WO2018128484A1 - Separator for battery to which functional binder is applied, and electrochemical device applying same - Google Patents

Abstract

The present invention relates to: a functional binder in a separator that comprises a porous polyolefin substrate and an organic-inorganic composite porous coating layer which includes a mixture of a binder compound with inorganic particles formed on at least one surface of the substrate; and a separator comprising the same, wherein the functional binder can increase adhesion between a binder and an inorganic material and between a substrate and a binder while pre-empting an internal short-circuit through a self-healing function for partial damage of the separator, improve adhesion of the separator to a cathode and an anode, and respond to elution of a cathode material transition metal. In the binder according to the present invention, the proportion of the hydroxyl group in each molecule is 10% by weight or more.

Description

Separator for battery with functional binder and electrochemical device

The present invention relates to a separator to which a functional binder is applied, and more particularly, to a separator including an inorganic particle coated on one surface of a polyolefin substrate and a functional binder having improved properties, and an electrochemical device including the same.

A lot of research has been conducted to increase the stability of the separator for batteries, in particular the separator for lithium ion secondary batteries. Currently in production, Safety Reinforced Separator (hereinafter referred to as 'SRS') is a surface coated with inorganic particles and a binder on a polyolefin-based substrate. The pore structure of the inorganic particles and the binder increases the space for the liquid electrolyte to increase the lithium ion conductivity and the electrolyte impregnation rate, thereby improving the performance and stability of the electrochemical device using the separator. . Patent Document 1 describes an organic / inorganic composite porous separator and an electrochemical device using the same.

In order to maintain the stability of the SRS, the adhesion properties of the binder-inorganic and substrate-binder to prevent the inorganic material from falling off the surface of the polyolefin substrate is very important. Currently used binders are PVDF-based, and since the adhesive property of the binder is low, it is necessary to develop a new binder to improve stability.

PVDF-based binders have excellent adhesion with the positive electrode, but have a disadvantage of poor adhesion with the negative electrode using SBR (Styrene-Butadiene Rubber) binder. In addition, since the PVDF-based binder is hydrophobic, the wettability of the separator with respect to the electrolyte is not good, and thus the output of the battery is reduced.

At present, the SRS has a problem that it cannot cope with the dissolution of the cathode material transition metal in the high temperature / high voltage state that can occur frequently in the driving of an electric vehicle. Conventional binders do not adsorb the eluted transition metal, which causes a problem of deterioration of battery life characteristics.

In addition, since the damage of the separator due to heat and pressure is irreversible, there is a problem in that the output reduction and the safety problem of the battery due to the damaged membrane once cannot be recovered.

Various attempts have been made to introduce compounds containing hydrophilic groups in order to improve the properties of the separator. Non-Patent Document 1 is to improve the commercial PP (Polypropylene) membrane wettability characteristics of a lithium ion battery, and has developed a surface coating method of dipping a PP substrate into tannic acid, a natural vegetable polyphenyl. However, since the surface of PP is hydrophobic, tannic acid containing a large number of hydroxyl groups may not be evenly distributed on the surface of PP, and coating may not have sufficient durability in manufacturing and charging and discharging electrochemical devices using the same.

Non-Patent Document 2 is for improving the wetting properties of a PP substrate used as a separator of a lithium ion battery, and describes a method of coating using pyrogallic acid. Non-Patent Literature 2 Also, as in Non-Patent Literature 1, since pyrogallic acid has a poor physical and chemical affinity with hydrophobic PP, a uniform coating can be obtained in a short time, but in the manufacture and charging / discharging of an electrochemical device using the coating, It does not have sufficient durability and uniformity.

In Non-Patent Documents 3 to 6, a binder having a self-healing function, such as a capsule-shaped binder for improving the characteristics of a negative electrode containing silicon, is introduced. In the case of using a high-capacity silicon cathode, since a conventional PVDF is weakly bonded to silicon, a new binder has been developed to improve this problem, which is difficult to apply to a current SRS binder.

Patent Document 2 describes a technique for adding a binder film to the SRS outermost layer in order to improve the wettability of the separator. The hydrophilicity is improved due to the film of the outermost layer, but there is a problem in that the access of the pores formed by the inorganic particles and the binder is limited and thus the performance and stability of the electrochemical device cannot be found.

Patent document 3 relates to a battery separator and a nonaqueous electrolyte battery using the same, wherein the battery separator includes a resin porous membrane having a thermoplastic resin as a main component and a multilayer porous membrane having a heat resistant porous layer containing heat resistant fine particles as a main component, wherein The thickness of a heat resistant porous layer is 1-15 micrometers, and the peeling strength in 180 degrees of the said resin porous film and the said heat resistant porous layer is 0.6 N / cm or more, It is related with the battery separator.

Both this invention and patent document 3 have a common point regarding the separator of the lithium secondary battery which improved thermal safety. However, in addition to thermal stability, the binder of the present invention has an object that is never recognized in Patent Document 3, such as adhesion improvement, adsorption of a cathode material transition metal, and self-healing, and thus there is a large difference in the molecular structure of the binder. The present invention is a binder containing a large number of -O and hydroxy (OH) functional groups in the molecule, while Patent Document 3 uses a polymer or water-soluble cellulose derivative of N-vinylacetamide and a crosslinked acrylic resin as a binder. There is a difference.

On the other hand, Patent Document 3 uses xanthan gum used as a binder in the present invention as a thickener. The binder and the thickener are basically different in the amount used. In patent document 3, the composition ratio of a binder is 1.1 mass parts or more with respect to 100 mass parts of heat resistant fine particles, and the composition ratio of a thickener uses 0.1 mass part or more with respect to 100 mass parts of heat resistant fine particles. Since the composition ratio is about 10 times the difference, it can be seen that the binder and the thickener are not mutually compatible. Although this invention and patent document 3 have some similarities in using xanthan gum, since specific uses differ, it can be seen that patent document 3 does not grasp the technical characteristic of the binder used by this invention at all.

Non-Patent Document 7 is a review paper on natural materials used in an electrochemical energy storage device and describes that natural materials amylopectin, xanthan gum, and the like are used as binders. However, all of the binders of Non-Patent Document 7 differ in their use and function from those of the separator used in the present invention as binders of positive or negative electrodes. In particular, since the binder for the separator of the present invention has a completely different property from the material used in the anode or the cathode in that the separator contains an inorganic material, the technical field of the separator may be different.

As mentioned above, in order to maintain thermal stability of the SRS separator containing inorganic particles, the adhesive force of the binder-inorganic material and the substrate-binder is increased, and at the same time, the internal short circuit is prevented through self-healing function against some damage of the separator. In order to improve the adhesion between the separator and the anode and the cathode, and to cope with the elution of the transition material of the cathode material, no clear solution has been proposed.

Republic of Korea Patent Publication No. 10-0775310.

Republic of Korea Patent Publication No. 10-1535198.

Republic of Korea Patent Publication No. 2011-0031998

Lei Pan et al., "Tannic-Acid-Coated Polypropylene Membrane as a Separator for Lithium-Ion Batteries", ACS Appl. Mater. Interfaces, 7 (29), 16003-16010 (2015).

Haibin Wang et al., "Pyrogallic acid coated polypropylene membranes as separators for lithium-ion batteries", J. Mater. Chem. A, 3, 20535-20540 (2015).

S.R. White et al., "Autonomic healing of polymer composites", Nature, 409, 794-797 (2001).

Benjamin C-K Tee et al., "Pressure and flexionsensitive electronic skin with repeatable ambient self-healing capability", Nature nanotechnology, 7, 825 (2012).

Chao Want et al., "Self-healing chemistry enables the stable operation of silicon microparticle anodes for high-energy lithium-ion batteries", Nature Chemistry, 5, 1042-1048 (2013).

You Kyeong Jeong et al., "Millipede-inspired Structural Design Principles for High Performance Polysaccharide Binders in Silicon Anodes", Energy & Environmental Science, 8 1224 (2015).

Hua Wang et al., “Nature-Inspired Electrochemical Energy-Storage Materials and Devices”, Adv. Energy Materials 1601709 (2016).

The present invention is a separator comprising a porous polyolefin substrate, an organic-inorganic composite porous coating layer comprising a binder compound and inorganic particles formed on at least one surface of the substrate, while increasing the adhesive strength of the binder-inorganic, substrate-binder, A self-healing function prevents internal short-circuit in advance and improves adhesion between the separator and the positive electrode and the negative electrode, and a functional binder capable of coping with dissolution of the positive electrode material transition metal and a battery separator including the same. It aims to provide.

The first aspect of the present invention for solving the above problems is (a) a polyolefin-based substrate; And (b) an active layer wherein at least one region selected from the group consisting of a surface of the substrate and a portion of the pores present in the substrate is coated with a mixture of inorganic particles and a binder, wherein the active layer is an inorganic material by a binder. In the separator for the battery is connected and fixed between the particles, the pore structure is formed due to the interstitial volume between the inorganic particles,

The binder provides a separator for a battery in which the proportion of hydroxy groups in each molecule is 10% by weight or more.

Specific examples of the binder may be at least one or more of tannic acid, pyrogallic acid, amylose, amylopectin, xanthan gum, or 1) at least one or more of tannic acid, pyrogallic acid, amylose, amylopectin and xanthan gum. 2) polyvinylidene fluoride-co-hexafluoropropylene, polyvinylidene fluoride-co-trichloroethylene, polymethyl methacrylate (polyvinylidene fluoride-co-hexafluoropropylene) polymethylmethacrylate, polyacrylonitrile, polyvinylpyrrolidone, polyvinylacetate, ethylene vinyl acetate copolymer, polyethylene oxide, cellulose acetate cellulose acetate, cellulose acetate butyrate, cellulite Cellulose acetate propionate, cyanoethylpullulan, cyanoethylpolyvinylalcohol, cyanoethylcellulose, cyanoethylsucrose, pullulan ), A mixture with carboxyl methyl cellulose, a mixture containing at least one of acrylonitrilestyrene-butadiene copolymer and polyimide.

The inorganic particles may be at least one selected from the group consisting of inorganic particles having a dielectric constant of 5 or more, inorganic particles having piezoelectricity, and inorganic particles having lithium ion transfer ability.

The inorganic particles having a dielectric constant of 5 or more are SrTiO ₃ , SnO ₂ , CeO ₂ , MgO, NiO, CaO, ZnO, ZrO ₂ , Y ₂ O ₃ , Al ₂ O ₃ , TiO ₂ or SiC; The inorganic particles having piezoelectricity are BaTiO ₃ , Pb (Zr, Ti) O ₃ (PZT), Pb _1-x La _x Zr _1-y Ti _y O ₃ (PLZT), PB (Mg ₃ Nb ₂ / ₃ ) O ₃ -PbTiO ₃ (PMN-PT) or hafnia (HfO ₂ ); The inorganic particles having the lithium ion transfer ability are lithium phosphate (Li ₃ PO ₄ ), lithium titanium phosphate (Li _x Ti _y (PO ₄ ) ₃ , 0 <x <2, 0 <y <3), lithium aluminum titanium phosphate (Li _x Al _y Ti _z (PO ₄ ) ₃ , 0 <x <2, 0 <y <1, 0 <z <3), (LiAlTiP) _x O _y series glass (0 <x <4, 0 <y <13), lithium lanthanum titanate (Li _x La _y TiO ₃ , 0 <x <2, 0 <y <3), lithium germanium thiophosphate (Li _x Ge _y P _z S _w , 0 < x <4, 0 <y <1, 0 <z <1, 0 <w <5), Lithium Nitride (Li _x N _y , 0 <x <4, 0 <y <2), SiS ₂ (Li _x Si _y S _z , 0 <x <3, 0 <y <2, 0 <z <4) series glass or P ₂ S ₅ (Li _x P _y S _z , 0 <x <3, 0 <y <3, 0 <z <7) series glass.

Specifically, the inorganic particles may include at least one of Al ₂ O ₃ , AlOOH, and Mg (OH) ₂ .

The polyolefin-based substrate may be at least one selected from the group consisting of high density polyethylene, low density polyethylene, linear low density polyethylene, ultra high molecular weight polyethylene, and polypropylene.

A second aspect according to the present invention comprises the steps of 1) dissolving a binder in a solvent to prepare a binder solution; 2) adding and mixing the inorganic particles to the binder solution of step 1); 3) A method of manufacturing a battery separator comprising coating and drying at least one region selected from the group consisting of a surface of a polyolefin-based substrate and a part of pores in the substrate with the solution of step 2). Provided is a method for manufacturing a battery separator according to the present invention, wherein the proportion of hydroxyl groups in the molecule is 10% by weight or more.

The solvent has a mixed weight ratio of water and acetone of 100: 0 to 0: 100, preferably 95: 5 to 0: 100, more preferably 75:25 to 0: 100, even more preferably 60:40 to 0: 100. Even more preferably 50:50 to 0: 100. The most preferred range is 40:60 to 0: 100. The optimal ratio according to an embodiment of the present invention is 75:25.

According to a third aspect of the present invention, there is provided an electrochemical device including the battery separator of the present invention. In this case, the electrochemical device may be a lithium secondary battery.

1 illustrates a unit structure of Amylose, which is an embodiment of the binder of the present invention.

Figure 2 shows the unit structure of Amylopectin (Amylopectin) which is one embodiment of the binder of the present invention.

3 shows a unit structure of Xanthan Gum, which is one embodiment of the binder of the present invention.

4 illustrates hydrogen bonding between an electrode and a separator when tannic acid is used as a binder according to an embodiment of the present invention.

Figure 5 is an illustration for the improvement of the wettability according to the use of tannic acid according to an embodiment of the present invention.

6 is an illustration of the adsorption mechanism for the cathode material transition metal by hydrogen bonding.

7 is a result of comparing the shrinkage with respect to heat when using tannic acid as a binder according to an embodiment of the present invention.

8 conceptually shows the structure of an SRS to which a binder according to the present invention is applied.

Figure 9 conceptually shows the self-healing function according to the application of the binder of the present invention.

10 is a measure of the physical properties of the separator according to an embodiment of the present invention.

11 is a measure of the physical properties of the separator according to the concentration of acetone according to an embodiment of the present invention.

The present invention not only exhibits excellent thermal safety, electrochemical stability, excellent lithium ion conductivity, electrolyte impregnation rate, self-healing function, etc., compared with the polyolefin-based separators used as conventional battery separators, but also contains a large amount of hydrophilic functional groups. The present invention provides a battery separator and a method of manufacturing the same, in which a binding force of the battery-separation membrane is improved and a functional binder capable of adsorbing a transition metal eluted from the positive electrode is applied.

The present invention (a) a polyolefin-based substrate; And (b) an active layer wherein at least one region selected from the group consisting of a surface of the substrate and a portion of the pores present in the substrate is coated with a mixture of inorganic particles and a binder, wherein the active layer is an inorganic material by a binder. In the separator for the battery is connected and fixed between the particles, the pore structure is formed due to the interstitial volume between the inorganic particles,

The binder provides a separator for a battery in which the proportion of hydroxy groups in each molecule is 10% by weight or more. The proportion of hydroxy groups in each molecule is preferably 12 wt% or more and 50 wt% or less, more preferably 15 wt% or more and 45 wt% or less, even more preferably 18 wt% or more and 40 wt% or less, even more preferably Preferably it is 18 weight% or more and 38 weight% or less. When the weight ratio of the hydroxy group is less than 10% by weight, the hydrogen bonding functional group of the binder is not sufficient, and thus the desired function in the present invention is not sufficiently realized. When the weight ratio of the hydroxy group is more than 50% by weight, there may be a problem that the movement of the electrolyte is limited due to the strong hydrogen bond.

Specific examples of the binder may be at least one or more of tannic acid, pyrogallic acid, amylose, amylopectin, xanthan gum, or 1) at least one or more of tannic acid, pyrogallic acid, amylose, amylopectin and xanthan gum. 2) polyvinylidene fluoride-co-hexafluoropropylene, polyvinylidene fluoride-co-trichloroethylene, polymethylmethacryl Polymethylmethacrylate, polyacrylonitrile, polyvinylpyrrolidone, polyvinylacetate, ethylene vinyl acetate copolymer, polyethylene oxide, Cellulose acetate, cellulose acetate butyrate, Cellulose acetate propionate, cyanoethylpullulan, cyanoethylpolyvinylalcohol, cyanoethylcellulose, cyanoethylsucrose, pullulan ( It may be a mixture with a mixture comprising at least one of pullulan, carboxyl methyl cellulose, acrylonitrilestyrene-butadiene copolymer, polyimide.

As an example of a binder having a hydroxy group occupying 10% by weight or more in each binder molecule, amylose (see FIG. 1), amylopectin (see FIG. 2), xanthan gum (see FIG. 3), and tannic acid (see FIG. 4) are illustrated. OH occupies 18%, 25%, and 32% in each of amylose, amylopectin and xanthan gum. It can be seen that the specific gravity of all the hydroxy (OH) groups is 10% by weight or more and can generate strong hydrogen bonds. Herein, considered as a hydroxyl group of each molecule, an OH group is excluded and carboxyl (COOH) is excluded.

The binder according to the present invention has an advantage of excellent bonding strength for both the positive electrode and the negative electrode by the hydrophilic functional group. The binding relationship in the molecular unit about this is shown typically in FIG.

In the case of using a hydrophilic binder, the conventional PE substrate has a poor affinity for water as a hydrophobic material, but it can be seen that the result of applying the tannin acid as the binder according to the present invention changes to hydrophilicity (see FIG. 5).

On the other hand, Figure 6 shows an example of the adsorption mechanism for the positive electrode material transition metal by the binder containing a hydrophilic group according to the present invention.

The conceptual diagram of the separator according to the present invention is shown in FIG. Conventional binders do not have a large attractive force between the binder ends or the middle, but the binder according to the present invention maintains strong hydrogen bonds due to -O / -OH groups. Triangle in FIG. 8 means a hydroxy group or a hydrophilic group. Circle means inorganic particles.

Meanwhile, as shown in the left side of FIG. 9, when a part of the separator is broken and an internal short circuit occurs, a portion damaged by the internal hydrogen bond of the binder may self-heal. This prevents internal short circuits.

Hereinafter, the present invention will be described in detail. Prior to this, the terms or words used in this specification and claims should not be construed as being limited to the ordinary or dictionary meanings, and the inventors should properly introduce the concept of terms in order to best explain their own inventions. It should be interpreted as meanings and concepts in accordance with the technical spirit of the present invention based on the principle that it can be defined. Therefore, the configurations presented in the embodiments described herein are only one of the most preferred embodiments of the present invention and do not represent all of the technical ideas of the present invention, and various equivalents may be substituted for them at the time of the present application. It should be understood that there may be variations.

<Example 1> Preparation of a separator for a lithium ion battery to which a functional binder is applied.

Polyvinylidene fluoride-chlorotrifluoroethylene copolymer (PVdF-CTFE) The polymer and tannic acid (50:50 by weight) are added to acetone by about 5% by weight, and then dissolved at a temperature of 50 ° C for about 12 hours or more. A polymer solution was prepared. BaTiO ₃ powder was added to the polymer solution such that BaTiO ₃ / (PVdF-CTFE and tannic acid) = 90/10 (% by weight), and the BaTiO ₃ powder was crushed and pulverized using a ball mill method for at least 12 hours. To prepare a slurry. BaTiO ₃ particle diameter of the slurry thus prepared may be controlled according to the size (particle size) of the beads used in the ball mill method and the application time of the ball mill method, but in Example 1, the slurry was pulverized to about 400 nm. The slurry thus prepared was coated on a polyethylene separator (porosity 45%) having a thickness of about 18 μm by using a dip coating method, and the coating thickness was adjusted to about 3 μm. The pore size and porosity in the active layer coated on the polyethylene separator were 0.5 μm and 58%, respectively, as measured by a porosimeter.

<Comparison of Example 2 and Comparative Example 1> Comparison of heat shrinkage characteristics of the separator for a lithium ion battery to which the functional binder is applied (see FIG. 7).

A battery separator was manufactured in the same manner as in Example 1, but Example 2 was prepared by changing the weight ratio of the binder and the inorganic material to 15:85 in the coating composition. Comparative Example 1 was prepared under the same conditions as in Example 2, but did not use tannic acid in the binder. Comparative Examples 1 and 2 were coated with a thickness of 5 μm and 3 μm, respectively. As a result of comparing the heat shrinkage of Example 2 and Comparative Example 1 at the same 150 ℃, Example 2 according to the present invention showed excellent physical properties compared to the conventional separation membrane (Comparative Example 1) does not contain tannic acid. In particular, Comparative Example 1 exhibited poor heat shrinkage properties compared to Example 2, although the thickness of the coating was thicker. In FIG. 7, MD is a machine direction and TD is a transverse direction, respectively, and shows the length of a horizontal direction and a vertical direction, respectively. Numerical values at the top of each table indicate the MD / TD shrinkage percentage (%) before and after heat shrink.

<Examples 3, 4, 5> Comparison of Characteristics of Separation Membranes According to Hydroxy Group in Binder Molecules

Examples 3, 4 and 5 were prepared in the same manner as in Example 1. However, as the inorganic particles, alumina and boehmite were used in a 85:15 weight ratio, and a mixing ratio of the inorganic material and the binder was 75:25 weight ratio. As a binder, a binder containing PVdF-HFP: PVdF-CTFE: hydroxy group was prepared in a 22: 1: 2 weight ratio, and the solvent was 100% acetone. Xanthan gum, tannic acid, and amylose were used as the hydroxyl group-containing binder, respectively. PP was used for the polyolefin substrate.

10 is a result of comparing the physical properties of the separator according to Examples 3, 4, 5. In the specification of the present invention, the fabric means a polyolefin substrate. As the weight ratio of the hydroxyl group in the binder was increased, the adhesion between the substrate and the inorganic coating layer was increased, and the ionic conductivity was also increased. The electrical resistance of the separator did not appear to change significantly. 10 and 11, the separator / fabric interface adhesion strength is a measure of the separation strength of the inorganic coating layer and the substrate when the substrate is separated after adhering the inorganic coating layer of the SRS to the remaining surface of the double-sided tape after attaching the double-sided tape on the glass surface, Separator / electrode interface adhesion is a measure of the separation strength of the electrode and the SRS when the substrate is separated after adhering the electrode to the other side of the double-sided tape after attaching the double-sided tape on the glass surface. ER and ionic conductivity were measured by the conventional method, and the membrane Gurely was measured for air permeability, and the air permeability was measured using Toyoseiki's Gurley type Densometer (No. 158) according to Japanese Industrial Standard Gurley measurement method. Measured. In other words, air permeability refers to the time (in seconds) that 100 cc of air passes through a 1 inch square membrane under constant air pressure of 4.8 inches.

The physical properties of the separators according to Examples 3, 4, and 5 are shown in Table 1 below.

<Example 6, 7, 8, 9, 10> Comparison of physical properties according to the acetone ratio of the solvent

Examples 6, 7, 8, 9, and 10 prepared a separator by the same method as in Example 3. At this time, tannic acid was used as the binder having a hydroxyl group. In the preparation of the solvent, the weight ratio of water and acetone was 100: 0, 95: 5, 50:50, 25:75, and 0: 100, respectively. The change in physical properties according to the weight ratio of water and acetone, respectively, is shown in FIG. 11.

The best effect was obtained when the ratio of water and acetone was 25:75. Considering the permeability, electrical resistance, ionic conductivity, and interfacial adhesion, the ratio of water and acetone was in the range of 50:50 or more and 0: 100. On the other hand, since the ratio of water and acetone will affect the structure according to drying of the coating layer, the optimum point may be changed by the proportion of hydroxy groups in the binder, and considering the ratio of hydroxy groups according to the present invention, from 60:40 to It can be extended to 0: 100.

The physical properties of the separators according to Examples 6, 7, 8, 9, and 10 are described in Table 2 below.

The present invention is a separator comprising a porous polyolefin substrate, an organic-inorganic composite porous coating layer comprising a binder compound and inorganic particles formed on at least one surface of the substrate, while increasing the adhesive strength of the binder-inorganic, substrate-binder, Self-healing function prevents internal short circuits in advance for some damage to the separator, improves the adhesion between the separator and the anode and the cathode, and can cope with the elution of the transition material of the cathode material.

Claims (12)

1. (a) a polyolefin-based substrate; And

   (b) at least one region selected from the group consisting of the surface of the substrate and a portion of the pores present in the substrate comprises an active layer coated with a mixture of inorganic particles and a binder, wherein the active layer is an inorganic particle by a binder In the separator of the battery is connected and fixed between, the pore structure is formed due to the interstitial volume between the inorganic particles,

   The binder is a battery separator, wherein the proportion of hydroxyl groups in each molecule is 10% by weight or more.
2. The method of claim 1,

   The binder is a battery separator comprising at least one of tannic acid, pyrogallic acid, amylose, amylopectin, xanthan gum.
3. The method of claim 1,

   The binder comprises 1) a mixture comprising at least one of tannic acid, pyrogallic acid, amylose, amylopectin, xanthan gum and 2) polyvinylidene fluoride-co-hexafluoropropylene. , Polyvinylidene fluoride-co-trichloroethylene, polymethylmethacrylate, polyacrylonitrile, polyvinylpyrrolidone, polyvinylacetate ( polyvinylacetate, polyethylene-co-vinyl acetate, polyethylene oxide, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate ), Cyanoethylpullulan, cyanoethyl Cyanoethylpolyvinylalcohol, cyanoethylcellulose, cyanoethylsucrose, pullulan, carboxyl methyl cellulose, acrylonitrilestyrene-butadiene Battery separator which is a mixture with a mixture containing at least one or more of a copolymer, polyimide (polyimide).
4. The method of claim 1,

   The inorganic particles are at least one selected from the group consisting of inorganic particles having a dielectric constant of 5 or more, inorganic particles having piezoelectricity, and inorganic particles having lithium ion transfer ability.
5. The inorganic particle having a dielectric constant of 5 or more is SrTiO ₃ , SnO ₂ , CeO ₂ , MgO, NiO, CaO, ZnO, ZrO ₂ , Y ₂ O ₃ , Al ₂ O ₃ , TiO ₂ or SiC. ;

   The inorganic particles having piezoelectricity are BaTiO ₃ , Pb (Zr, Ti) O ₃ (PZT), Pb _1-x La _x Zr _1-y Ti _y O ₃ (PLZT), PB (Mg ₃ Nb ₂ / ₃ ) O ₃ -PbTiO ₃ (PMN-PT) or hafnia (HfO ₂ );

   The inorganic particles having a lithium ion transfer capacity include lithium phosphate (Li ₃ PO ₄ ), lithium titanium phosphate (Li _x Ti _y (PO ₄ ) ₃ , 0 <x <2, 0 <y <3), and lithium aluminum titanium phosphate (Li _x Al _y Ti _z (PO ₄ ) ₃ , 0 <x <2, 0 <y <1, 0 <z <3), (LiAlTiP) _x O _y series glass (0 <x <4, 0 <y <13), lithium lanthanum titanate (Li _x La _y TiO ₃ , 0 <x <2, 0 <y <3), lithium germanium thiophosphate (Li _x Ge _y P _z S _w , 0 <x <4 , 0 <y <1, 0 <z <1, 0 <w <5), lithium nitride (Li _x N _y , 0 <x <4, 0 <y <2), SiS ₂ (Li _x Si _y S _z , 0 <x <3, 0 <y <2, 0 <z <4) series glass or P ₂ S ₅ (Li _x P _y S _z , 0 <x <3, 0 <y <3, 0 <z <7) A separator for a battery which is a series glass.
6. The method of claim 4, wherein

   The inorganic particles are at least one of Al ₂ O ₃ , AlOOH, and Mg (OH) ₂ separator for a battery.
7. The method of claim 1,

   The polyolefin-based substrate is a battery separator for at least one selected from the group consisting of high density polyethylene, low density polyethylene, linear low density polyethylene, ultra high molecular weight polyethylene and polypropylene.
8. 1) dissolving the binder in a solvent to prepare a binder solution;

   2) adding and mixing the inorganic particles to the binder solution of step 1);

   3) A method of manufacturing a separator for a battery comprising coating and drying at least one region selected from the group consisting of a surface of a polyolefin-based substrate and a portion of pores in the substrate with the solution of step 2),

   The binder is a manufacturing method of a battery separator according to any one of claims 1 to 7, wherein the hydroxy group occupies 10% by weight or more in each molecule.
9. The method of claim 8,

   The solvent is a method of manufacturing a separator for a battery in which the mixing weight ratio of water and acetone is 50:50 to 0: 100.
10. A separator for a battery produced by the manufacturing method of claim 8.
11. An electrochemical device comprising the separator for batteries according to any one of claims 1 to 7.
12. The method of claim 11,

    The electrochemical device is a lithium secondary battery electrochemical device.

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