CN103724951A - Polyester porous diaphragm for secondary lithium battery and preparation method of polyester porous diaphragm - Google Patents
Polyester porous diaphragm for secondary lithium battery and preparation method of polyester porous diaphragm Download PDFInfo
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- CN103724951A CN103724951A CN201310740610.0A CN201310740610A CN103724951A CN 103724951 A CN103724951 A CN 103724951A CN 201310740610 A CN201310740610 A CN 201310740610A CN 103724951 A CN103724951 A CN 103724951A
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Abstract
The invention discloses a polyester porous diaphragm for a secondary lithium battery. The polyester porous diaphragm is characterized by consisting of the following components in percentage by mass: 40-79 percent of polymer A, 15-30 percent of polymer B, 5-15 percent of a compatilizer and 1-15 percent of a pore-forming agent, wherein the thickness of the diaphragm is 0.01-0.05mm. The method for preparing the diaphragm comprises the following steps: uniformly mixing the polymer A, the polymer B, the compatilizer and the pore-forming agent, melting, mixing and granulating through a double-screw extruder, drying, performing melt extrusion through a single screw extruder, performing cold blast casting, longitudinally stretching for 2-8 times at the temperature of 80-150 DEG C, synchronously and longitudinally stretching for 2-6 times and transversely stretching for 1.5-8 times at the temperature of 80-150 DEG C, performing heat setting treatment, and preparing the polyester porous diaphragm. The polyester porous diaphragm has excellent mechanical strength, heat shrinkable property and closure characteristics, can be used for production and manufacture of the secondary lithium battery and is particularly suitable for the secondary lithium battery which works at the temperature of over 160 DEG C.
Description
Technical field
The invention belongs to barrier film and preparation thereof for lithium cell, relate to polyester micro-pore septum and preparation method thereof for a kind of serondary lithium battery.Polyester micro-pore septum of the present invention is applicable to the manufacturing of serondary lithium battery, is particularly useful as the serondary lithium battery polyester micro-pore septum in 160 ℃ of above work of temperature.
Background technology
In prior art, the diaphragm material that is applied in lithium cell aspect mainly contains polypropylene, polyethylene, polyimide, polyvinylidene difluoride (PVDF), is generally single or multiple lift film, and its processing method mainly adopts is two kinds of dry method and wet methods.Adopting polypropylene, the individual layer of polyethylene kind material or the closing temperature of laminated diaphragm of dry process is 130 ℃～160 ℃, is difficult to guarantee the safety of lithium cell in more than 160 ℃ individual work situation; Because it surpasses more than 15% at more than 150 ℃ percent thermal shrinkage, very easily cause electrode plates to expose and short circuit; And adopting dry method unilateral stretching technique longitudinal tensile strength can reach 150MPa, transverse tensile strength is but less than 15MPa; The ventilation property of room temperature lower diaphragm plate is in 500s/100mL left and right, along with lithium cell temperature is elevated to 160 ℃ of closures of barrier film micropores above, the air penetrability of this type of barrier film can decline rapidly, and passing through of obstacle electrolyte ion, has a strong impact on the safe handling of lithium cell and the charge and discharge process under hot conditions.As patent EP1-942-000A1 discloses a kind of multi-layer cell barrier film, it is the porous-film being formed by polyvinyl resin layer and acrylic resin layer.Although good physical strength, percent thermal shrinkage, closing temperature and temperature of fusion under normal temperature, in battery use procedure, temperature ion when reaching 160 ℃ of left and right is very large by the degradation of barrier film, has had a strong impact on the charge and discharge process of battery.CN103097440A discloses the micro-pore septum of a kind of thickness≤19.0 μ m, the micro-pore septum being formed by the polyvinyl resin of two kinds of different molecular weights, its basic craft course is after two kinds of different molecular weights and the polyvinyl resin melting film extrusion that contains pore former (this patent claims " thinner "), to stretch for the first time, after removing pore former, to stretch for the second time and make polyethylene micropore separator product.This production technique is only suitable for producing thinner polyethylene micropore separator product, and wherein the content of thinner is larger on the ventilation property impact of barrier film, and complete processing is had relatively high expectations.
Summary of the invention
Object of the present invention is intended to overcome above-mentioned deficiency of the prior art, and polyester micro-pore septum and preparation method thereof for a kind of serondary lithium battery is provided.The present invention is directed to that existing polyolefins barrier film percent thermal shrinkage under more than 160 ℃ condition is high, degradation is not enough under ventilation property, what a kind of individual layer was provided take polyester material as body material, and more than 160 ℃ can meet polyester micro-pore septum and preparation method thereof for serondary lithium battery of the normal trouble-free service of lithium cell.
Content of the present invention is: serondary lithium battery polyester micro-pore septum, it is characterized in that: this barrier film is comprised of mass percent and the component of 40～79% polymer A, 15～30% polymer B, 5～15% compatilizers and 1～15% pore former, membrane thicknesses is 0.01～0.05mm.
Described polymer A is one or more the mixture in polyethylene terephthalate (be called for short PET), polybutylene terephthalate (being called for short PBT), Poly(Trimethylene Terephthalate) (being called for short PTT).
Described polymer B is polyhexamethylene sebacamide (being called for short PA610), polycaprolactam (being called for short PA6), polyhexamethylene adipamide (being called for short PA66), nylon 1010 (being called for short PA1010), poly-11 lactan (being called for short PA11), nylon 12 (being called for short PA12), poly-12-1,12-bis-acyl hexanediamines (be called for short PA612), polyenanthoamide (being called for short PA7), poly-13 lactan (being called for short PA13), and any in bisphenol A polycarbonate (being called for short PC) and poly(4-methyl-1-pentene) (abbreviation PMP).Also can be other polymeric amide (being called for short PA).Preferred polyhexamethylene sebacamide (being called for short PA610), polycaprolactam (being called for short PA6), polyhexamethylene adipamide (being called for short PA66), bisphenol A polycarbonate (being called for short PC), poly(4-methyl-1-pentene) (abbreviation PMP).
Described compatilizer is maleic anhydride grafted polyethylene (being called for short PE-g-MAH); Preferably for percentage of grafting is that 1.03MAH%(MAH is maleic anhydride, the massfraction of the maleic anhydride of grafting in the polyethylene particles of MAH% representation unit quality), melting index is that 1.0g/10min(testing standard is ASTM D1238, condition is 190 ℃, 2.16kg), density is 0.94g/cm
3, 130～135 ℃ of fusing points maleic anhydride grafted polyethylene.
Described pore former is that particle diameter is that 40～80nm(is 60～80nm preferably) nano silicon.
In content of the present invention: the thickness of described barrier film is 0.02～0.03mm preferably.
In content of the present invention: preferred in described polymer A: the density of polyethylene terephthalate is 1.40g/cm
3, fusing point within the scope of 255～260 ℃, limiting viscosity is 0.55dL/g; The density of Poly(Trimethylene Terephthalate) is 1.32g/cm
3, fusing point within the scope of 225～240 ℃, limiting viscosity is 0.83dL/g; The density of polybutylene terephthalate is 1.31g/cm
3, fusing point is within the scope of 225～232 ℃, limiting viscosity is 0.57dL/g.
Preferred in described polymer B: the density of polyhexamethylene sebacamide (being called for short PA610) is 1.09g/cm
3, fusing point within the scope of 215～222 ℃, heat-drawn wire is 60 ℃ (testing standard is ASTMD648, and condition is 1.82MPa); The density of polycaprolactam (being called for short PA6) is 1.14g/cm
3, fusing point within the scope of 215～225 ℃, heat-drawn wire is 65 ℃ (testing standard is ASTM D648, and condition is 1.82MPa); The density of polyhexamethylene adipamide (being called for short PA66) is 1.15g/cm
3, fusing point is within the scope of 255～263 ℃, heat-drawn wire is 75 ℃ (testing standard is ASTM D648, and condition is 1.82MPa); The density of poly-11 lactan (being called for short PA11) is 1.05g/cm
3, fusing point is within the scope of 185 ℃～190 ℃, and heat-drawn wire is 54 ℃ (testing standard is ASTM D648, and condition is 1.82MPa); The density of nylon 12 (being called for short PA12) is 1.02g/cm
3, fusing point is within the scope of 173～180 ℃, and heat-drawn wire is 54.5 ℃ (testing standard is ASTM D648, and condition is 1.82MPa); The density of poly-12-1,12-, bis-acyl hexanediamines (being called for short PA612) is 1.06g/cm
3, fusing point is within the scope of 218～222 ℃, and heat-drawn wire is 62 ℃ (testing standard is ASTM D648, and condition is 1.82MPa); The density of nylon 1010 (being called for short PA1010) is 1.08g/cm
3, fusing point is within the scope of 200～210 ℃, and heat-drawn wire is 40 ℃ (testing standard is ASTM D648, and condition is 1.82MPa); The density of polyenanthoamide (being called for short PA7) is 1.11g/cm
3, fusing point is within the scope of 225～230 ℃, and heat-drawn wire is 58 ℃ (testing standard is ASTMD648, and condition is 1.82MPa); The density of poly-13 lactan (being called for short PA13) is 1.01g/cm
3, fusing point is within the scope of 180～183 ℃, and heat-drawn wire is 50.5 ℃ (testing standard is ASTM D648, and condition is 1.82MPa); The density of bisphenol A polycarbonate (being called for short PC) is 1.20g/cm
3, fusing point within the scope of 247～254 ℃, heat-drawn wire is that 135 ℃ of (testing standard is ASTM D648, and condition is 1.82MPa), melting index are that 6g/10min(testing standard is ASTM D1238, condition is 300 ℃, 1.2kg); The fusing point of poly(4-methyl-1-pentene) (be called for short PMP) within the scope of 238～242 ℃, heat-drawn wire is 80 ℃ (testing standard is ASTM D648, condition is 0.45MPa), melting index is that 215g/10min(testing standard is ASTM D1238, condition is 260 ℃, 5kg).
In content of the present invention: described polymer A is polyethylene terephthalate or polybutylene terephthalate preferably, or the mixture of polyethylene terephthalate and polybutylene terephthalate, or the mixture of polyethylene terephthalate and Poly(Trimethylene Terephthalate).
Another content of the present invention is: the preparation method of polyester micro-pore septum for serondary lithium battery, is characterized in that comprising the following steps:
A, batching and pre-treatment:
By the mass percent of 40～79% polymer A, 15～30% polymer B, 5～15% compatilizers and 1～15% pore former and component, get each raw material.
Described polymer A is one or more the mixture in polyethylene terephthalate, polybutylene terephthalate, Poly(Trimethylene Terephthalate); And by described polyethylene terephthalate 160 ℃ of dry 4 hours, polybutylene terephthalate 120 ℃ of dry 8 hours, polybutylene terephthalate 120 ℃ of dry 8 hours, Poly(Trimethylene Terephthalate) 120 ℃ dry 8 hours, standby.
Described polymer B is any in polyhexamethylene sebacamide (being called for short PA610), polycaprolactam (being called for short PA6), polyhexamethylene adipamide (being called for short PA66), nylon 1010 (being called for short PA1010), poly-11 lactan (being called for short PA11), nylon 12 (being called for short PA12), poly-12-1,12-, bis-acyl hexanediamines (being called for short PA612), polyenanthoamide (being called for short PA7), poly-13 lactan (being called for short PA13) and bisphenol A polycarbonate (being called for short PC) and poly(4-methyl-1-pentene) (being called for short PMP).Also can be other polymeric amide (being called for short PA).Preferred polyhexamethylene sebacamide (being called for short PA610), polycaprolactam (being called for short PA6), polyhexamethylene adipamide (being called for short PA66), bisphenol A polycarbonate (being called for short PC), poly(4-methyl-1-pentene) (abbreviation PMP).And described polyhexamethylene sebacamide is dried to 12 hours at 90 ℃, polycaprolactam is dried 10 hours at 100 ℃, polyhexamethylene adipamide is dried 5 hours at 90 ℃, nylon 1010 is dried 5 hours at 95 ℃, poly-11 lactan are dried 7 hours at 85 ℃, nylon 12 is dried 5 hours at 85 ℃, poly-12-1, 12-bis-acyl hexanediamines are dried 12 hours at 105 ℃, polyenanthoamide is dried 6 hours at 90 ℃, poly-13 lactan are dried 6 hours at 80 ℃, bisphenol A polycarbonate is dried 6 hours at 120 ℃, poly(4-methyl-1-pentene) is dried 5 hours at 80 ℃, standby.
Described compatilizer is maleic anhydride grafted polyethylene (being called for short PE-g-MAH); Preferably for percentage of grafting is that 1.03MAH%(MAH is maleic anhydride, the massfraction of the maleic anhydride of grafting in the polyethylene particles of MAH% representation unit quality), melting index is that 1.0g/10min(testing standard is ASTM D1238, condition is 190 ℃, 2.16kg), density is 0.94g/cm
3, 130～135 ℃ of fusing points maleic anhydride grafted polyethylene.
Described pore former is that particle diameter is that 40～80nm(is 60～80nm preferably) nano silicon.
B, prepare serondary lithium battery polyester micro-pore septum:
Polymer A, polymer B, compatilizer and pore former are mixed through high-speed mixer, through twin screw extruder, at the temperature of 240 ℃～320 ℃, after melting mixing, extrude, be cut into particle, the particle obtaining be again dried to moisture content lower than 200ppm after, dropping in single screw extrusion machine melting mixing at the temperature of 240 ℃～320 ℃ again and extrude, is that the cold drum of 10 ℃～60 ℃ is cooling and be cast into the sheet that thickness is 0.2～0.3mm through temperature; First sheet is carried out at the temperature of 80 ℃～150 ℃ again after 2～8 times of longitudinal stretchings, it by temperature, is the drying tunnel preheating of 80 ℃～150 ℃, 1.5～8 times of 2～6 times of synchronous longitudinal stretchings and cross directional stretchs at the temperature of 80 ℃～150 ℃ again, last heat setting type processing at the temperature of 120 ℃～150 ℃, makes 0.01～0.05mm polyester micro-pore septum.
In another content of the present invention: prepare described in step b that serondary lithium battery is also replaceable with polyester micro-pore septum is: polymer A, polymer B, compatilizer and pore former (through high mixer) are mixed, through twin screw extruder, at the temperature of 250 ℃～290 ℃, after melting mixing, extrude, be cut into particle, the particle obtaining be again dried to moisture content lower than 200ppm after, dropping in single screw extrusion machine melting mixing at the temperature of 250 ℃～290 ℃ again and extrude, is that the cold drum of 20 ℃～40 ℃ is cooling and be cast into the sheet that thickness is 0.2～0.3mm through temperature; First sheet is carried out at the temperature of 90 ℃～135 ℃ again after 2～6 times of longitudinal stretchings, it by temperature, is the drying tunnel preheating of 90 ℃～135 ℃, 2～3.5 times of 2～6 times of synchronous longitudinal stretchings and cross directional stretchs at the temperature of 90 ℃～135 ℃ again, last heat setting type processing at the temperature of 120 ℃～150 ℃, makes 0.01～0.05mm polyester micro-pore septum.
In another content of the present invention: the thickness of described barrier film is 0.02～0.03mm preferably.
In another content of the present invention: in described polymer A: the density of polyethylene terephthalate is 1.40g/cm
3, fusing point within the scope of 255～260 ℃, limiting viscosity is 0.55dL/g; The density of Poly(Trimethylene Terephthalate) is 1.32g/cm
3, fusing point within the scope of 225～240 ℃, limiting viscosity is 0.83dL/g; The density of polybutylene terephthalate is 1.31g/cm
3, fusing point is within the scope of 225～232 ℃, limiting viscosity is 0.57dL/g.
In described polymer B: the density of polyhexamethylene sebacamide (being called for short PA610) is 1.09g/cm
3, fusing point within the scope of 215～222 ℃, heat-drawn wire is 60 ℃ (testing standard is ASTM D648, and condition is 1.82MPa); The density of polycaprolactam (being called for short PA6) is 1.14g/cm
3, fusing point within the scope of 215～225 ℃, heat-drawn wire is 65 ℃ (testing standard is ASTM D648, and condition is 1.82MPa); The density of polyhexamethylene adipamide (being called for short PA66) is 1.15g/cm
3, fusing point is within the scope of 255～263 ℃, heat-drawn wire is 75 ℃ (testing standard is ASTM D648, and condition is 1.82MPa); The density of poly-11 lactan (being called for short PA11) is 1.05g/cm
3, fusing point is within the scope of 185 ℃～190 ℃, and heat-drawn wire is 54 ℃ (testing standard is ASTM D648, and condition is 1.82MPa); The density of nylon 12 (being called for short PA12) is 1.02g/cm
3, fusing point is within the scope of 173～180 ℃, and heat-drawn wire is 54.5 ℃ (testing standard is ASTM D648, and condition is 1.82MPa); The density of poly-12-1,12-, bis-acyl hexanediamines (being called for short PA612) is 1.06g/cm
3, fusing point is within the scope of 218～222 ℃, and heat-drawn wire is 62 ℃ (testing standard is ASTM D648, and condition is 1.82MPa); The density of nylon 1010 (being called for short PA1010) is 1.08g/cm
3, fusing point is within the scope of 200～210 ℃, and heat-drawn wire is 40 ℃ (testing standard is ASTM D648, and condition is 1.82MPa); The density of polyenanthoamide (being called for short PA7) is 1.11g/cm
3, fusing point is within the scope of 225～230 ℃, and heat-drawn wire is 58 ℃ (testing standard is ASTMD648, and condition is 1.82MPa); The density of poly-13 lactan (being called for short PA13) is 1.01g/cm
3, fusing point is within the scope of 180～183 ℃, and heat-drawn wire is 50.5 ℃ (testing standard is ASTM D648, and condition is 1.82MPa); The density of bisphenol A polycarbonate (being called for short PC) is 1.20g/cm
3, fusing point within the scope of 247～254 ℃, heat-drawn wire is that 135 ℃ of (testing standard is ASTM D648, and condition is 1.82MPa), melting index are that 6g/10min(testing standard is ASTM D1238, condition is 300 ℃, 1.2kg); The fusing point of poly(4-methyl-1-pentene) (be called for short PMP) within the scope of 238～242 ℃, heat-drawn wire is 80 ℃ (testing standard is ASTM D648, condition is 0.45MPa), melting index is that 215g/10min(testing standard is ASTM D1238, condition is 260 ℃, 5kg).
In another content of the present invention: described polymer A is polyethylene terephthalate or polybutylene terephthalate preferably, or the mixture of polyethylene terephthalate and polybutylene terephthalate, or the mixture of polyethylene terephthalate and Poly(Trimethylene Terephthalate).
Compared with prior art, the present invention has following feature and beneficial effect:
(1) the present invention mixes polymer A, polymer B, compatilizer and pore former by a certain percentage, by twin screw extruder extruding pelletization, dry, through twin screw extruder, extrude again, after cold founding sheet, first carry out longitudinal stretching, then two-way stretch, serondary lithium battery polyester micro-pore septum obtained; The method preparation that polyester micro-pore septum takes physical blowing and two-way stretch to combine, has good physical strength, heat-shrinkable and closing property, can be used for the manufacturing of serondary lithium battery, functional;
(2) adopt polyester micro-pore septum of the present invention and preparation method thereof, because body material is used polyester material, make the barrier film that makes be less than 10% at the percent thermal shrinkage of 160 ℃; More even through the vertical lateral performance of synchronous bidirectional stretching metacneme, its tensile strength is all greater than 35MPa; The ventilation property of room temperature lower diaphragm plate can reach 500s/100mL; Broken through existing can only be with the restriction of polyolefine material, solved adopt dry process using polyester material as serondary lithium battery the technical barrier with micro-pore septum base material;
(3) adopt the present invention, barrier film production technique is simple, and high temperature percent thermal shrinkage is little, and barrier film is in length and breadth to more even, good permeability (as shown in table 1); The lithium ion battery or the lithium cell that can be used for plurality of specifications, as button (individual layer), slim (multilayer folding), cylinder shape (multilaminate coiled) battery; Barrier film can be used in each occasion, as in the battery of mobile telephone, notebook computer, electronic toy, power tool etc., to mention especially, barrier film is applicable to the lithium cell of the high current charge-discharge in electromobile and Moped Scooter field, of many uses, practical.
Embodiment
Embodiment given below intends so that the invention will be further described; but can not be interpreted as it is limiting the scope of the invention; some nonessential improvement and adjustment that person skilled in art makes the present invention according to the content of the invention described above, still belong to protection scope of the present invention.
Embodiment 1-1,1-2:
After each component materials with certain proportion umber given in table 1 is dry under different condition, through twin screw extruder, after 280 ℃ of melting mixings, extrude and be cut into particle, the particle obtaining is dried to after moisture content 200ppm again, dropping into single screw extrusion machine melting mixing under 280 ℃ of conditions extrudes again, be cast into the sheet that thickness is 0.2～0.3mm through the cold drums of 20 ℃～40 ℃ are cooling, first under 120 ℃ of conditions, carry out after 2 times of longitudinal stretchings, again by the drying tunnel preheating of 135 ℃, under 135 ℃ of conditions, carry out synchronous bidirectional stretching, 2.5 times of 2 times of longitudinal stretchings and cross directional stretchs, at 135 ℃, heat setting type is processed again, obtain polyester micro-pore septum.
Embodiment 2-1,2-2:
After each component materials with certain proportion umber given in table 1 is dry under different condition, through twin screw extruder, after 275 ℃ of melting mixings, extrude and be cut into particle, the particle obtaining is dried to after moisture content 200ppm again, dropping into single screw extrusion machine melting mixing under 275 ℃ of conditions extrudes again, be cast into the sheet that thickness is 0.2～0.3mm through the cold drums of 20 ℃～40 ℃ are cooling, first under 100 ℃ of conditions, carry out after 2 times of longitudinal stretchings, by the drying tunnel preheating of 110 ℃, under 110 ℃ of conditions, carry out synchronous bidirectional stretching, 3 times of 2 times of longitudinal stretchings and cross directional stretchs, at 145 ℃, heat setting type is processed again, obtain polyester micro-pore septum.
Embodiment 3-1,3-2:
After each component materials with certain proportion umber given in table 1 is dry under different condition, through twin screw extruder, after 285 ℃ of melting mixings, extrude and be cut into particle, the particle obtaining is dried to after moisture content 200ppm again, dropping into single screw extrusion machine melting mixing under 285 ℃ of conditions extrudes again, be cast into the sheet that thickness is 0.2～0.3mm through the cold drums of 20 ℃～40 ℃ are cooling, first under 105 ℃ of conditions, carry out after 2 times of longitudinal stretchings, by the drying tunnel preheating of 115 ℃, under 115 ℃ of conditions, carry out synchronous bidirectional stretching, 2.8 times of 2 times of longitudinal stretchings and cross directional stretchs, at 150 ℃, heat setting type is processed again, obtain polyester micro-pore septum.
Embodiment 4-1,4-2:
After each component materials with certain proportion umber given in table 1 is dry under different condition, through twin screw extruder, after 280 ℃ of melting mixings, extrude and be cut into particle, the particle obtaining is dried to after moisture content 200ppm again, dropping into single screw extrusion machine melting mixing under 280 ℃ of conditions extrudes again, be cast into the sheet that thickness is 0.2～0.3mm through the cold drums of 20 ℃～40 ℃ are cooling, first under 100 ℃ of conditions, carry out after 2 times of longitudinal stretchings, by the drying tunnel preheating of 105 ℃, under 105 ℃ of conditions, carry out synchronous bidirectional stretching, 2.5 times of 2.2 times of longitudinal stretchings and cross directional stretchs, at 145 ℃, heat setting type is processed again, obtain polyester micro-pore septum.
Embodiment 5-1,5-2:
After each component materials with certain proportion umber given in table 1 is dry under different condition, through twin screw extruder, after 275 ℃ of melting mixings, extrude and be cut into particle, the particle obtaining is dried to after moisture content 200ppm again, dropping into single screw extrusion machine melting mixing under 275 ℃ of conditions extrudes again, be cast into the sheet that thickness is 0.2～0.3mm through the cold drums of 20 ℃～40 ℃ are cooling, first under 90 ℃ of conditions, carry out after 2 times of longitudinal stretchings, by the drying tunnel preheating of 90 ℃, under 90 ℃ of conditions, carry out synchronous bidirectional stretching, 2.5 times of 3 times of longitudinal stretchings and cross directional stretchs, at 120 ℃, heat setting type is processed again, obtain polyester micro-pore septum.
Embodiment 6-1,6-2:
After each component materials with certain proportion umber given in table 1 is dry under different condition, through twin screw extruder, after 260 ℃ of melting mixings, extrude and be cut into particle, the particle obtaining is dried to after moisture content 200ppm again, dropping into single screw extrusion machine melting mixing under 260 ℃ of conditions extrudes again, be cast into the sheet that thickness is 0.2～0.3mm through the cold drums of 20 ℃～40 ℃ are cooling, first under 90 ℃ of conditions, carry out after 2 times of longitudinal stretchings, by the drying tunnel preheating of 95 ℃, under 95 ℃ of conditions, carry out synchronous bidirectional stretching, 2.5 times of 2.5 times of longitudinal stretchings and cross directional stretchs, at 120 ℃, heat setting type is processed again, obtain polyester micro-pore septum.
Embodiment 7-1,7-2:
After each component materials with certain proportion umber given in table 1 is dry under different condition, through twin screw extruder, after 270 ℃ of melting mixings, extrude and be cut into particle, the particle obtaining is dried to after moisture content 200ppm again, dropping into single screw extrusion machine melting mixing under 270 ℃ of conditions extrudes again, be cast into the sheet that thickness is 0.2～0.3mm through the cold drums of 20 ℃～40 ℃ are cooling, first under 105 ℃ of conditions, carry out after 2 times of longitudinal stretchings, by the drying tunnel preheating of 115 ℃, under 115 ℃ of conditions, carry out synchronous bidirectional stretching, 2.8 times of 2 times of longitudinal stretchings and cross directional stretchs, at 125 ℃, heat setting type is processed again, obtain polyester micro-pore septum.
Embodiment 8-1,8-2:
By continued 1(1) in given each component materials with certain proportion umber dry under different condition after, through twin screw extruder, after 265 ℃ of melting mixings, extrude and be cut into particle, the particle obtaining is dried to after moisture content 200ppm again, dropping into single screw extrusion machine melting mixing under 265 ℃ of conditions extrudes again, be cast into the sheet that thickness is 0.2～0.3mm through the cold drums of 20 ℃～40 ℃ are cooling, first under 100 ℃ of conditions, carry out after 2 times of longitudinal stretchings, by the drying tunnel preheating of 110 ℃, under 110 ℃ of conditions, carry out synchronous bidirectional stretching, 2.5 times of 2.2 times of longitudinal stretchings and cross directional stretchs, at 135 ℃, heat setting type is processed again, obtain polyester micro-pore septum.
Embodiment 9-1,9-2:
By continued 1(1) in given each component materials with certain proportion umber dry under different condition after, through twin screw extruder, after 275 ℃ of melting mixings, extrude and be cut into particle, the particle obtaining is dried to after moisture content 200ppm again, dropping into single screw extrusion machine melting mixing under 275 ℃ of conditions extrudes again, be cast into the sheet that thickness is 0.2～0.3mm through the cold drums of 20 ℃～40 ℃ are cooling, first under 100 ℃ of conditions, carry out after 2 times of longitudinal stretchings, by the drying tunnel preheating of 105 ℃, under 105 ℃ of conditions, carry out synchronous bidirectional stretching, 2.5 times of 2.5 times of longitudinal stretchings and cross directional stretchs, at 135 ℃, heat setting type is processed again, obtain polyester micro-pore septum.
Embodiment 10-1,10-2:
By continued 1(1) in given each component materials with certain proportion umber dry under different condition after, through twin screw extruder, after 270 ℃ of melting mixings, extrude and be cut into particle, the particle obtaining is dried to after moisture content 200ppm again, dropping into single screw extrusion machine melting mixing under 270 ℃ of conditions extrudes again, be cast into the sheet that thickness is 0.2～0.3mm through the cold drums of 20 ℃～40 ℃ are cooling, first under 100 ℃ of conditions, carry out after 2 times of longitudinal stretchings, by the drying tunnel preheating of 105 ℃, under 105 ℃ of conditions, carry out synchronous bidirectional stretching, 2.8 times of 2.3 times of longitudinal stretchings and cross directional stretchs, at 145 ℃, heat setting type is processed again, obtain polyester micro-pore septum.
Embodiment 11-1,11-2:
By continued 1(1) in given each component materials with certain proportion umber dry under different condition after, through twin screw extruder, after 265 ℃ of melting mixings, extrude and be cut into particle, the particle obtaining is dried to after moisture content 200ppm again, dropping into single screw extrusion machine melting mixing under 265 ℃ of conditions extrudes again, be cast into the sheet that thickness is 0.2～0.3mm through the cold drums of 20 ℃～40 ℃ are cooling, first under 95 ℃ of conditions, carry out after 2 times of longitudinal stretchings, by the drying tunnel preheating of 100 ℃, under 100 ℃ of conditions, carry out synchronous bidirectional stretching, 3 times of 2 times of longitudinal stretchings and cross directional stretchs, at 140 ℃, heat setting type is processed again, obtain polyester micro-pore septum.
Embodiment 12-1,12-2:
By continued 1(1) in given each component materials with certain proportion umber dry under different condition after, through twin screw extruder, after 265 ℃ of melting mixings, extrude and be cut into particle, the particle obtaining is dried to after moisture content 200ppm again, dropping into single screw extrusion machine melting mixing under 265 ℃ of conditions extrudes again, be cast into the sheet that thickness is 0.2～0.3mm through the cold drums of 20 ℃～40 ℃ are cooling, first under 100 ℃ of conditions, carry out after 2 times of longitudinal stretchings, by the drying tunnel preheating of 105 ℃, under 105 ℃ of conditions, carry out synchronous bidirectional stretching, 2.5 times of 2.5 times of longitudinal stretchings and cross directional stretchs, at 145 ℃, heat setting type is processed again, obtain polyester micro-pore septum.
Embodiment 13-1,13-2:
By continued 1(2) in given each component materials with certain proportion umber dry under different condition after, through twin screw extruder, after 275 ℃ of melting mixings, extrude and be cut into particle, the particle obtaining is dried to after moisture content 200ppm again, dropping into single screw extrusion machine melting mixing under 275 ℃ of conditions extrudes again, be cast into the sheet that thickness is 0.2～0.3mm through the cold drums of 20 ℃～40 ℃ are cooling, first under 120 ℃ of conditions, carry out after 2.5 times of longitudinal stretchings, by the drying tunnel preheating of 125 ℃, under 125 ℃ of conditions, carry out synchronous bidirectional stretching, 2.5 times of 2.5 times of longitudinal stretchings and cross directional stretchs, at 150 ℃, heat setting type is processed again, obtain polyester micro-pore septum.
Embodiment 14-1,14-2:
By continued 1(2) in given each component materials with certain proportion umber dry under different condition after, through twin screw extruder, after 275 ℃ of melting mixings, extrude and be cut into particle, the particle obtaining is dried to after moisture content 200ppm again, dropping into single screw extrusion machine melting mixing under 275 ℃ of conditions extrudes again, be cast into the sheet that thickness is 0.2～0.3mm through the cold drums of 20 ℃～40 ℃ are cooling, first under 110 ℃ of conditions, carry out after 2.3 times of longitudinal stretchings, by the drying tunnel preheating of 120 ℃, under 120 ℃ of conditions, carry out synchronous bidirectional stretching, 2.8 times of 2.5 times of longitudinal stretchings and cross directional stretchs, at 150 ℃, heat setting type is processed again, obtain polyester micro-pore septum.
Embodiment 15-1,15-2:
By continued 1(2) in given each component materials with certain proportion umber dry under different condition after, through twin screw extruder, after 280 ℃ of melting mixings, extrude and be cut into particle, the particle obtaining is dried to after moisture content 200ppm again, dropping into single screw extrusion machine melting mixing under 280 ℃ of conditions extrudes again, be cast into the sheet that thickness is 0.2～0.3mm through the cold drums of 20 ℃～40 ℃ are cooling, first under 130 ℃ of conditions, carry out after 3 times of longitudinal stretchings, by the drying tunnel preheating of 135 ℃, under 135 ℃ of conditions, carry out synchronous bidirectional stretching, 2 times of 2.5 times of longitudinal stretchings and cross directional stretchs, at 145 ℃, heat setting type is processed again, obtain polyester micro-pore septum.
The formula of table 1 embodiment and test result
Continued 1(1)
Continued 1(2)
Embodiment 16～22:
Serondary lithium battery polyester micro-pore septum, is characterized in that: this barrier film is comprised of mass percent and the component of 40～79% polymer A, 15～30% polymer B, 5～15% compatilizers and 1～15% pore former;
In embodiment 16～22, the mass percent consumption of each component sees the following form:
Described polymer A is one or more the mixture in polyethylene terephthalate (be called for short PET), polybutylene terephthalate (being called for short PBT), Poly(Trimethylene Terephthalate) (being called for short PTT);
Described polymer B is any in polyhexamethylene sebacamide (being called for short PA610), polycaprolactam (being called for short PA6), polyhexamethylene adipamide (being called for short PA66), nylon 1010 (being called for short PA1010), poly-11 lactan (being called for short PA11), nylon 12 (being called for short PA12), poly-12-1,12-, bis-acyl hexanediamines (being called for short PA612), polyenanthoamide (being called for short PA7), poly-13 lactan (being called for short PA13) and bisphenol A polycarbonate (being called for short PC) and poly(4-methyl-1-pentene) (being called for short PMP).
Described compatilizer is maleic anhydride grafted polyethylene (being called for short PE-g-MAH); Preferably for percentage of grafting is that 1.03MAH%(MAH is maleic anhydride, the massfraction of the maleic anhydride of grafting in the polyethylene particles of MAH% representation unit quality), melting index is that 1.0g/10min(testing standard is ASTM D1238, condition is 190 ℃, 2.16kg), density is 0.94g/cm
3, 130～135 ℃ of fusing points maleic anhydride grafted polyethylene;
Described pore former is that particle diameter is that 40～80nm(is 60～80nm preferably) nano silicon.
In described polymer A: the density of polyethylene terephthalate is 1.40g/cm
3, fusing point within the scope of 255～260 ℃, limiting viscosity is 0.55dL/g; The density of Poly(Trimethylene Terephthalate) is 1.32g/cm
3, fusing point within the scope of 225～240 ℃, limiting viscosity is 0.83dL/g; The density of polybutylene terephthalate is 1.31g/cm
3, fusing point is within the scope of 225～232 ℃, limiting viscosity is 0.57dL/g;
In described polymer B: the density of polyhexamethylene sebacamide (being called for short PA610) is 1.09g/cm
3, fusing point within the scope of 215～222 ℃, heat-drawn wire is 60 ℃ (testing standard is ASTM D648, and condition is 1.82MPa); The density of polycaprolactam (being called for short PA6) is 1.14g/cm
3, fusing point within the scope of 215～225 ℃, heat-drawn wire is 65 ℃ (testing standard is ASTM D648, and condition is 1.82MPa); The density of polyhexamethylene adipamide (being called for short PA66) is 1.15g/cm
3, fusing point is within the scope of 255～263 ℃, heat-drawn wire is 75 ℃ (testing standard is ASTM D648, and condition is 1.82MPa); The density of poly-11 lactan (being called for short PA11) is 1.05g/cm
3, fusing point is within the scope of 185 ℃～190 ℃, and heat-drawn wire is 54 ℃ (testing standard is ASTM D648, and condition is 1.82MPa); The density of nylon 12 (being called for short PA12) is 1.02g/cm
3, fusing point is within the scope of 173～180 ℃, and heat-drawn wire is 54.5 ℃ (testing standard is ASTM D648, and condition is 1.82MPa); The density of poly-12-1,12-, bis-acyl hexanediamines (being called for short PA612) is 1.06g/cm
3, fusing point is within the scope of 218～222 ℃, and heat-drawn wire is 62 ℃ (testing standard is ASTM D648, and condition is 1.82MPa); The density of nylon 1010 (being called for short PA1010) is 1.08g/cm
3, fusing point is within the scope of 200～210 ℃, and heat-drawn wire is 40 ℃ (testing standard is ASTM D648, and condition is 1.82MPa); The density of polyenanthoamide (being called for short PA7) is 1.11g/cm
3, fusing point is within the scope of 225～230 ℃, and heat-drawn wire is 58 ℃ (testing standard is ASTM D648, and condition is 1.82MPa); The density of poly-13 lactan (being called for short PA13) is 1.01g/cm
3, fusing point is within the scope of 180～183 ℃, and heat-drawn wire is 50.5 ℃ (testing standard is ASTM D648, and condition is 1.82MPa); The density of bisphenol A polycarbonate (being called for short PC) is 1.20g/cm
3, fusing point within the scope of 247～254 ℃, heat-drawn wire is that 135 ℃ of (testing standard is ASTM D648, and condition is 1.82MPa), melting index are that 6g/10min(testing standard is ASTM D1238, condition is 300 ℃, 1.2kg); The fusing point of poly(4-methyl-1-pentene) (be called for short PMP) within the scope of 238～242 ℃, heat-drawn wire is 80 ℃ (testing standard is ASTM D648, condition is 0.45MPa), melting index is that 215g/10min(testing standard is ASTM D1238, condition is 260 ℃, 5kg).
Described polymer A is polyethylene terephthalate or polybutylene terephthalate preferably, or the mixture of polyethylene terephthalate and polybutylene terephthalate, or the mixture of polyethylene terephthalate and Poly(Trimethylene Terephthalate).
Embodiment 23～29:
5, the preparation method of polyester micro-pore septum for serondary lithium battery, is characterized in that comprising the following steps:
A, batching and pre-treatment:
By the mass percent of 40～79% polymer A, 15～30% polymer B, 5～15% compatilizers and 1～15% pore former and component, get each raw material;
In embodiment 23～29, the mass percent consumption of each component sees the following form:
Described polymer A is one or more the mixture in polyethylene terephthalate, polybutylene terephthalate, Poly(Trimethylene Terephthalate); And by described polyethylene terephthalate 160 ℃ of dry 4 hours, polybutylene terephthalate 120 ℃ of dry 8 hours, polybutylene terephthalate 120 ℃ of dry 8 hours, Poly(Trimethylene Terephthalate) 120 ℃ dry 8 hours, standby;
Described polymer B is any in polyhexamethylene sebacamide (being called for short PA610), polycaprolactam (being called for short PA6), polyhexamethylene adipamide (being called for short PA66), nylon 1010 (being called for short PA1010), poly-11 lactan (being called for short PA11), nylon 12 (being called for short PA12), poly-12-1,12-, bis-acyl hexanediamines (being called for short PA612), polyenanthoamide (being called for short PA7), poly-13 lactan (being called for short PA13) and bisphenol A polycarbonate (being called for short PC) and poly(4-methyl-1-pentene) (being called for short PMP).And described polyhexamethylene sebacamide is dried to 12 hours at 90 ℃, polycaprolactam is dried 10 hours at 100 ℃, polyhexamethylene adipamide is dried 5 hours at 90 ℃, nylon 1010 is dried 5 hours at 95 ℃, poly-11 lactan are dried 7 hours at 85 ℃, nylon 12 is dried 5 hours at 85 ℃, poly-12-1, 12-bis-acyl hexanediamines are dried 12 hours at 105 ℃, polyenanthoamide is dried 6 hours at 90 ℃, poly-13 lactan are dried 6 hours at 80 ℃, bisphenol A polycarbonate is dried 6 hours at 120 ℃, poly(4-methyl-1-pentene) is dried 5 hours at 80 ℃, standby,
Described compatilizer is maleic anhydride grafted polyethylene (being called for short PE-g-MAH); Preferably for percentage of grafting is that 1.03MAH%(MAH is maleic anhydride, the massfraction of the maleic anhydride of grafting in the polyethylene particles of MAH% representation unit quality), melting index is that 1.0g/10min(testing standard is ASTM D1238, condition is 190 ℃, 2.16kg), density is 0.94g/cm
3, 130～135 ℃ of fusing points maleic anhydride grafted polyethylene;
Described pore former is that particle diameter is that 40～80nm(is 60～80nm preferably) nano silicon.
B, prepare serondary lithium battery polyester micro-pore septum:
Polymer A, polymer B, compatilizer and pore former are mixed through high-speed mixer, through twin screw extruder, at the temperature of 240 ℃～320 ℃, after melting mixing, extrude, be cut into particle, the particle obtaining be again dried to moisture content lower than 200ppm after, dropping in single screw extrusion machine melting mixing at the temperature of 240 ℃～320 ℃ again and extrude, is that the cold drum of 10 ℃～60 ℃ is cooling and be cast into the sheet that thickness is 0.2～0.3mm through temperature; First sheet is carried out at the temperature of 80 ℃～150 ℃ again after 2～8 times of longitudinal stretchings, it by temperature, is the drying tunnel preheating of 80 ℃～150 ℃, 1.5～8 times of 2～6 times of synchronous longitudinal stretchings and cross directional stretchs at the temperature of 80 ℃～150 ℃ again, last heat setting type processing at the temperature of 120 ℃～150 ℃, makes 0.01～0.05mm polyester micro-pore septum.
Embodiment 30:
The preparation method of polyester micro-pore septum for serondary lithium battery, described in step b, preparing serondary lithium battery replaces with polyester micro-pore septum: polymer A, polymer B, compatilizer and pore former are mixed through high-speed mixer, through twin screw extruder, at the temperature of 240 ℃, after melting mixing, extrude, be cut into particle, the particle obtaining be again dried to moisture content lower than 200ppm after, dropping in single screw extrusion machine melting mixing at the temperature of 240 ℃ again and extrude, is that the cold drum of 10 ℃ is cooling and be cast into the sheet that thickness is 0.2mm through temperature; First sheet is carried out at the temperature of 80 ℃ again after 2 times of longitudinal stretchings, it by temperature, is the drying tunnel preheating of 80 ℃, 1.5 times of 2 times of synchronous longitudinal stretchings and cross directional stretchs at the temperature of 80 ℃ again, last at the temperature of 120 ℃ heat setting type process, make 0.01～0.05mm polyester micro-pore septum.Arbitrary in the other the same as in Example 2 3～29, omit.
Embodiment 31:
The preparation method of polyester micro-pore septum for serondary lithium battery, described in step b, preparing serondary lithium battery replaces with polyester micro-pore septum: polymer A, polymer B, compatilizer and pore former are mixed through high-speed mixer, through twin screw extruder, at the temperature of 320 ℃, after melting mixing, extrude, be cut into particle, the particle obtaining be again dried to moisture content lower than 200ppm after, dropping in single screw extrusion machine melting mixing at the temperature of 320 ℃ again and extrude, is that the cold drum of 60 ℃ is cooling and be cast into the sheet that thickness is 0.3mm through temperature; First sheet is carried out at the temperature of 150 ℃ again after 8 times of longitudinal stretchings, it by temperature, is the drying tunnel preheating of 150 ℃, 8 times of 6 times of synchronous longitudinal stretchings and cross directional stretchs at the temperature of 150 ℃ again, last at the temperature of 150 ℃ heat setting type process, make 0.01～0.05mm polyester micro-pore septum.Arbitrary in the other the same as in Example 2 3～29, omit.
Embodiment 32:
The preparation method of polyester micro-pore septum for serondary lithium battery, described in step b, preparing serondary lithium battery replaces with polyester micro-pore septum: polymer A, polymer B, compatilizer and pore former are mixed through high-speed mixer, through twin screw extruder, at the temperature of 280 ℃, after melting mixing, extrude, be cut into particle, the particle obtaining be again dried to moisture content lower than 200ppm after, dropping in single screw extrusion machine melting mixing at the temperature of 280 ℃ again and extrude, is that the cold drum of 40 ℃ is cooling and be cast into the sheet that thickness is 0.25mm through temperature; First sheet is carried out at the temperature of 120 ℃ again after 5 times of longitudinal stretchings, it by temperature, is the drying tunnel preheating of 120 ℃, 5 times of 4 times of synchronous longitudinal stretchings and cross directional stretchs at the temperature of 120 ℃ again, last at the temperature of 130 ℃ heat setting type process, make 0.01～0.05mm polyester micro-pore septum.Arbitrary in the other the same as in Example 2 3～29, omit.
Embodiment 33:
The preparation method of polyester micro-pore septum for serondary lithium battery, described in step b, preparing serondary lithium battery replaces with polyester micro-pore septum: by polymer A, polymer B, compatilizer and pore former mix through high-speed mixer, through twin screw extruder, at the temperature of 250 ℃～290 ℃, after melting mixing, extrude, be cut into particle, the particle obtaining be again dried to moisture content lower than 200ppm after, dropping in single screw extrusion machine melting mixing at the temperature of 250 ℃～290 ℃ extrudes again, through temperature, be that the cold drum of 20 ℃～40 ℃ is cooling and be cast into the sheet that thickness is 0.2～0.3mm, first sheet is carried out at the temperature of 90 ℃～135 ℃ again after 2～6 times of longitudinal stretchings, it by temperature, is the drying tunnel preheating of 90 ℃～135 ℃, 2～3.5 times of 2～6 times of synchronous longitudinal stretchings and cross directional stretchs at the temperature of 90 ℃～135 ℃ again, last heat setting type processing at the temperature of 120 ℃～150 ℃, makes 0.01～0.05mm polyester micro-pore septum.Arbitrary in the other the same as in Example 2 3～29, omit.
Embodiment 34:
The preparation method of polyester micro-pore septum for serondary lithium battery, described in step b, preparing serondary lithium battery replaces with polyester micro-pore septum: polymer A, polymer B, compatilizer and pore former are mixed through high-speed mixer, through twin screw extruder, at the temperature of 290 ℃, after melting mixing, extrude, be cut into particle, the particle obtaining be again dried to moisture content lower than 200ppm after, dropping in single screw extrusion machine melting mixing at the temperature of 290 ℃ again and extrude, is that the cold drum of 40 ℃ is cooling and be cast into the sheet that thickness is 0.3mm through temperature; First sheet is carried out at the temperature of 135 ℃ again after 6 times of longitudinal stretchings, it by temperature, is the drying tunnel preheating of 135 ℃, 3.5 times of 6 times of synchronous longitudinal stretchings and cross directional stretchs at the temperature of 135 ℃ again, last heat setting type processing at the temperature of 150 ℃, makes 0.01～0.05mm polyester micro-pore septum.Arbitrary in the other the same as in Example 2 3～29, omit.
Embodiment 35:
The preparation method of polyester micro-pore septum for serondary lithium battery, described in step b, preparing serondary lithium battery replaces with polyester micro-pore septum: polymer A, polymer B, compatilizer and pore former are mixed through high-speed mixer, through twin screw extruder, at the temperature of 250 ℃, after melting mixing, extrude, be cut into particle, the particle obtaining be again dried to moisture content lower than 200ppm after, dropping in single screw extrusion machine melting mixing at the temperature of 250 ℃ again and extrude, is that the cold drum of 20 ℃ is cooling and be cast into the sheet that thickness is 0.2mm through temperature; First sheet is carried out at the temperature of 90 ℃ again after 2 times of longitudinal stretchings, it by temperature, is the drying tunnel preheating of 90 ℃, 2 times of 2 times of synchronous longitudinal stretchings and cross directional stretchs at the temperature of 90 ℃ again, last at the temperature of 120 ℃ heat setting type process, make 0.01～0.05mm polyester micro-pore septum.Arbitrary in the other the same as in Example 2 3～29, omit.
Embodiment 36:
The preparation method of polyester micro-pore septum for serondary lithium battery, described in step b, preparing serondary lithium battery replaces with polyester micro-pore septum: polymer A, polymer B, compatilizer and pore former are mixed through high-speed mixer, through twin screw extruder, at the temperature of 270 ℃, after melting mixing, extrude, be cut into particle, the particle obtaining be again dried to moisture content lower than 200ppm after, dropping in single screw extrusion machine melting mixing at the temperature of 270 ℃ again and extrude, is that the cold drum of 30 ℃ is cooling and be cast into the sheet that thickness is 0.25mm through temperature; First sheet is carried out at the temperature of 115 ℃ again after 4 times of longitudinal stretchings, it by temperature, is the drying tunnel preheating of 115 ℃, 2.8 times of 4 times of synchronous longitudinal stretchings and cross directional stretchs at the temperature of 115 ℃ again, last heat setting type processing at the temperature of 135 ℃, makes 0.01～0.05mm polyester micro-pore septum.Arbitrary in the other the same as in Example 2 3～29, omit.
In above-described embodiment 23～36: in described polymer A: the density of polyethylene terephthalate is 1.40g/cm
3, fusing point within the scope of 255～260 ℃, limiting viscosity is 0.55dL/g; The density of Poly(Trimethylene Terephthalate) is 1.32g/cm
3, fusing point within the scope of 225～240 ℃, limiting viscosity is 0.83dL/g; The density of polybutylene terephthalate is 1.31g/cm
3, fusing point is within the scope of 225～232 ℃, limiting viscosity is 0.57dL/g;
In described polymer B: the density of polyhexamethylene sebacamide (being called for short PA610) is 1.09g/cm
3, fusing point within the scope of 215～222 ℃, heat-drawn wire is 60 ℃ (testing standard is ASTM D648, and condition is 1.82MPa); The density of polycaprolactam (being called for short PA6) is 1.14g/cm
3, fusing point within the scope of 215～225 ℃, heat-drawn wire is 65 ℃ (testing standard is ASTM D648, and condition is 1.82MPa); The density of polyhexamethylene adipamide (being called for short PA66) is 1.15g/cm
3, fusing point is within the scope of 255～263 ℃, heat-drawn wire is 75 ℃ (testing standard is ASTM D648, and condition is 1.82MPa); The density of poly-11 lactan (being called for short PA11) is 1.05g/cm
3, fusing point is within the scope of 185 ℃～190 ℃, and heat-drawn wire is 54 ℃ (testing standard is ASTM D648, and condition is 1.82MPa); The density of nylon 12 (being called for short PA12) is 1.02g/cm
3, fusing point is within the scope of 173～180 ℃, and heat-drawn wire is 54.5 ℃ (testing standard is ASTM D648, and condition is 1.82MPa); The density of poly-12-1,12-, bis-acyl hexanediamines (being called for short PA612) is 1.06g/cm
3, fusing point is within the scope of 218～222 ℃, and heat-drawn wire is 62 ℃ (testing standard is ASTM D648, and condition is 1.82MPa); The density of nylon 1010 (being called for short PA1010) is 1.08g/cm
3, fusing point is within the scope of 200～210 ℃, and heat-drawn wire is 40 ℃ (testing standard is ASTM D648, and condition is 1.82MPa); The density of polyenanthoamide (being called for short PA7) is 1.11g/cm
3, fusing point is within the scope of 225～230 ℃, and heat-drawn wire is 58 ℃ (testing standard is ASTM D648, and condition is 1.82MPa); The density of poly-13 lactan (being called for short PA13) is 1.01g/cm
3, fusing point is within the scope of 180～183 ℃, and heat-drawn wire is 50.5 ℃ (testing standard is ASTM D648, and condition is 1.82MPa); The density of bisphenol A polycarbonate (being called for short PC) is 1.20g/cm
3, fusing point within the scope of 247～254 ℃, heat-drawn wire is that 135 ℃ of (testing standard is ASTM D648, and condition is 1.82MPa), melting index are that 6g/10min(testing standard is ASTM D1238, condition is 300 ℃, 1.2kg); The fusing point of poly(4-methyl-1-pentene) (be called for short PMP) within the scope of 238～242 ℃, heat-drawn wire is 80 ℃ (testing standard is ASTM D648, condition is 0.45MPa), melting index is that 215g/10min(testing standard is ASTM D1238, condition is 260 ℃, 5kg).
In above-described embodiment 23～36: described polymer A is polyethylene terephthalate or polybutylene terephthalate preferably, or the mixture of polyethylene terephthalate and polybutylene terephthalate, or the mixture of polyethylene terephthalate and Poly(Trimethylene Terephthalate).
In above-described embodiment 16～36: the thickness of described barrier film is 0.02～0.03mm preferably.
In above-described embodiment: in the percentage adopting, do not indicate especially, be quality (weight) percentage (wt% is mass percent); In the ratio adopting, do not indicate especially, be quality (weight) ratio; Described weight part can be all kilogram or ton.
In above-described embodiment: the processing parameter in each step (temperature, time, concentration etc.) and each amounts of components numerical value etc. are scope, and any point is all applicable.
The not concrete same prior art of technology contents of narrating in content of the present invention and above-described embodiment, described starting material are commercially available prod.
The invention is not restricted to above-described embodiment, all can implement and have described good result described in content of the present invention.
Claims (10)
1. serondary lithium battery polyester micro-pore septum, is characterized in that: this barrier film is comprised of mass percent and the component of 40～79% polymer A, 15～30% polymer B, 5～15% compatilizers and 1～15% pore former, and membrane thicknesses is 0.01～0.05mm;
Described polymer A is one or more the mixture in polyethylene terephthalate, polybutylene terephthalate, Poly(Trimethylene Terephthalate);
Described polymer B is any in polyhexamethylene sebacamide, polycaprolactam, polyhexamethylene adipamide, nylon 1010, poly-11 lactan, nylon 12, poly-12-1,12-, bis-acyl hexanediamines, polyenanthoamide, poly-13 lactan, bisphenol A polycarbonate and poly(4-methyl-1-pentene);
Described compatilizer is maleic anhydride grafted polyethylene;
Described pore former is that particle diameter is the nano silicon of 40～80nm.
2. by serondary lithium battery claimed in claim 1 polyester micro-pore septum, it is characterized in that: the thickness of described barrier film is 0.02～0.03mm.
3. by the serondary lithium battery polyester micro-pore septum described in claim 1 or 2, it is characterized in that:
In described polymer A: the density of polyethylene terephthalate is 1.40g/cm
3, fusing point within the scope of 255～260 ℃, limiting viscosity is 0.55dL/g; The density of Poly(Trimethylene Terephthalate) is 1.32g/cm
3, fusing point within the scope of 225～240 ℃, limiting viscosity is 0.83dL/g; The density of polybutylene terephthalate is 1.31g/cm
3, fusing point is within the scope of 225～232 ℃, limiting viscosity is 0.57dL/g;
In described polymer B: the density of polyhexamethylene sebacamide is 1.09g/cm
3, fusing point within the scope of 215～222 ℃, heat-drawn wire is 60 ℃; The density of polycaprolactam is 1.14g/cm
3, fusing point within the scope of 215～225 ℃, heat-drawn wire is 65 ℃; The density of polyhexamethylene adipamide is 1.15g/cm
3, fusing point is within the scope of 255～263 ℃, heat-drawn wire is 75 ℃; The density of poly-11 lactan is 1.05g/cm
3, fusing point is within the scope of 185 ℃～190 ℃, and heat-drawn wire is 54 ℃; The density of nylon 12 is 1.02g/cm
3, fusing point is within the scope of 173～180 ℃, and heat-drawn wire is 54.5 ℃; The density of poly-12-1,12-, bis-acyl hexanediamines is 1.06g/cm
3, fusing point is within the scope of 218～222 ℃, and heat-drawn wire is 62 ℃; The density of nylon 1010 is 1.08g/cm
3, fusing point is within the scope of 200～210 ℃, and heat-drawn wire is 40 ℃; The density of polyenanthoamide is 1.11g/cm
3, fusing point is within the scope of 225～230 ℃, and heat-drawn wire is 58 ℃; The density of poly-13 lactan is 1.01g/cm
3, fusing point is within the scope of 180～183 ℃, and heat-drawn wire is 50.5 ℃; The density of bisphenol A polycarbonate is 1.20g/cm
3, fusing point within the scope of 247～254 ℃, heat-drawn wire is that 135 ℃, melting index are 6g/10min; The fusing point of poly(4-methyl-1-pentene) within the scope of 238～242 ℃, heat-drawn wire is that 80 ℃, melting index are 215g/10min.
4. by the serondary lithium battery polyester micro-pore septum described in claim 1 or 2, it is characterized in that: described polymer A is polyethylene terephthalate or polybutylene terephthalate, or the mixture of polyethylene terephthalate and polybutylene terephthalate, or the mixture of polyethylene terephthalate and Poly(Trimethylene Terephthalate).
5. the preparation method of polyester micro-pore septum for serondary lithium battery, is characterized in that comprising the following steps:
A, batching and pre-treatment:
By the mass percent of 40～79% polymer A, 15～30% polymer B, 5～15% compatilizers and 1～15% pore former and component, get each raw material;
Described polymer A is one or more the mixture in polyethylene terephthalate, polybutylene terephthalate, Poly(Trimethylene Terephthalate); And by described polyethylene terephthalate 160 ℃ of dry 4 hours, polybutylene terephthalate 120 ℃ of dry 8 hours, polybutylene terephthalate 120 ℃ of dry 8 hours, Poly(Trimethylene Terephthalate) 120 ℃ dry 8 hours, standby;
Described polymer B is any in polyhexamethylene sebacamide, polycaprolactam, polyhexamethylene adipamide, nylon 1010, poly-11 lactan, nylon 12, poly-12-1,12-, bis-acyl hexanediamines, polyenanthoamide, poly-13 lactan, bisphenol A polycarbonate and poly(4-methyl-1-pentene), and described polyhexamethylene sebacamide is dried to 12 hours at 90 ℃, polycaprolactam is dried 10 hours at 100 ℃, polyhexamethylene adipamide is dried 5 hours at 90 ℃, nylon 1010 is dried 5 hours at 95 ℃, poly-11 lactan are dried 7 hours at 85 ℃, nylon 12 is dried 5 hours at 85 ℃, poly-12-1, 12-bis-acyl hexanediamines are dried 12 hours at 105 ℃, polyenanthoamide is dried 6 hours at 90 ℃, poly-13 lactan are dried 6 hours at 80 ℃, bisphenol A polycarbonate is dried 6 hours at 120 ℃, poly(4-methyl-1-pentene) is dried 5 hours at 80 ℃, standby,
Described compatilizer is maleic anhydride grafted polyethylene;
Described pore former is that particle diameter is the nano silicon of 40～80nm;
B, prepare serondary lithium battery polyester micro-pore septum:
Polymer A, polymer B, compatilizer and pore former are mixed, through twin screw extruder, at the temperature of 240 ℃～320 ℃, after melting mixing, extrude, be cut into particle, the particle obtaining be again dried to moisture content lower than 200ppm after, dropping in single screw extrusion machine melting mixing at the temperature of 240 ℃～320 ℃ again and extrude, is that the cold drum of 10 ℃～60 ℃ is cooling and be cast into the sheet that thickness is 0.2～0.3mm through temperature; First sheet is carried out at the temperature of 80 ℃～150 ℃ again after 2～8 times of longitudinal stretchings, it by temperature, is the drying tunnel preheating of 80 ℃～150 ℃, 1.5～8 times of 2～6 times of synchronous longitudinal stretchings and cross directional stretchs at the temperature of 80 ℃～150 ℃ again, last heat setting type processing at the temperature of 120 ℃～150 ℃, makes 0.01～0.05mm polyester micro-pore septum.
6. by serondary lithium battery described in claim 5, use the preparation method of polyester micro-pore septum, it is characterized in that: described in step b, prepare serondary lithium battery and replace with polyester micro-pore septum: by polymer A, polymer B, compatilizer and pore former mix, through twin screw extruder, at the temperature of 250 ℃～290 ℃, after melting mixing, extrude, be cut into particle, the particle obtaining be again dried to moisture content lower than 200ppm after, dropping in single screw extrusion machine melting mixing at the temperature of 250 ℃～290 ℃ extrudes again, through temperature, be that the cold drum of 20 ℃～40 ℃ is cooling and be cast into the sheet that thickness is 0.2～0.3mm, first sheet is carried out at the temperature of 90 ℃～135 ℃ again after 2～6 times of longitudinal stretchings, it by temperature, is the drying tunnel preheating of 90 ℃～135 ℃, 2～3.5 times of 2～6 times of synchronous longitudinal stretchings and cross directional stretchs at the temperature of 90 ℃～135 ℃ again, last heat setting type processing at the temperature of 120 ℃～150 ℃, makes 0.01～0.05mm polyester micro-pore septum.
7. the preparation method with polyester micro-pore septum by serondary lithium battery described in claim 5, is characterized in that: the thickness of described barrier film is 0.02～0.03mm.
8. the preparation method with polyester micro-pore septum by serondary lithium battery described in claim 6, is characterized in that: the thickness of described barrier film is 0.02～0.03mm.
9. by serondary lithium battery described in claim 5,6,7 or 8, use the preparation method of polyester micro-pore septum, it is characterized in that:
In described polymer A: the density of polyethylene terephthalate is 1.40g/cm
3, fusing point within the scope of 255～260 ℃, limiting viscosity is 0.55dL/g; The density of Poly(Trimethylene Terephthalate) is 1.32g/cm
3, fusing point within the scope of 225～240 ℃, limiting viscosity is 0.83dL/g; The density of polybutylene terephthalate is 1.31g/cm
3, fusing point is within the scope of 225～232 ℃, limiting viscosity is 0.57dL/g;
In described polymer B: the density of polyhexamethylene sebacamide is 1.09g/cm
3, fusing point within the scope of 215～222 ℃, heat-drawn wire is 60 ℃; The density of polycaprolactam is 1.14g/cm
3, fusing point within the scope of 215～225 ℃, heat-drawn wire is 65 ℃; The density of polyhexamethylene adipamide is 1.15g/cm
3, fusing point is within the scope of 255～263 ℃, heat-drawn wire is 75 ℃; The density of poly-11 lactan is 1.05g/cm
3, fusing point is within the scope of 185 ℃～190 ℃, and heat-drawn wire is 54 ℃; The density of nylon 12 is 1.02g/cm
3, fusing point is within the scope of 173～180 ℃, and heat-drawn wire is 54.5 ℃; The density of poly-12-1,12-, bis-acyl hexanediamines is 1.06g/cm
3, fusing point is within the scope of 218～222 ℃, and heat-drawn wire is 62 ℃; The density of nylon 1010 is 1.08g/cm
3, fusing point is within the scope of 200～210 ℃, and heat-drawn wire is 40 ℃; The density of polyenanthoamide is 1.11g/cm
3, fusing point is within the scope of 225～230 ℃, and heat-drawn wire is 58 ℃; The density of poly-13 lactan is 1.01g/cm
3, fusing point is within the scope of 180～183 ℃, and heat-drawn wire is 50.5 ℃; The density of bisphenol A polycarbonate is 1.20g/cm
3, fusing point within the scope of 247～254 ℃, heat-drawn wire is that 135 ℃, melting index are 6g/10min; The fusing point of poly(4-methyl-1-pentene) within the scope of 238～242 ℃, heat-drawn wire is that 80 ℃, melting index are 215g/10min.
10. by serondary lithium battery described in claim 5,6,7 or 8, use the preparation method of polyester micro-pore septum, it is characterized in that: described polymer A is polyethylene terephthalate or polybutylene terephthalate, or the mixture of polyethylene terephthalate and polybutylene terephthalate, or the mixture of polyethylene terephthalate and Poly(Trimethylene Terephthalate).
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101766960A (en) * | 2008-12-31 | 2010-07-07 | 中国纺织科学研究院 | Composite hollow fiber membrane and preparation method thereof |
-
2013
- 2013-12-27 CN CN201310740610.0A patent/CN103724951B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101766960A (en) * | 2008-12-31 | 2010-07-07 | 中国纺织科学研究院 | Composite hollow fiber membrane and preparation method thereof |
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