SEPARATOR FOR SECONDARY BATTERY AND LITHIUM SECONDARY BATTERY INCLUDING SAME

Hereinafter, one embodiment of the present invention detailed the on-sensors other. 　But, this is by way of example number so that when, the range of the present invention is defined by the present invention refers to one category number 802.11a packets not the after alcoholic beverage it will do claimed only disclosed.

In one embodiment according to secondary cell separator hereinafter described as follows.

Figure 1 shows a secondary cell separator also in one embodiment according to the show are disclosed.

With reference to the 1 also, in one implementation according to secondary cell separator (10) includes a porous substrate (20), and porous substrate (20) positioned one or two surfaces of the thermal porous layer (30) comprises.

Porous substrate (20) includes a plurality of having pores with a conventional porous can be used for electrochemical element may be used. Porous substrate (20) include non-number limited to polyethylene, polypropylene polyolefin, polyethylene terephthalate, polybutylene terephthalate such as polyester, polyacetal, polyamide, polyimide, polycarbonate, polyether ether keton, polyaryl ether ketone, polyether-imide, polyamide-imide, polybenzimidazole, polyethersulfone, poly phenyl [leyn[leyn] oxide, cyclic olefin copolymer, polyphenylene sulfide, polyethylene naphthalate, glass fiber, Teflon (tetrafluoroethylene, TEFLON), and polytetrafluoroethylene (PTFE) selected from the group consisting of at least one polymer formed from a mixture of either polymer or among these 2 main disclosed. Specifically, the porous base material (20) which includes a polyolefin it will be a record, polyolefin substrate shutdown (shut down) cathode can be money results. Polyolefin substrate e.g. polyethylene film, single layer polypropylene, polyethylene/polypropylene double film, polypropylene/polyethylene/polypropylene and polyethylene/polypropylene/polyethylene triple film triple film can be selected from the group consisting. In addition, polyolefin resin in addition to the non-olefin resin or olefin resin, olefin and a non-olefin monomers can be copolymer.

Porous substrate (20) have a thickness of about 1 micro m to 40 micro m may have, for example 1 to 30 micro m micro m, 1 m to 20 micro micro m, 5 m to 15 m micro micro, m may have a thickness of 5 to 10 micro micro m.

Heat-resistant porous layer (30) comprising the filler and binder.

Said filler such as inorganic fillers, organic filler, filler or preparation methods can be a combination of these. Said inorganic filler can be improved heat resistance can be ceramic material, for example metal oxide, metalloid oxide, metal fluoride, metal hydroxide or combinations thereof can be. Example Al said inorganic filler₂ O₃ , SiO₂ , TiO₂ , SnO₂ , CeO₂ , MgO, NiO, CaO, GaO, ZnO, ZrO₂ , Y₂ O₃ ,SrTiO₃ , BaTiO₃ , Mg (OH)₂ Or combinations thereof but, limited to are not correct. Said organic filler acryl compounds, imide compound, amide compound or combinations thereof but, limited to are not correct. Said organic filler core - shell (core-a shell) structure but, limited to are not correct.

About 1 nm to 2000 nm sized said filler may be spherical or plate-like, about 100 nm to 1000 nm in size of said range may have, about 100 nm to 500 nm within said implementation being. The implementation being girdle and have an average particle diameter or size. By using the filler size in the range of said heat porous layer (30) can be suitable for imparting strength. Said filler is different from at least one different size or is hereinafter on 2 can be mixed. Improved heat-resistance temperature abruptly contracted by said filler insertion separator can be further prevent deformation.

Said binder filler said porous substrate (20) fixed on performing serves, heat-resistant porous layer (30) of in one aspect porous substrate (20) and in other aspects (not shown) adheres well to electrode to adhere well and adhesion can be under public affairs number.

Said binder (vinylidene fluoride) vinylidene fluoride, and hexafluoropropylene (hexafluoropropylene) and at least one monomer having a carboxyl group (hereinafter 'carboxyl containing monomer' is equal to) can be obtained from the copolymer.

Said structural units derived from vinylidene fluoride copolymers, structural units derived from hexafluoropropylene and carboxylic containing monomers can be derived from structural units. The structural units derived from vinylidene fluoride, and hexafluoropropylene unit which is derived from the ratio of structural units derived from a divalent aliphatic cyclic group and carboxylic vinylidene fluoride, hexafluoropropylene and carboxylic containing monomers and supply ratio substantially the same as that thereof can.

Example (meta) acrylic acid or a derivative thereof said carboxyl monomer, (meta) acrylic with the jade city which rises acetic acid or a derivative thereof, (meta) acrylic with the jade city which rises alkyl acid or a derivative thereof, or a derivative thereof itaconic, maleic acid or a derivative thereof, their anhydrides or combinations thereof can be.

(Meta) acrylic acid or a derivative thereof said for example acrylic acid, methacrylic acid, alkyl acrylate, alkyl methacrylate, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, carboxylic alkyl acrylate, carboxylic diplopia alkyl meta [khu[khu] relay [thu[thu], acrylic with the jade hour alkyl which rises [swuk[swuk] new it buys, meta the [khu[khu] the jade hour alkyl which rises with the reel [swuk[swuk] new it buys, acrylic with the jade hour alkyl [phu[phu] mask which rises it buys, meta the [khu[khu] the jade hour alkyl [phu[phu] mask which rises with the reel it buys or combinations thereof can be. (Meta) acrylic acid or a derivative thereof said for example acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxy ethyl meta [khu[khu] relay [thu[thu], carboxylic ethyl acrylate, carboxylic diplopia ethyl meta [khu[khu] relay [thu[thu], acrylic with the jade hour ethyl which rises [swuk[swuk] new it buys, meta the [khu[khu] the jade hour ethyl which rises with the reel [swuk[swuk] new it buys, acrylic with the jade hour ethyl [phu[phu] mask which rises it buys, meta the [khu[khu] the jade hour ethyl [phu[phu] mask which rises with the reel it buys or combinations thereof can be.

3 - (meta) acrylic with the jade city which rises profile with the jade city which rises alkyl acid example said acrylic acid, 3 - new triflusal profile acid, 4 - acrylic with the jade city which rises butyric acid, 4 - can be new triflusal butyric acid or combinations thereof.

For example maleic acid or a derivative thereof said maleic anhydride (2, 5 - furan dyon), 3 - methyl - 2, 5 - furan dyon, 3 - ethyl - 2, 5 - furan dyon, 3 - propyl - 2, 5 - furan dyon, 3 - butyl - 2, 5 - furan dyon, 3 - cyclopentyl - 2, 5 - furan dyon, dyon 3 - hexyl - 2, 5 - furan, 3 - furan - 2, 5 - [heyp[heyp]dyon, dyon can be 3 - octyl - 2, 5 - furan or a combination of these.

In one example, said structural units derived from vinylidene fluoride and hexafluoropropylene copolymer is used as a main skeleton is derived from structural units derived from carboxyl containing monomer units and optionally may have distributed structure. For example, structural units are alternately distributed said alternating polymer, optionally distributed random polymer, such as a graft polymer may have the form of graft units or partially structured.

The, said said hexafluoropropylene copolymer is derived from a 10% by weight to about 4 units can be included. Said structural units derived from propylene is included in said range by heat-resistant porous layer hexafluoropropylene (30) solubility can be improved while securing in that astigmatism solvent to roadways. The controller signal is detected without using heat-resistant porous layerthat astigmatism solvent (30) can be formed, by using an aeration degrees boiling point solvent can be inevitably occurs can be prevented from being lowered. Example that astigmatism solvent having about 80 °C hereinafter may be said boiling point solvent, such as acetone, methyl ethyl ketone, ethyl isobutyl ketone, tetrahydrofuran mixable, dimethyl formaldehyde, cyclohexane can be a solvent or a combination of, limited to are not correct. For example said copolymers having solvents with a boiling point of 80 °C hereinafter, 40 °C may have a solubility of about 20 hereinafter. In said range, said hexafluoropropylene about 5 to 7% by weight of said ethylene-vinyl acetate copolymer is derived from a unit is for example can be included.

Said structural units derived from carboxyl containing monomers and about 1 to 7% by weight the copolymer can be included. Structural units derived from carboxyl containing monomers is included in said range by said porous substrate (20) and electrodes porous layer resistant (30) can be of improving adhesion. Said structural units derived from carboxyl containing monomers within said for example about 1. 5 to 5 weight % can be included.

Said structural units derived from vinylidene fluoride and hexafluoropropylene units the structural units derived from carboxyl containing monomers is derived from said external grudge content number can be, for example about 83 to 95 weight % can be included. Within said example 88 to 93. 5% by weight can be included.

In one example, hexafluoropropylene said structural units derived from carboxyl containing monomer is derived from said unit is equal to or can be outputs. For example said hexafluoropropylene copolymer is derived from a carboxyl containing monomer units derived from said said structural units can be about 1:1 to 4:1 for example the weight ratio. Said carboxyl containing monomer units derived from hexafluoropropylene is derived from said ratio by said structural units is included in the heat resistant porous layer (30) can be of the same time as the function of adhesion to the electrodes.

Said copolymer may have a weight average molecular weight of about 800, 000g/mol to 1,500,000g/mol, within said weight average molecular weight of about 800, 000g/mol to 1,200,000g/mol may have. Said heat comprising a copolymer has an average molecular weight by weight ranging by porous layer (30) can be ensure adhesion.

A total content of at least 50% by weight of said copolymer and said filler at an said filler can be. By securing heat resistance by said range included can be modified by a temperature rise in the separator prevent. For example about 50 to 99% by weight and said filler within said be included with the, for example about 60 to 95% by weight and within said be included with the, for example about 70 to 90% by weight can be included within said.

In addition to said copolymer further comprises at least one binder 1 species or 2 said binder can be.

Said binder further comprises a crosslinked structure can be for example a crosslinked binder.

In response to heat and/or cross-linking binder curable functionality monomer, oligomer and/or polymer can be obtained from, for example at least 2 curable functionality of a polyfunctional monomer, a polyfunctional oligomers and/or polyfunctional polymer can be obtained from. For example crosslinked binder 2 30 may have two atoms curable functional groups, said curable functional groups of atoms within 2 20 may have, within the range 3 15 atoms of said curable functional groups may have.

Said curable functional groups are vinyl group, (meta) acrylic the [ley[ley] sprouting,, epoxy, oxetane group, ether group, cyano four sprouting,, ISO at the time of knows sprouting,, hydroxy, carboxyl group, molecular weight, amino group, alkoxy or combinations thereof but, limited to are not correct.

In one example, at least 2 crosslinked binder of vinyl, a (meta) acrylate, epoxy, oxetane group, ether group, cyano four sprouting,, ISO at the time of knows sprouting,, hydroxy, carboxyl group, molecular weight, amino group, alkoxy group or a combination thereof including monomer, oligomers and/or polymers can be obtained from.

In one example, crosslinked binder of (meta) acrylate group having at least 2 monomer, oligomer and/or polymer can be produced by curing, such as ethylene glycol di (meth) acrylate, propylene glycol di (meta) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butanediol di (meta) acrylate, hexamethylene glycol di (meta) acrylate, (meta) acrylate trimethylolpropane tree, glycerin tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, (meth) acrylate or a combination thereof d glycerin process can be achieved by curing.

In one example, at least 2 epoxy groups in a cross-linked binder having monomer, oligomer and/or polymer can be produced by curing, for example bisphenol A ether, ether bisphenol F, hexahydrophthalic acid glycidyl ester or a combination thereof can be achieved by curing.

In one example, cross-linked binder having at least 2 isocyanate group of monomer, oligomer and/or polymer can be produced by curing, for example diphenylmethane diisocyanates, 1, 6 - hexamethylene diisocyanate, 2, 2, 4 (2, 2, 4) - trimethyl hexamethylene diisocyanate, phenylene diisocyanate, 4, 4 '- claw between D [heyk[heyk] thread methane diisocyanate, 3, 3' - dimethyl diphenyl - 4, 4' - diisocyanate, xylene diisocyanate, naphthalene diisocyanate, 1, 4 - cyclohexyl diisocyanate or a combination thereof can be achieved by curing.

Weight average molecular weight of crosslinked binder 50g/mol to 80, 000g/mol may have, within said weight average molecular weight of 100g/mol to 60, 000g/mol may have. Said cross-linkable binder has an average molecular weight by weight ranging by heat resistance can be secured.

For example non-crosslinked binder can be further comprises said binder.

Said non-crosslinked binder such as polyvinylidene fluoride (PVdF) homopolymer, or copolymer of vinylidene fluoride and hexafluoropropylene (PVdF non-HFP) polyvinylidene - polymer, polymethylmethacrylate, polyacrylonitrile, polyvinyl pyrrolidone, polyvinyl acetate, polyethylene - vinyl acetate copolymer, polyethylene oxide, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, cyano roh ethyl grass base column (cyanoethylpullulan), cyano roh ethyl pulley vinyl alcohol, cyano roh ethyl cellulose, cyano roh ethyl possibility crow five [su[su], or jellies (pullulan), carboxymethylcellulose, acrylonitrile - styrene - butadiene copolymer or combinations thereof can be a, limited to are not correct.

Heat-resistant porous layer (30) is about 0. 01 micro m to 20 micro m may have a thickness of, about 1 micro m to 10 micro m may have a thickness of said range, said range in thickness of about 1 to 5 micro m micro m may have.

Secondary cell separator e.g. porous substrate (20) woven porous layer alcohol film can be heat formed and then dried.

Said heat-resistant porous layer composition the aforementioned binder, filler and a solvent aforementioned can be. Said solvent comprises the above-described binder and solubilizing or dispersing the aforementioned filler if a specifically defined uninhabitable. For example the low-boiling solvent having the boiling point of said solvent 80 °C hereinafter can be, for example acetone, methyl ethyl ketone, ethyl isobutyl ketone, tetrahydrofuran mixable, dimethyl formaldehyde, cyclohexane can be a solvent or a combination of, limited to are not correct.

Said application such as spin coating, dip coating, bar coating, die coating, slit coating, roll coating, such as inkjet printing can be a, limited to are not correct.

Said drying such as air drying, hot air, hot air or low humidity air by drying, vacuum drying, far infrared, but method such as electron beam irradiation can be carried out, is not limited. Drying can be carried out at a temperature of 25 to 120 said example.

Secondary cell separator in addition to the aforementioned method, e.g. lamination (lamination), coextrusion method (coextrusion) number of the bath can also be disclosed.

Hereinafter the aforementioned secondary battery including lithium secondary battery is described as follows.

Depending on the type of electrolyte separator using lithium secondary battery has the lithium ion battery, lithium ion polymer battery and lithium polymer battery or the like can be classification, according to cylindrical, square-shaped, coin-shaped, pouch-type or the like can be classification, size bulk type thin film type according sites disclosed. These electric cell and this manufacturing method is widely known in the field description dispensed to each other.

Here a prismatic lithium secondary battery as one example of lithium secondary battery is illustratively described as follows.

Figure 2 shows a decomposition of the lithium secondary battery according to sensors mounted thereon also in one implementation are disclosed.

The reference 2 also, in one implementation according to lithium secondary battery (100) comprises a positive electrode (40) and a cathode (50) between a separator (10) is attached with a it became [kwin[kwin] electrode assembly (60) and the electrode assembly (60) incorporating the case (70) having a predetermined wavelength.

Electrode assembly (60) the susceptor includes a separator (10) through a positive electrode (40) and a cathode (50) formed jelly roll layering (jelly roll) may be in the form disclosed.

Anode (40), cathode (50) and separators (10) (not shown) to electrolyte is impregnated disclosed.

Anode (40) has an anode current collector and said anode cathode active material layer formed on the anode current collector can be. qualitative layer said positive active material for lithium secondary battery, binder and optionally comprising a conductive material can be.

Said anode current collector of aluminium (Al), nickel (Ni) etc. but, is not limited.

Said positive electrode active material include lithium reversibly intercalation and calais which is a D [syen[syen] this compounds can be possible. Specifically cobalt, manganese, nickel, aluminum, iron or combinations of those metal lithium composite oxide or composite phosphate 1 can be one or more than species in cargo. More specifically, lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, lithium iron phosphate cargo or a combination thereof can be used.

Said binder as well as a positive electrode active material particles don't be attached to the anode current collector adheres well to serve as an anode active material, specific examples include polyvinyl alcohol, carboxymethylcellulose, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylic it became luck misfire polyvinyl chloride, poly the vinyl [phul[phul] base come the id, ethylene oxide-containing polymer, polyvinyl pyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene - butadiene rubber, upper part of a styrene - butadiene rubber acrylic, epoxy resin, nylon is provided to be used, is not limited. 2 alone or they can be mixed at least one.

Said conductive material is a conductive electrode imparting, and vertically moving the natural graphite, artificial graphite, carbon black, carbon fiber, metal powder, metal fiber is provided to be used, is not limited. 2 alone or they can be mixed at least one. Said metal powder and said metal fiber has a copper, nickel, aluminum, the like can be used.

Cathode (50) the cathode current collector and said cathode current collector cathode can be formed on the cathode active material layer.

Said cathode current collector has a copper (Cu), gold (Au), nickel (Ni), copper alloy etc. but, is not limited.

Said negative electrode active material for negative electrode active material qualitative layer, binder and optionally comprising a conductive material can be.

Said anode active material include lithium ions reversibly intercalation and calais which is a D will do [syen[syen] substance, lithium metal, lithium metal alloy, lithium dope and also the mask will do the [phu[phu] substance, can be using transition metal oxide or combinations thereof.

Said lithium ions reversibly intercalation and calais which is a D will do [syen[syen] title and the carbon-containing substance is cited, examples thereof amorphous carbon, amorphous carbon or a combination thereof is cited. Examples of said amorphous carbon is amorphous, plate, scale-like (flake), natural graphite or artificial graphite spherical or fiber-type is cited. Examples of soft carbon or hard carbon (hard carbon) (soft carbon) said amorphous carbon, carbide battery negative electrode material, mixture of calcined coke or the like is cited. Said lithium lithium metal alloy include Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, Ra, Ge, composed of a metal selected from the group consisting Al and Sn can be produced. Said also the mask will do the [phu[phu] dope and lithium substance include Si, SiO_x (0<x<2), Si-a C composite, Si a-Y alloy, Sn, SnO₂ , Sn-a C composite, such as Sn-a Y cited, in addition at least one of these and SiO₂ Mixed a disapproval. Said element Y include Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Tc, Re, Bh, Fe, Pb, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, Tl, Ge, P, As, Sb, Bi, S, Se, Te, and the film can be selected from the group consisting Po. Said transition metal oxide include vanadium oxide, lithium vanadium oxide or the like as is cited.

Said conductive material with a binder which processed the kind of binder used in the aforementioned anode such as conductive material thereof can.

Anode (40) and a cathode (50) selectively conductive material incorporated in each active material and binder solvent each active material composition number and high pressure liquid coolant, said active material composition can be applied to a number each collector high pressure liquid coolant. the solvent is N - methylpyrrolidone etc. but, is not limited. The present invention relates to the field of widely known such electrode number bath method is a detailed specification description it is dispensed the on-sensors other.

Separator (10) is the aforementioned efined.

Said electrolyte comprising a lithium salt in an organic solvent.

The electrochemical reaction of said organic solvent is involved in medium can move the ions could be bonded each other. Its specific examples, carbonate-based solvent, ester-based solvent, ether-based solvent, ketone-based solvent, alcohol solvent and aprotic solvent can be selected.

Said organic solvent e.g. carbonate-based, ester-based, ether-based, ketone-based, alcohol or aprotic solvent can be used. Dimethyl carbonate (DMC) said carbonate-based solvent, diethyl carbonate (DEC), dipropyl carbonate (DPC), methyl propyl carbonate (MPC), (EPC) ethyl propyl carbonate, methyl ethyl carbonate (MEC), ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC) can be is used as the alkali, said ester-based solvent methyl acetate, ethyl acetate, n - propyl acetate, 1, 1 - dimethyl ethyl acetate, methyl propionate, ethyl propionate, γ - butyrolactone, the car it is yellow the id (decanolide), ballet with [lak[lak] ton, roh maul manifestation [lak[lak] ton (mevalonolactone), is used as the polycaprolactone (caprolactone) can be. Said ether solvent dibutyl ether, tetra glycol Lyme, being a D writing,, d maul [thok[thok] hour ethane, 2 - methyl tetra draw [phyu[phyu] column, is used as the tetra draw [phyu[phyu] column can be, said ketone-based solvent can be cyclohexanone is used as the alkali. In addition said alcohol solvent ethyl alcohol, isopropyl alcohol can be used, said aprotic solvent R a-CN(R is C2 to C20 linear, branched or ring structure hydrocarbon group, an aromatic ring double bonds can be bond or ether) amides such as dimethyl formamide such as nitrile current, 1, 3 - dioxolane d jade brush turbulent flow sulfonyl such as cancer (sulfolane) or the like can be used.

Said at least one organic solvent can be either alone or by weight of 2, 2 by weight of at least one battery when desired according to the blending ratio of the performance can be properly controlled.

Said lithium salt is dissolved in an organic solvent, in the underlying source of lithium ions in the cell of a lithium secondary battery supported at and acting, between cathode and anode and the material that promoting the movement of lithium ions. Said examples lithium salt, LiPF₆ , LiBF₄ , LiSbF₆ , LiAsF₆ , LiN (SO₃ C₂ F₅ )₂ , LiN (CF₃ SO₂ )₂ , LiC₄ F₉ SO₃ , LiClO₄ , LiAlO₂ , LiAlCl₄ , LiN (C_x F_{2x + 1} SO₂ ) (C_y F_{2y + 1} SO₂ ) (X and y is natural number), LiCl, LiI, LiB (C₂ O₄ )₂ Or a combination thereof including but, limited to are not correct.

Said lithium salt concentration 0. 1M to 2. 0M range can be use in. When said lithium salt concentration range, suitable electrolytic solution excellent in performance in the periphery of the electrolyte conductivity and viscosity may be, lithium ions can be effectively.

The aforementioned separator including lithium secondary battery has 4. 2V or more can be high voltage operating, the capacity lithium secondary battery without degradation of the life can be implementing.

Hereinafter, in the embodiment of the present invention sides more specifically described above through the substrate. But, in the embodiment of the present invention to form a number range which is described only for purposes of relayed are not correct.

Synthesis of copolymer

Synthesis example 1

1L desalinated water 1295g autoclave reactor, methylcellulose 0. 75g, chemical profile 4. 0g, vinylidene fluoride (VDF) 467. 8g, hexafluoropropylene (HFP) 24. 8g, acrylic acid (AA) 7. 4g which can be, 28 °C 60 in time his suspension polymerization. After completion of the polymerization, suspension polymer slurry dewatering degassing processing, after flushing and dehydration, 80 °C 24 hours in an oven drying copolymer are obtained.

Min 1,120,000g/mol obtained copolymer a weight average molecular weight.

Synthesis example 2

1L desalinated water 1295g autoclave reactor, methylcellulose 0. 75g, chemical profile 4. 0g, vinylidene fluoride (VDF) 457. 6g, hexafluoropropylene (HFP) 32. 5g, methacrylic acid (MAA) 9. 90g which can be, 28 °C 60 in time his suspension polymerization. After completion of the polymerization, suspension polymer slurry dewatering degassing processing, after flushing and dehydration, 80 °C 24 hours in an oven drying copolymer are obtained.

Min 1,140,000g/mol obtained copolymer a weight average molecular weight.

Synthesis example 3

1L desalinated water 1295g autoclave reactor, methylcellulose 0. 75g, chemical profile 4. 0g, vinylidene fluoride (VDF) 465. 0g, and hexafluoropropylene (HFP) 25. 0g, hydroxyethyl acrylate (HEA) 10. 0g which can be, 28 °C 60 in time his suspension polymerization. After completion of the polymerization, suspension polymer slurry dewatering degassing processing, after flushing and dehydration, 80 °C 24 hours in an oven drying copolymer are obtained.

Min 1,115,000g/mol obtained copolymer a weight average molecular weight.

Synthesis example 4

1L desalinated water 1295g autoclave reactor, methylcellulose 0. 75g, chemical profile 4. 0g, vinylidene fluoride (VDF) 455. 0g, and hexafluoropropylene (HFP) 30. 0g, hydroxy ethyl meta [khu[khu] relay [thu[thu] (HEMA) 15. 0g which can be, 28 °C 60 in time his suspension polymerization. After completion of the polymerization, suspension polymer slurry dewatering degassing processing, after flushing and dehydration, 80 °C 24 hours in an oven drying copolymer are obtained.

Min 1,110,000g/mol obtained copolymer a weight average molecular weight.

Synthesis example 5

1L desalinated water 1295g autoclave reactor, methylcellulose 0. 75g, chemical profile 4. 0g, vinylidene fluoride (VDF) 465. 0g, and hexafluoropropylene (HFP) 25. 0g, hydroxypropyl acrylate (HPA) 10. 0g which can be, 28 °C 60 in time his suspension polymerization. After completion of the polymerization, suspension polymer slurry dewatering degassing processing, after flushing and dehydration, 80 °C 24 hours in an oven drying copolymer are obtained.

Min 1,105,000g/mol obtained copolymer a weight average molecular weight.

Synthesis example 6

1L desalinated water 1295g autoclave reactor, methylcellulose 0. 75g, chemical profile 4. 0g, vinylidene fluoride (VDF) 450. 0g, and hexafluoropropylene (HFP) 35. 0g, hydroxy butyl acrylate (HBA) 15. 0g which can be, 28 °C 60 in time his suspension polymerization. After completion of the polymerization, suspension polymer slurry dewatering degassing processing, after flushing and dehydration, 80 °C 24 hours in an oven drying copolymer are obtained.

Min 1,103,000g/mol obtained copolymer a weight average molecular weight.

Comparison synthetic example 1

Polyvinylidene fluoride polymer (KF-a 9300, Kureha) was prepared.

Comparison synthetic example 2

1L desalinated water 1295g autoclave reactor, methylcellulose 0. 75g, chemical profile 4. 0g, vinylidene fluoride (VDF) 445. 0g, and hexafluoropropylene (HFP) 15. 0g, acrylic acid (AA) which can be 40g, 28 °C 60 in time his suspension polymerization. After completion of the polymerization, suspension polymer slurry dewatering degassing processing, after flushing and dehydration, 80 °C 24 hours in an oven drying copolymer are obtained.

Weight average molecular weight of about 100 g/mol obtained copolymer only min.

Comparison synthetic example 3

1L desalinated water 1295g autoclave reactor, methylcellulose 0. 75g, chemical profile 4. 0g, vinylidene fluoride (VDF) 437. 5g, hexafluoropropylene (HFP) 12. 0g, acrylic acid (AA) 0. 5g which can be, 28 °C 60 in time his suspension polymerization. After completion of the polymerization, suspension polymer slurry dewatering degassing processing, after flushing and dehydration, 80 °C 24 hours in an oven drying copolymer are obtained.

Min only about 80 g/mol obtained copolymer a weight average molecular weight.

Evaluation 1

Synthesis example 1 to 3 according to copolymer 1 to 6 synthetic example compared with controlling, intrinsic viscosity (η) melting point (Tm) and table 1 is such as disclosed.

Differential scanning calorimetry (DSC) have melting point is measured, the capillary viscosity measuring method using an intrinsic viscosity with right bell five [tu[tu] granular were measured.

Evaluation 2

Synthesis example synthetic examplesin that astigmatism solvent according to copolymer compared with solubility was assessed.

To 10% by weight acetone solubility compared with synthetic example in that astigmatism solventsynthetic examples according to copolymer in a concentration of 120 minutes mixing in 45 °C been rapidly, to it did and determines whether there is a cosmetic gel was assessed.

Table 2 result such as disclosed.

The reference table 2, synthesis examples according to well dissolved acetone it is that astigmatism solvent copolymer is present and closes the comparison according to copolymer gel cosmetic it did andsynthetic example cosmetic it did and gel can verify the presence a large amount. Examples speaker according to high solubility in acetone copolymers can be confirmed.

Separator Number bath

In the embodiment 1 - 1

Synthesis example 1 according to copolymer, alumina (LS235A, KBM provided 503) and acetone was the mouldable composition by mixing. 10% by weight alumina weight ratio 1:2 copolymer composition of 90% by weight acetone on high solids without using a tool.

7 micro m thickness polyethylene substrate (SK innovation co.) after 20 seconds in dip coating composition to said high pressure liquid coolant separator 80 °C drying his number.

In the embodiment 1 - 2

Copolymer and 1:4 weight ratio in the range of 0.1 and alumina in the embodiment 1 - 1 was prepared the same method number under the outside number separator composition consists of high pressure liquid coolant.

In the embodiment 1 - 3

Copolymer and the weight ratio in the range of 0.1 and 1:5 alumina composition consists of the same method in the embodiment 1 - 1 was prepared number number under the outside separator high pressure liquid coolant.

In the embodiment 1 - 4

Copolymer and the weight ratio in the range of 0.1 and 1:7 alumina composition consists of the same method in the embodiment 1 - 1 was prepared number number under the outside separator high pressure liquid coolant.

In the embodiment 2 - 1

Synthesis example 1 according to copolymer instead in the embodiment 1 - 1 in the range of 0.1 and 2 according to the same method number under the outside synthesis example copolymer composition consists of high pressure liquid coolant separator number was prepared.

In the embodiment 2 - 2

Copolymer and 1:4 weight ratio in the range of 0.1 in the embodiment 2 - 1 alumina composition consists of the same number and high pressure liquid coolant separator was prepared under the outside method number.

In the embodiment 2 - 3

Copolymer and the weight ratio in the range of 0.1 and 1:5 alumina composition consists of the same method in the embodiment 2 - 1 was prepared number number under the outside separator high pressure liquid coolant.

In the embodiment 2 - 4

Copolymer and the weight ratio in the range of 0.1 and 1:7 alumina composition consists of the same method in the embodiment 2 - 1 was prepared number number under the outside separator high pressure liquid coolant.

In the embodiment 3 - 1

Synthesis example 3 according to synthesis example 1 according to copolymer instead of in the range of 0.1 and number the same method in the embodiment 1 - 1 copolymer prepared under the outside separator high pressure liquid coolant composition consists of his number.

In the embodiment 3 - 2

Copolymer and 1:4 weight ratio in the range of 0.1 in the embodiment 3 - 1 alumina composition consists of the same number and high pressure liquid coolant separator was prepared under the outside method number.

In the embodiment 3 - 3

The weight ratio in the range of 0.1 in the embodiment 3 - 1 copolymer alumina 1:5 under the outside number and the same method to prepare and high pressure liquid coolant separator composition consists of his number.

In the embodiment 3 - 4

Copolymer and the weight ratio in the range of 0.1 and 1:7 alumina composition consists of the same method in the embodiment 3 - 1 was prepared number number under the outside separator high pressure liquid coolant.

In the embodiment 4 - 1

Synthesis example 1 according to copolymer instead in the embodiment 1 - 1 in the range of 0.1 and the same method number under the outside synthesis example 4 according to copolymer composition consists of high pressure liquid coolant separator number was prepared.

In the embodiment 4 - 2

Copolymer and 1:4 weight ratio in the range of 0.1 in the embodiment 4 - 1 alumina composition consists of the same number and high pressure liquid coolant separator was prepared under the outside method number.

In the embodiment 4 - 3

Copolymer and the weight ratio in the range of 0.1 and 1:5 alumina composition consists of the same number in the embodiment 4 - 1 was prepared under the outside method number separator high pressure liquid coolant.

In the embodiment 4 - 4

Copolymer and the weight ratio in the range of 0.1 and 1:7 alumina composition consists of the same number in the embodiment 4 - 1 was prepared under the outside method number separator high pressure liquid coolant.

In the embodiment 5 - 1

Synthesis example 1 according to copolymer instead in the embodiment 1 - 1 in the range of 0.1 and 5 according to the same method number under the outside synthesis example copolymer prepared separator high pressure liquid coolant composition consists of his number.

In the embodiment 5 - 2

Copolymer and 1:4 weight ratio in the range of 0.1 in the embodiment 5 - 1 alumina composition consists of the same number and high pressure liquid coolant separator was prepared under the outside method number.

In the embodiment 5 - 3

Copolymer and the weight ratio in the range of 0.1 and 1:5 alumina in the embodiment 5 - 1 was prepared the same method number under the outside number separator composition consists of high pressure liquid coolant.

In the embodiment 5 - 4

Copolymer and the weight ratio in the range of 0.1 and 1:7 alumina composition consists of the same number in the embodiment 5 - 1 was prepared under the outside method number separator high pressure liquid coolant.

In the embodiment 6 - 1

Synthesis example 1 according to copolymer instead in the embodiment 1 - 1 in the range of 0.1 and 6 according to the same method under the outside copolymer synthesis example number number separator was prepared composition consists of high pressure liquid coolant.

In the embodiment 6 - 2

Copolymer and 1:4 weight ratio in the range of 0.1 in the embodiment 6 - 1 alumina composition consists of the same number and high pressure liquid coolant separator was prepared under the outside method number.

In the embodiment 6 - 3

The weight ratio in the range of 0.1 in the embodiment 6 - 1 copolymer alumina 1:5 under the outside number and the same method to prepare and high pressure liquid coolant separator composition consists of his number.

In the embodiment 6 - 4

The weight ratio in the range of 0.1 in the embodiment 6 - 1 copolymer alumina 1:7 under the outside composition consists of the same number and method number was prepared separator high pressure liquid coolant.

Comparison example 1 - 1

Synthesis example 1 according to copolymer instead in the embodiment 1 - 1 in the range of 0.1 and 1 according to the same method number under the outside comparison synthetic example polymer composition consists of high pressure liquid coolant separator number was prepared.

Comparison example 1 - 2

Polymer and alumina 1:4 weight ratio in the range of 0.1 under the outside example number 1 - 1 compares the same method to prepare and high pressure liquid coolant separator composition consists of his number.

Comparison example 1 - 3

Polymer weight ratio in the range of 0.1 example 1:5 alumina under the outside number 1 - 1 compares the same method to prepare and high pressure liquid coolant separator composition consists of his number.

Comparison example 1 - 4

Polymer weight ratio in the range of 0.1 number under the outside 1:7 alumina and compares the same method number was prepared separator high pressure liquid coolant composition consists of example 1 - 1.

Comparison example 2 - 1

Synthesis example 1 according to copolymer instead of in the range of 0.1 and 2 according to the same method in the embodiment 1 - 1 under the outside number comparison synthetic example copolymer composition consists of high pressure liquid coolant separator number was prepared.

Comparison example 3 - 1

Synthesis example 1 according to copolymer instead in the embodiment 1 - 1 in the range of 0.1 and 3 according to the same method number under the outside comparison synthetic example copolymer composition consists of high pressure liquid coolant separator number was prepared.

Evaluation 3

In the embodiment embodiments number prepared by the separator air permeability compared was assessed.

The breathable involves the following method was assessed.

Each separator 1 diameter put in the water at the point of two different sized won entrance guide vane 10 a pro base ball 10 then number of sample work grudge, ventilation measuring device using said each sample (asahitax nose yarn) 100 cc air pass time were measured. Each time said measured average value so that the wafer can then was observed every five vent road. Breathable air through filters for a larger signal from breathable smaller time is longer. The result table 3 such as disclosed.

Evaluation 4

Lithium secondary battery such as a lithium secondary battery separator high pressure liquid coolant the insect it discharged method number after adhesion, capacity retention rate and variable ratio of thickness was assessed.

LiCoO₂ , N - methylpyrrolidone (NMP) solvent 96:2:2 polyvinylidene and carbon black weight ratio number was high pressure liquid coolant is added to the slurry. Said aluminum thin film coating and drying by rolling a number anode slurry (Al) was high pressure liquid coolant.

Graphite, 98:1:1 N - methylpyrrolidone (NMP) solvent weight ratio polyvinylidene and carbon black slurry was high pressure liquid coolant is added to the number. Said slurry copper foil (Cu foil) was applied and drying by rolling a number cathode high pressure liquid coolant.

The electrolyte comprises ethylene carbonate (EC), ethyl methyl carbonate (EMC) and diethyl carbonate (DEC) mixed solvent mixed at a volumetric ratio of 3:5:2 a 1. 15M of LiPF₆ By adding, electrolyte number was high pressure liquid coolant.

In the embodiment according to comparison examples via an anode and a cathode prepared by the number of strip-like electrodes and separator assembly Royal jelly roll. Then case said electrode assembly is used to fix said lithium secondary battery was high pressure liquid coolant injecting an electrolyte and sealing number.

(1) adhesion evaluation

0 lithium rechargeable battery is inserted. 2C charging 0. 2C discharge 0. 5C the insect it discharged charging condition after the anode, separator and cathode for disassembling the him. Then the separator surface to form a cathode electrode measuring area and a separator layer is assessed. The speed of the transfer area of the total surface of the adhesion of the electrode between the electrode and a separator was assessed as a percentage. The result table 3 such as disclosed.

(2) variable ratio of thickness

0 lithium rechargeable battery. 7C conditions after 500 times the insect it discharged anode, separator and cathode for disassembling the him. Then measure the initial thickness and thickness as compared to the rate of change of charge before the separator was assessed as a percentage. The result table 3 such as disclosed.

(3) capacity retention

0 lithium rechargeable battery. 7C conditions the insect it discharged capacity retention rate after 500 times was assessed.

The result table 3 such as disclosed.

* Polyethylene based ventilation also: 150 seconds

With reference to the table 3, in the embodiment according to separator according to comparison examples are excellent air permeability compared to the separator, the separator in the embodiment according to comparison examples using the lithium secondary battery using the lithium secondary battery according to separator compared to adhesion of charge, variable ratio of thickness and good capacity retention can be confirmed.

Of the present invention preferred embodiment of the present invention detailed above for the SFC but not limited to rights range and then basic general outline of the present invention defined in the claims of which using one skilled in addition of the present invention in a range of various modified and improved form rights are disclosed.