents like toluene and xylene, may be used without any special restrictions.

[0136] It is preferable to use a solvent in an amount of about 20 to about 300 parts by weight relative to 100 parts by weight of the total monomer to ensure smooth progress of the polymerization reaction.

[0138] In addition, the polymerization initiator used during polymerization is a radical photopolymerization or thermal polymerization initiator generally used in the polymerization reaction of the monomer described above, and its type is not particularly limited. However, it may be preferable to use a thermal polymerization initiator to ensure the smooth progress of the polymerization reaction.

[0139] The above thermal polymerization initiator may specifically use azo series or peroxide series initiators such as, for example, 2,2'-azobis-isobutyronitrile (AIBN), 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2'-azobis-(4-methoxy-2,4-dimethylvaleronitrile), benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, and 1,1'-bis-(bis-t-butylperoxy)cyclohexane.

[0140] The initiator can be used in an amount of about 0.05 to 5 parts by weight, or about 0.1 to about 3 parts by weight, relative to 100 parts by weight of the total monomer.

[0141] These initiators may be prepared by being included in the monomer mixture described above from the beginning, or they may be added separately after the prepared monomer mixture has been heated to an appropriate polymerization temperature.

[0143] The polymerization reaction may be carried out at a temperature of room temperature to about 100°C, and it may be preferable to carry out the reaction at a temperature of about 40°C or higher, or about 50°C or higher, and at a temperature of about 90°C or lower, or about 80°C or lower.

[0145] When polymerization is carried out using vinyl acetate-based monomers that have not had a flame-retardant group introduced, a flame-retardant group is introduced after polymerization through a separate addition reaction, etc., next to the electron-withdrawing group.

[0146] The addition reaction may proceed continuously following the aforementioned polymerization reaction, or it may proceed separately.

[0147] Addition reactions can be represented by the following reaction mechanism.

[0148]

[0149] In step 1, a base is introduced into the polymer. The base removes a hydrogen from the adjacent site of the CN group to form a carbon anion on the corresponding carbon, and this carbon anion can be maintained stably due to the inductive and resonance effects of the adjacent electron-withdrawing group.

[0150] Here, a flame-retardant compound of R32' is added. R32' is a precursor of the R32 flame-retardant group of the aforementioned chemical formula 3, and a compound containing carbon-carbon unsaturated bonds within the molecule in addition to the flame-retardant group is used.

[0151] The non-covalent electron pair of the aforementioned carbon anion is connected to the carbon-carbon unsaturated bond of R32' through an addition reaction, and a new carbon anion is formed at the adjacent carbon, to which hydrogen is supplied from the acid, and the reaction can be completed.

[0153] According to another embodiment of the invention, the weight average molecular weight value of the flame-retardant group-containing polymer may be 150,000 to 500,000 g / mol, the lower limit may be about 200,000 g / mol or more, or about 240,000 g / mol or more, and the upper limit may be about 500,000 g / mol or less, or about 450,000 g / mol or less, or about 350,000 g / mol or less.

[0154] By complex factors such as the ratio of each repeating unit and the molecular weight of the polymer described above, the adhesive strength of the inorganic filler can be improved, and it can also be effectively dispersed.

[0155] At this time, the weight-average molecular weight value can be measured by gel permeation chromatography (GPC) using polystyrene as a standard.

[0157] Composition and separator for non-aqueous electrolyte battery

[0158] Meanwhile, according to another aspect of the invention, a dispersant composition for a non-aqueous electrolyte cell separator is provided, comprising a polymer containing flame-retardant groups.

[0159] The above-mentioned dispersant composition for a non-aqueous electrolyte battery separator may further include an inorganic filler.

[0160] The above-mentioned inorganic filler is not particularly limited as long as it has a melting point of about 200°C or higher, high electrical insulation, is electrochemically stable, and is stable in an electrolyte or a solvent used in a slurry for forming a heat-resistant porous layer.

[0161] The above-mentioned inorganic filler may include one or more selected from the group consisting of inorganic oxides, inorganic nitrides, sparingly soluble ionic crystal microparticles, covalent crystals, clay, materials derived from mineral resources, lithium titanium phosphate, and combinations thereof.

[0162] The above-mentioned inorganic filler is, more specifically, for example, iron oxide, SiO2 (silica), Al2O3 (alumina), TiO2, BaTiO3, ZrO, PB (Mg3Nb 2 / 3 Inorganic oxide fine particles such as )O3-PbTiO3 (PMN-PT), hafnia (HfO2), SrTiO3, SnO2, CeO2, MgO, NiO, CaO, ZnO, ZrO2, Y2O3, etc.; inorganic nitride fine particles such as aluminum nitride, silicon nitride, etc.; sparingly soluble ionic crystal fine particles such as calcium fluoride, barium fluoride, barium sulfate, etc.; covalent crystalline fine particles such as silicon, diamond, etc.; clay fine particles such as talc, montmorillonite, etc.; materials derived from mineral resources such as boehmite, zeolite, apatite, kaolin, mullite, spinel, olivine, sericite, bentonite, etc., or lithium titanium phosphate (Li x Ti y (PO4)3, in the formula, x and y are 0 <x<2, 0<y<3을 만족하는 수임); 또는 이들의 조합 등을 들 수 있다.

[0163] The particle size of the above-mentioned inorganic filler is not particularly limited, but in order to form a heat-resistant porous layer of uniform thickness and obtain an appropriate porosity, an average particle size of about 5 nm to about 5 μm may be used, and preferably, about 0.01 to about 1 μm may be used.

[0164] Meanwhile, here, the average particle size can be measured by a measuring device based on the laser diffraction scattering method.

[0165] If the diameter of the inorganic filler is too small, dispersibility is reduced, which may lead to problems where it is difficult to control the physical properties of the separator.

[0166] In addition, if the diameter of the inorganic filler is too large, problems may arise such as a decrease in the strength of the heat-resistant porous layer and a decrease in the smoothness of the surface, and there is also a concern that the mechanical properties may deteriorate as the heat-resistant porous layer being manufactured becomes thicker.

[0168] In addition, the composition used to form a heat-resistant porous layer in a non-aqueous electrolyte battery separator may further include, as necessary, resins such as cyanoethyl-containing polymers, ethylene-vinyl acetate copolymers (EVA, having 20 to 35 mol% of structural units derived from vinyl acetate), acrylate copolymers, styrene-butadiene rubber (SBR), polyvinyl butyral (PVB), polyvinylpyrrolidone (PVP), polyurethane, polyvinylidene fluoride-hexafluoropropylene, polyvinylidene fluoride-trichloroethylene, polyvinylidene fluoride-chlorotrifluoroethylene copolymers, polyvinylidene fluoride-hexafluoropropylene, polyvinylidene fluoride-trichloroethylene, cellulose acetate, cellulose acetate butyrate, and cellulose acetate propionate, in addition to the flame-retardant group-containing polymers described above.

[0169] When using these resins additionally, the resins can be mixed and used in an amount of about 10 to about 1,000 parts by weight relative to 100 parts by weight of the flame-retardant group-containing polymer.

[0171] Meanwhile, according to another aspect of the invention, a separator for a non-aqueous electrolyte battery is provided, comprising a porous substrate and a heat-resistant porous layer formed on at least one surface of the porous substrate, wherein the heat-resistant porous layer comprises the aforementioned dispersant composition for a non-aqueous electrolyte battery separator.

[0172] The above heat-resistant porous layer may further include an inorganic filler.

[0174] Specifically, the separator for a non-aqueous electrolyte battery according to the present invention may be a separator comprising a heat-resistant porous layer including the dispersant composition and an inorganic filler, and a porous substrate, wherein the heat-resistant porous layer may be formed on one or both sides of the surface of the porous substrate and may have a structure having a plurality of pores resulting from the voids between the inorganic fillers inside.

[0175] If the heat-resistant porous layer is formed on only one side of the porous substrate surface, it may be installed on either the anode side surface or the cathode side surface.

[0177] Meanwhile, there are no particular limitations on the method for forming a heat-resistant porous layer, but for example, a slurry in which an inorganic filler is dispersed in the dispersant composition described above can be prepared, coated onto a porous substrate, and then a method such as drying to remove the solvent can be used.

[0178] Here, the solvent used in the dispersant composition is not particularly limited as long as it is capable of dissolving the flame-retardant group-containing polymer described above, and may be, for example, acetone, tetrahydrofuran, cyclohexanone, ethylene glycol monomethyl ether, methyl ethyl ketone, acetonitrile, furfuryl alcohol, tetrahydrofurfuryl alcohol, methyl acetoacetate, nitromethane, N,N-dimethylformamide (DMF), N-methyl-2-pyrrolidone, γ-butyrolactone, propylene carbonate, etc.

[0179] These solvents can be used in a ratio of about 300 to about 5,000 parts by weight relative to 100 parts by weight of the flame-retardant group-containing polymer and resin components.

[0180] In addition, known stirrers, dispersers, grinders, etc., can be used as a method for dispersing an inorganic filler in the above-described dispersant composition, and specifically, a ball mill method can be used.

[0181] The relative content ratio between the dispersant composition and the inorganic filler in the above slurry is not particularly limited and can be adjusted differently depending on the thickness, average pore diameter, and porosity of the heat-resistant porous layer to be manufactured.

[0182] Specifically, the content of the inorganic filler in the heat-resistant porous layer may be about 50 weight% or more, or about 95 weight% or less.

[0183] If the content of the inorganic filler is too low, the ratio of pores in the heat-resistant porous layer decreases, which may result in reduced battery performance or insufficient heat resistance. If the content of the inorganic filler is too high, the heat-resistant porous layer becomes brittle, which may result in difficulties in handling.

[0185] Meanwhile, the heat-resistant porous layer can be made low-resistance because ion conduction paths are secured by the pores. The average pore diameter is not particularly limited as long as it is large enough for lithium ions in the electrolyte described later to pass through, but from the perspective of the mechanical strength of the heat-resistant porous layer, it may be about 5 nm to about 5 μm, preferably about 0.1 to about 3 μm, and the porosity may be in the range of about 5 to about 95%, preferably about 20 to about 70%.

[0186] Here, the average pore diameter can be measured by a mercury indentation type pore meter, and the porosity can be calculated by the following formula after determining the true density (d) of the inorganic filler, the volume (v) of the heat-resistant porous layer, and the mass (m) of the heat-resistant porous layer.

[0187] Porosity (%) = {1 - m / (vd)} × 100

[0189] A heat-resistant porous layer having an average pore diameter and porosity value within the above range can be obtained by controlling the particle size or content of the inorganic filler as described above.

[0191] Meanwhile, the porous substrate may contain a thermoplastic resin component.

[0192] A porous substrate containing a thermoplastic resin component can melt and close its pores when the temperature rises above a certain level, thereby blocking the movement of ions and preventing current from flowing, which can suppress heat generation or ignition.

[0193] Thermoplastic resins that can be used as porous substrates may be polyolefin resins such as low-density polyethylene, high-density polyethylene, ultra-high molecular weight polyethylene, and polypropylene; polyester resins such as polyethylene terephthalate and polybutylene terephthalate; polyacetal resin, polyamide resin, polycarbonate resin, polyimide resin, polyetheretherketone resin, polyethersulfone resin, or a combination thereof.

[0195] Meanwhile, the porous substrate may preferably have the form of a film, and although its thickness is not particularly limited, it is preferably about 2 to about 50 μm. If the thickness is too thin, there may be a problem in maintaining mechanical properties, and if the thickness is too thick, a problem may occur in that it acts as a resistance layer.

[0196] In addition, there are no particular limitations on the average pore diameter and porosity of the porous substrate, but it may be preferable that the average pore diameter be about 0.1 to about 30 μm and the porosity be about 10% to about 90%.

[0197] If the pore size is too small or the porosity is too low, a problem of poor ion conductivity may occur; if the average pore diameter is too large or the porosity is too high, a problem may arise where the mechanical strength is reduced, rendering it unable to function as a substrate.

[0198] The average pore diameter can be measured in the same way as in the case of a heat-resistant porous layer. Meanwhile, the porosity can be calculated by determining the true density (d) of the porous substrate, the volume (v) of the porous substrate, and the mass (m) of the porous substrate, and by the following formula.

[0199] Porosity (%) = {1 - m / (vd)} × 100

[0201] Meanwhile, as a method for coating the above-mentioned slurry onto a porous substrate, conventional coating methods in the relevant technical field may be used, and any method capable of realizing the required layer thickness or coating area is not particularly limited. For example, methods such as gravure coater, reverse roll coater, transfer roll coater, kiss coater, deep coater, knife coater, air doctor coater, blade coater, rod coater, squeeze coater, cast coater, die coater, screen printing, and spray coating may be used.

[0203] The total thickness of the non-aqueous electrolyte battery separator obtained as described above is not particularly limited and can be adjusted considering the use and performance of the battery, and may be within the range of about 2 to about 55 μm from the perspective of more effectively separating the positive and negative electrodes.

[0205] non-aqueous electrolyte battery

[0206] Meanwhile, a non-aqueous electrolyte battery according to one aspect of the present invention may include a positive electrode, a negative electrode, a separator for the non-aqueous electrolyte battery described above, and an electrolyte.

[0207] Specifically, a non-aqueous electrolyte battery can be manufactured by placing a separator for the non-aqueous electrolyte battery between the positive and negative electrodes and impregnating it with an electrolyte.

[0208] When using a separator for a non-aqueous electrolyte battery in which a heat-resistant porous layer is provided on only one side of a porous substrate, the side having the heat-resistant porous layer may be positioned on either the positive side or the negative side.

[0209] The non-aqueous electrolyte battery of the present invention may include, for example, a lithium secondary battery comprising a lithium metal secondary battery, a lithium ion secondary battery, a lithium polymer secondary battery, or a lithium ion polymer secondary battery.

[0211] Meanwhile, the above anode and cathode can generally be manufactured by applying an electrode mixture, in which an anode or cathode active material and a conductive agent are dispersed in a solution in which a binder is dissolved, to a current collector.

[0212] As a positive active material, Li 1+x MO2(-0.1 <x<0.1, M: Co, Ni, Mn, Al, Mg, Zr, Ti, Sn 등)의 화학식으로 대표되는 층상 구조의 리튬 함유 전이 금속 산화물, LiMn2O4이나 그의 원소의 일부를 다른 원소로 치환한 스피넬 구조의 리튬망간 산화물, LiMPO4(M: Co, Ni, Mn, Fe 등)로 표시되는 올리빈형 화합물 등을 이용하는 것이 모두 가능하다.

[0213] The above-mentioned layered lithium-containing transition metal oxide is, for example, LiCoO2 or LiNi 1-x Co x-y Al y O2 (0.1≤x≤0.3, 0.01≤y≤0.2), etc., and oxides (LiMn) containing at least Co, Ni and Mn 1 / 3 Ni 1 / 3 Co 1 / 3 O2, LiMn 5 / 12 Ni 5 / 12 Co 1 / 6 O2, LiNi 3 / 5 Mn 1 / 5 Co 1 / 5 Examples include O2, etc.

[0215] Meanwhile, cathode active materials include, for example, lithium alloys such as lithium metal and lithium aluminum alloy, carbonaceous materials capable of absorbing and releasing lithium, cokes such as graphite, phenolic resin and furan resin, carbon fibers, glassy carbon, pyrolytic carbon, activated carbon, etc.

[0217] Meanwhile, the positive current collector may be a thin metal body manufactured from, for example, aluminum, nickel, or a combination thereof, and the negative current collector may be a thin metal body manufactured from, for example, copper, gold, nickel, a copper alloy, or a combination thereof.

[0219] Meanwhile, conductive agents may include, for example, carbon black such as acetylene black or ketjen black; metal fibers such as aluminum or nickel; natural graphite, thermally expanded graphite, carbon fibers, ruthenium oxide, titanium oxide, etc. Among these, acetylene black or ketjen black, which can secure the desired conductivity with a small amount of formulation, may be preferably used.

[0220] Meanwhile, various known binders may be used as binders, and examples include polytetrafluoroethylene, polyvinylidene fluoride, carboxymethylcellulose, fluoroolefin copolymer crosslinked polymer, styrene-butadiene copolymer, polyacrylonitrile, polyvinyl alcohol, etc.

[0221] The above binder may be used in a solution, and as a solvent, for example, N-methyl-2-pyrrolidone (NMP) may be used.

[0223] Meanwhile, a solution of a lithium salt dissolved in an organic solvent is used as the electrolyte. As for the lithium salt, Li dissociates in the solvent. + There are no particular restrictions as long as it forms ions and is unlikely to cause side reactions such as decomposition within the voltage range used as a battery.

[0224] For example, inorganic lithium salts such as LiClO4, LiPF6, LiBF4, LiAsF6, LiSbF6, LiCF3SO3, LiCF3CO2, Li2C2F4(SO3)2, LiN(CF3SO2)2, LiC(CF3SO2)3, LiCnF 2n+1Organic lithium salts such as SO3(n≥2) and LiN(RfOSO2)2 (wherein Rf represents a fluoroalkyl group) can be used. Preferred lithium salts are LiPF6, LiClO4, LiAsF6, LiBF4, LiCF3SO3, and Li(CF3SO2)2N.

[0226] Meanwhile, regarding the organic solvent used in the electrolyte, there are no particular restrictions as long as it dissolves the lithium salt mentioned above and does not cause side reactions such as decomposition within the voltage range used as a battery. Examples include cyclic carbonate esters such as propylene carbonate and ethylene carbonate, chain carbonate esters such as ethylmethyl carbonate, diethyl carbonate, dimethyl carbonate, and dipropyl carbonate, or mixtures thereof, but are not limited thereto.

[0227] When using a mixture of cyclic carbonate esters and chain carbonate esters, the volume ratio of the cyclic carbonate esters to the chain carbonate esters is preferably about 4:1 to about 1:4 in terms of optimizing dielectric constant and viscosity.

[0229] Meanwhile, the form of the non-aqueous electrolyte battery of the present invention may be a polyhedral or cylindrical type using a steel can, an aluminum can, etc. as an outer body (outer can), or a package battery using a laminate film with a metal deposited thereon as an outer body, but is not particularly limited. Effects of the invention

[0231] The separator composition for a non-aqueous electrolyte battery according to the present invention can firmly adhere an inorganic filler when forming a heat-resistant porous layer of the separator, effectively disperse it to further improve the heat resistance of the separator, and prevent fires that may occur during charging and discharging. Specific details for implementing the invention

[0233] The operation and effects of the invention will be described in more detail below through specific embodiments. However, these embodiments are merely examples of the invention and do not define the scope of the invention.

[0235] <Example>

[0236] Preparation of polymers

[0237] Example 1

[0238] (polymerization)

[0239] 100 parts by weight of vinyl acetate and 20 parts by weight of vinyl 2-cyanoacetate were added to a 2L reactor containing 100 parts by weight of methanol, and 20 parts by weight of ethylene were added, and then waited until there was no change in the internal pressure of the reactor.

[0240] After raising the temperature to 70 ℃, 0.3 parts by weight of AIBN were dissolved in 5 parts by weight of methanol as an initiator and introduced into a reactor, and the polymerization reaction was carried out by stirring at 200 rpm for 6 hours, after which the reactor was cooled to room temperature to obtain a copolymer of the following chemical formula.

[0241]

[0242] In the above chemical formula, R1 is hydrogen, R21 is acetate (CH3COO-), and R31 is -C(=O)-O-.

[0244] (Addition reaction)

[0245] 5 parts by weight of potassium carbonate was dissolved in 5 parts by weight of methanol as a basic component, added to the cooled reactor, and stirred for 1 hour.

[0246] Here, 3 parts by weight of maleic acid were dissolved in 5 parts by weight of methanol and added to the reactor, and stirred again for 1 hour.

[0247] Subsequently, 5 parts by weight of tetraethyl ethyne-1,2-diyldiphosphonate, represented by the following chemical formula, were added to a reactor.

[0248]

[0249] This was stirred again for 1 hour, and the remaining solvent, etc. were drained to obtain a copolymer of the following chemical formula.

[0250]

[0251] In the above chemical formula, R1 is hydrogen, R21 is acetate (CH3COO-), R31 is -C(=O)-O-, and R32 is a flame-retardant group represented by the following chemical formula, introduced from tetraethyl ethane-1,2-diyldiphosphonate.

[0252]

[0254] Example 2

[0255] A copolymer of the following chemical formula was obtained by proceeding in the same manner as in Example 1, except that 20 parts by weight of ethenyl-3-oxobutanoate was used instead of 20 parts by weight of vinyl 2-cyanoacetate in the polymerization step.

[0256]

[0257] In the above chemical formula, R1 is hydrogen, R21 is acetate (CH3COO-), R31 is -C(=O)-O-, and R32 is a flame-retardant group represented by the following chemical formula, introduced from tetraethyl ethane-1,2-diyldiphosphonate.

[0258]

[0260] Example 3

[0261] A copolymer of the following chemical formula was obtained by proceeding in the same manner as in Example 1, except that 150 parts by weight of vinyl acetate and 20 parts by weight of vinyl 2-cyanoacetate were introduced into a 2L reactor containing 100 parts by weight of methanol, 15 parts by weight of ethylene, and 0.3 parts by weight of AIBN were used as an initiator.

[0262]

[0263] In the above chemical formula, R1 is hydrogen, R21 is acetate (CH3COO-), R31 is -C(=O)-O-, and R32 is a flame-retardant group represented by the following chemical formula, introduced from tetraethyl ethane-1,2-diyldiphosphonate.

[0264]

[0266] Example 4

[0267] A copolymer of the following chemical formula was obtained by proceeding in the same manner as in Example 1, except that 10 parts by weight of potassium carbonate, 10 parts by weight of maleic acid, and 15 parts by weight of tetraethyl ethane-1,2-diyldiphosphonate were used in the addition step.

[0268]

[0269] In the above chemical formula, R1 is hydrogen, R21 is acetate (CH3COO-), R31 is -C(=O)-O-, and R32 is a flame-retardant group represented by the following chemical formula, introduced from tetraethyl ethane-1,2-diyldiphosphonate.

[0270]

[0272] Example 5

[0273] A copolymer of the following chemical formula was obtained by proceeding in the same manner as in Example 1 above, except that t-butanol was used instead of methanol.

[0274]

[0275] In the above chemical formula, R1 is hydrogen, R21 is acetate (CH3COO-), R31 is -C(=O)-O-, and R32 is a flame-retardant group represented by the following chemical formula, introduced from tetraethyl ethane-1,2-diyldiphosphonate.

[0276]

[0278] Example 6

[0279] A copolymer of the following chemical formula was obtained by proceeding in the same manner as in Example 1 above, except that ethyne-1,2-diyldiphosphinic acid was used instead of tetraethyl ethyne-1,2-diyldiphosphonate in the addition step.

[0280]

[0281] In the above chemical formula, R1 is hydrogen, R21 is acetate (CH3COO-), R31 is -C(=O)-O-, and R32 is a flame-retardant group represented by the following chemical formula, introduced from ethyne-1,2-diyldiphosphine acid.

[0282]

[0284] Comparative Example 1

[0285] A copolymer was obtained by proceeding in the same manner as in Example 1, except that vinyl propionate was used instead of vinyl-2-cyanoacetate in the polymerization step.

[0287] Comparative Example 2

[0288] A copolymer was obtained by proceeding in the same manner as in Example 1, except that diethyl ethyne-1,2-diyldicarboxylate was used instead of tetraethyl ethyne-1,2-diyldiphosphonate in the addition step.

[0290] Measurement of repeat unit ratio

[0291] Each repeating unit of the polymer is, 1 The procedure was performed using H-NMR.

[0292] The peak areas were measured based on hydrogen of the ethylene group: about 1.0 to 1.2 ppm; hydrogen of the methyl group of vinyl acetate: about 2.0 ppm; and hydrogen bonded to the double bond carbon of the flame-retardant substituent group: about 6.1 to about 6.4 ppm, and each ratio was calculated.

[0294] Weight-average molecular weight measurement

[0295] Analysis was performed using GPC equipped with a column PLgel Mixed B * 2 containing DMF (HPLC) and 0.05M LiBr (0.45 μm filtered) as solvents and a detector waters RI instrument, and other measurement conditions are as follows.

[0296] Device: Gel Penetration Chromatography GPC (Instrument Name: Alliance e2695; Manufacturer: WATERS)

[0297] Detector: Parallax Refractive Index Detector (Measuring Instrument Name: W2414; Manufacturer: WATERS)

[0298] Column: DMF Column

[0299] Flow rate: 1 mL / min

[0300] Column temperature: 65℃

[0301] Injection volume: 0.100 mL (2.0 mg / ml in DMSO)

[0302] Standardized Sample: Polymethyl methacrylate tertiary correction

[0304] Slurry manufacturing

[0305] 1 part by weight of the polymer obtained from each of the above examples and comparative examples and 7 parts by weight of polyvinylidene fluoride-hexafluoropropylene as a binder were added to 320 parts by weight of acetone and dissolved at 50°C for 12 hours. Thereupon, 72 parts by weight of Al2O3 with a number average particle size of 500 nm were added as inorganic particles, and a slurry was prepared using a ball mill method, and the particle size characteristics and sedimentation rate of the slurry were measured.

[0307] Separator manufacturing

[0308] A slurry of flame-retardant group-containing polymer and inorganic particles prepared above was applied to one side of a polyethylene porous substrate using a doctor blade and dried to produce a separator with a porous coating layer formed thereon.

[0310] Sedimentation velocity measurement

[0311] To verify the dispersion power, the slurries prepared in the examples and comparative examples were rotated at approximately 300 rpm using a dispersion stability disperser (LUMiSizer), and the sedimentation rate of alumina was measured at 25°C. The results are shown in the table below. For reference, the better the dispersion power of the flame-retardant group-containing polymer, the better the alumina is dispersed and the slower it settles.

[0313] Heat shrinkage evaluation

[0314] The separators prepared in the above examples and comparative examples were placed in a heat-resistant oven at 150°C and left for 2 hours.

[0315] Subsequently, the separator was removed, and its lengths in the MD and TD directions were measured. The percentage of reduction was indicated by comparing it to its size before heating.

[0317] Adhesion strength evaluation

[0318] A cathode slurry was prepared by mixing artificial graphite, carbon black, CMC, and a binder with water in a weight ratio of 96:1:1:2. The cathode slurry was coated onto a copper foil with a thickness of 50 μm, dried at 80°C for more than 1 hour, and then pressed to produce a cathode.

[0319] The above cathode and separator were placed in a lamination device to bond them, and the sample was peeled using a UTM device at a speed of 100 mm / min, while measuring the force required to peel off the bonding surface of the electrode and the separator.

[0320] The measurement results are summarized in the table below.

[0322] Adhesion (gf / 25mm) Sedimentation velocity (㎛ / s) Flame retardancy Thermal shrinkage rate (MD / TD, %) Weight average molecular weight (100,000) Repeating unit ratio (ethylene, vinyl acetate, flame retardant, based on total 100) Example 1 150 5 V0 15, 18 2.5 25, 65, 10 Example 2 130 7 V0 18, 20 3.3 17, 73, 10 Example 3 140 10 V1 25, 25 1.8 32, 63, 5 Example 4 145 15 V1 20, 17 2.2 42, 48, 10 Example 5 130 10 V1 15, 18 3.5 35, 60, 5 Example 6 130 8 V1 16, 22 1.9 27, 53, 20 Comparative Example 1 110 20 HB 30, 35 1.4 - Comparative Example 2 120 20 HB 30, 35 1.4 -

[0323] Referring to the table above, it can be seen that the slurry prepared using the flame-retardant group-containing polymer according to one embodiment of the present invention has adhesive strength or dispersion strength that is similar to or superior to that of conventional materials.

[0324] In addition, it can be clearly confirmed that the separator manufactured using such a flame-retardant group-containing polymer possesses excellent flame retardancy and also exhibits excellent thermal stability.

Claims

Claim 1 A flame-retardant group-containing polymer comprising a first repeating unit represented by the following chemical formula 1, a second repeating unit represented by the following chemical formula 2, and a third repeating unit represented by the following chemical formula 3: [Chemical Formula 1] In the above Chemical Formula 1, R1 is hydrogen or an alkyl having 1 to 8 carbon atoms, and [Chemical Formula 2] In the above Chemical Formula 2, R21 is an acetate (CH3COO-) group, and [Chemical Formula 3] In the above chemical formula 3, R31 is -(C=O)O-, R32 is a phosphorus-based flame retardant group, and R33 is an electron withdrawing group. Claim 2 In claim 1, the R32 is a flame-retardant group-containing polymer comprising one or more flame-retardant groups selected from the group consisting of the following chemical formulas: , , , , , In the above chemical formula, R1 and R2 are each independently hydrogen, a monovalent metal cation, an ammonium ion, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or an alkylaryl group having 7 to 10 carbon atoms. Claim 3 In paragraph 2, a flame-retardant group-containing polymer, wherein R1 and R2 are each independently hydrogen, ammonium ions, alkyl groups having 1 to 5 carbon atoms, or phenyl groups. Claim 4 A flame-retardant group-containing polymer according to claim 1, wherein the ratio of the number of repetitions of the first repeating unit to the total number of repetitions of the first to third repeating units within the flame-retardant group-containing polymer is 0.1 to 0.

5. Claim 5 A flame-retardant group-containing polymer according to claim 1, wherein the ratio of the number of repetitions of the second repeating unit to the total number of repetitions of the first to third repeating units within the flame-retardant group-containing polymer is 0.3 to 0.

8. Claim 6 A flame-retardant group-containing polymer according to claim 1, wherein the ratio of the number of repetitions of the third repeating unit to the total number of repetitions of the first to third repeating units within the flame-retardant group-containing polymer is 0.01 to 0.

3. Claim 7 A flame-retardant group-containing polymer having a weight average molecular weight of 100,000 to 500,000 in claim 1. Claim 8 A dispersant composition for a non-aqueous electrolyte battery separator comprising a flame-retardant group-containing polymer according to any one of claims 1 to 7. Claim 9 A dispersant composition for a non-aqueous electrolyte battery separator, further comprising an inorganic filler in claim 8. Claim 10 A dispersant composition for a non-aqueous electrolyte battery separator according to claim 9, wherein the inorganic filler comprises one or more selected from the group consisting of inorganic oxides, inorganic nitrides, sparingly soluble ionic crystal microparticles, covalent crystals, clay, mineral resource-derived materials, lithium titanium phosphate, and combinations thereof. Claim 11 A separator for a non-aqueous electrolyte battery comprising a porous substrate and a heat-resistant porous layer formed on at least one surface of the porous substrate, wherein the heat-resistant porous layer comprises a dispersant composition for a non-aqueous electrolyte battery separator according to claim 8. Claim 12 A separator for a non-aqueous electrolyte battery according to claim 11, wherein the porous substrate is composed of one or more resins selected from the group consisting of polyolefin resin, polyester resin, polyacetal resin, polyamide resin, polycarbonate resin, polyimide resin, polyetheretherketone resin, polyethersulfone resin, and combinations thereof. Claim 13 A non-aqueous electrolyte battery comprising a positive electrode, a negative electrode, a separator for a non-aqueous electrolyte battery according to claim 11, and an electrolyte.

Images