CN103724951B - Serondary lithium battery polyester micro-pore septum and preparation method thereof - Google Patents

Serondary lithium battery polyester micro-pore septum and preparation method thereof Download PDF

Info

Publication number
CN103724951B
CN103724951B CN201310740610.0A CN201310740610A CN103724951B CN 103724951 B CN103724951 B CN 103724951B CN 201310740610 A CN201310740610 A CN 201310740610A CN 103724951 B CN103724951 B CN 103724951B
Authority
CN
China
Prior art keywords
poly
fusing point
density
temperature
scope
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201310740610.0A
Other languages
Chinese (zh)
Other versions
CN103724951A (en
Inventor
赵贵红
马雅琳
胡俊祥
罗春明
李建学
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SICHUAN DONGFANG INSULATING MATERIAL CO Ltd
Original Assignee
SICHUAN DONGFANG INSULATING MATERIAL CO Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by SICHUAN DONGFANG INSULATING MATERIAL CO Ltd filed Critical SICHUAN DONGFANG INSULATING MATERIAL CO Ltd
Priority to CN201310740610.0A priority Critical patent/CN103724951B/en
Publication of CN103724951A publication Critical patent/CN103724951A/en
Application granted granted Critical
Publication of CN103724951B publication Critical patent/CN103724951B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Landscapes

  • Cell Separators (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

The invention discloses a kind of serondary lithium battery polyester micro-pore septum, it is characterized in that: the mass percent of barrier film consists of 40 ~ 79% polymer A, 15 ~ 30% polymer B, 5 ~ 15% compatilizers and 1 ~ 15% pore former; The thickness of barrier film is 0.01 ~ 0.05mm; Polymer A, polymer B, compatilizer and pore former mix by the preparation method of barrier film, through the granulation of twin screw extruder melting mixing, dry, melt extrude through single screw extrusion machine again, through cold founding sheet, longitudinal stretching 2 ~ 8 times at 80 DEG C ~ 150 DEG C, then at 80 DEG C ~ 150 DEG C synchronous longitudinal stretching 2 ~ 6 times and cross directional stretch 1.5 ~ 8 times, heat setting type process, i.e. obtained polyester micro-pore septum.Polyester micro-pore septum of the present invention has good physical strength, heat-shrinkable and closing property, can be used for the manufacturing of serondary lithium battery, is particularly useful as the serondary lithium battery worked temperature more than 160 DEG C and uses.

Description

Serondary lithium battery polyester micro-pore septum and preparation method thereof
Technical field
The invention belongs to the barrier film for lithium cell and preparation thereof, relate to a kind of serondary lithium battery polyester micro-pore septum and preparation method thereof.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 worked temperature more than 160 DEG C.
Background technology
In prior art, the diaphragm material being applied in lithium cell aspect mainly contains polypropylene, polyethylene, polyimide, polyvinylidene difluoride (PVDF), is generally single or multiple lift film, and what its processing method mainly adopted is dry method and wet method two kinds.The closing temperature adopting the polypropylene of dry process, the individual layer of polyvinyls or laminated diaphragm is 130 DEG C ~ 160 DEG C, is difficult to ensure the safety of lithium cell more than 160 DEG C in individual work situation; Because its percent thermal shrinkage more than 150 DEG C, more than more than 15%, very easily causes 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 at about 500s/100mL, along with lithium cell temperature is elevated to the closed of more than 160 DEG C diaphragm micro-hole, the air penetrability of this type of barrier film can decline rapidly, passing through of obstacle electrolyte ion, has a strong impact on the charge and discharge process under the safe handling of lithium cell and hot conditions.As patent EP1-942-000A1 discloses a kind of multi-layer cell barrier film, it is the porous-film be made up of polyvinyl resin layer and polypropylene resin layer.Although physical strength good under normal temperature, percent thermal shrinkage, closing temperature and temperature of fusion, in battery use procedure, temperature ion when reaching about 160 DEG C 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 μm, the micro-pore septum be made up of the polyvinyl resin of two kinds of different molecular weights, its basic craft course is by two kinds of different molecular weights and stretches containing carrying out first time after the polyvinyl resin melting film extrusion of pore former (this patent claims " thinner "), carries out second time stretching again and make polyethylene micropore separator product after removing pore former.This production technique is only suitable for producing thinner polyethylene micropore separator product, and wherein the ventilation property impact of content on barrier film of thinner is comparatively large, requires higher to complete processing.
Summary of the invention
Object of the present invention is intended to overcome above-mentioned deficiency of the prior art, provides a kind of serondary lithium battery polyester micro-pore septum and preparation method thereof.The present invention is directed to existing polyolefins barrier film more than 160 DEG C under condition under high, the ventilation property of percent thermal shrinkage degradation not enough, what provide a kind of individual layer take polyester material as body material, and serondary lithium battery polyester micro-pore septum that can meet the work of lithium cell normal safe more than 160 DEG C and preparation method thereof.
Content of the present invention is: serondary lithium battery polyester micro-pore septum, it is characterized in that: this barrier film by 40 ~ 79% polymer A, 15 ~ 30% polymer B, 5 ~ 15% compatilizers and 1 ~ 15% pore former percent mass when component form, membrane thicknesses is 0.01 ~ 0.05mm.
Described polymer A is one or more the mixture in polyethylene terephthalate (being 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-ten two-1,12-bis-acyl hexanediamine (be called for short PA612), polyenanthoamide (being called for short PA7), poly-13 lactan (being called for short PA13), and any one 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) (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 1.03MAH%(MAH and maleic anhydride, the massfraction of the maleic anhydride of grafting in the polyethylene particles of MAH% representation unit quality), melting index be 1.0g/10min(testing standard is ASTMD1238, condition is 190 DEG C, 2.16kg), density is 0.94g/cm 3, fusing point 130 ~ 135 DEG C maleic anhydride grafted polyethylene.
Described pore former is particle diameter be 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: in described polymer A preferably: the density of polyethylene terephthalate is 1.40g/cm 3, fusing point within the scope of 255 ~ 260 DEG C, 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 DEG C, 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 DEG C, limiting viscosity is 0.57dL/g.
In described polymer B preferably: the density of polyhexamethylene sebacamide (being called for short PA610) is 1.09g/cm 3, fusing point within the scope of 215 ~ 222 DEG C, heat-drawn wire is 60 DEG C (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 DEG C, heat-drawn wire is 65 DEG C (testing standard is ASTMD648, 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 DEG C, heat-drawn wire is 75 DEG C (testing standard is ASTMD648, 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 DEG C ~ 190 DEG C, and heat-drawn wire is 54 DEG C (testing standard is ASTMD648, 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 DEG C, and heat-drawn wire is 54.5 DEG C (testing standard is ASTMD648, and condition is 1.82MPa); The density of poly-ten two-1,12-bis-acyl hexanediamines (being called for short PA612) is 1.06g/cm 3, fusing point is within the scope of 218 ~ 222 DEG C, and heat-drawn wire is 62 DEG C (testing standard is ASTMD648, 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 DEG C, and heat-drawn wire is 40 DEG C (testing standard is ASTMD648, 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 DEG C, and heat-drawn wire is 58 DEG C (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 DEG C, and heat-drawn wire is 50.5 DEG C (testing standard is ASTMD648, 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 DEG C, heat-drawn wire is 135 DEG C (testing standard is ASTMD648, and condition is 1.82MPa), melting index be 6g/10min(testing standard is ASTMD1238, condition is 300 DEG C, 1.2kg); The fusing point of poly(4-methyl-1-pentene) (be called for short PMP) within the scope of 238 ~ 242 DEG C, heat-drawn wire is 80 DEG C (testing standard is ASTMD648, condition is 0.45MPa), melting index be 215g/10min(testing standard is ASTMD1238, condition is 260 DEG C, 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 serondary lithium battery polyester micro-pore septum, is characterized in that comprising the following steps:
A, batching and pre-treatment:
By 40 ~ 79% polymer A, 15 ~ 30% polymer B, 5 ~ 15% compatilizers and 1 ~ 15% pore former percent mass when 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 at 160 DEG C of dryings 4 hours, polybutylene terephthalate at 120 DEG C of dryings 8 hours, polybutylene terephthalate in 120 DEG C of dryings 8 hours, Poly(Trimethylene Terephthalate) 120 DEG C of dryings 8 hours, for subsequent use.
Described polymer B is polyhexamethylene sebacamide (be called for short PA610), any one in 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-ten two-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) (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) (being called for short PMP).And by described polyhexamethylene sebacamide 90 DEG C of dryings 12 hours, polycaprolactam was 100 DEG C of dryings 10 hours, polyhexamethylene adipamide was 90 DEG C of dryings 5 hours, nylon 1010 at 95 DEG C dry 5 hours, poly-11 lactan at 85 DEG C dry 7 hours, nylon 12 at 85 DEG C dry 5 hours, poly-ten two-1, 12-bis-acyl hexanediamine at 105 DEG C dry 12 hours, polyenanthoamide at 90 DEG C dry 6 hours, poly-13 lactan at 80 DEG C dry 6 hours, bisphenol A polycarbonate was 120 DEG C of dryings 6 hours, poly(4-methyl-1-pentene) was 80 DEG C of dryings 5 hours, for subsequent use.
Described compatilizer is maleic anhydride grafted polyethylene (being called for short PE-g-MAH); Preferably for percentage of grafting is 1.03MAH%(MAH and maleic anhydride, the massfraction of the maleic anhydride of grafting in the polyethylene particles of MAH% representation unit quality), melting index be 1.0g/10min(testing standard is ASTMD1238, condition is 190 DEG C, 2.16kg), density is 0.94g/cm 3, fusing point 130 ~ 135 DEG C maleic anhydride grafted polyethylene.
Described pore former is particle diameter be 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, extrude after melting mixing at the temperature of 240 DEG C ~ 320 DEG C through twin screw extruder, be cut into particle, the particle obtained is dried to moisture content again lower than after 200ppm, to drop in single screw extrusion machine melting mixing at the temperature of 240 DEG C ~ 320 DEG C again to extrude, the cold drum being 10 DEG C ~ 60 DEG C through temperature cools and is cast into the sheet that thickness is 0.2 ~ 0.3mm; First after sheet being carried out longitudinal stretching 2 ~ 8 times at the temperature of 80 DEG C ~ 150 DEG C again, by the drying tunnel preheating that temperature is 80 DEG C ~ 150 DEG C, synchronous longitudinal stretching 2 ~ 6 times and cross directional stretch 1.5 ~ 8 times at the temperature of 80 DEG C ~ 150 DEG C again, last heat setting type process at the temperature of 120 DEG C ~ 150 DEG C, i.e. obtained 0.01 ~ 0.05mm polyester micro-pore septum.
In another content of the present invention: prepare serondary lithium battery polyester micro-pore septum described in step b and also can be replaced: polymer A, polymer B, compatilizer and pore former (through high mixer) are mixed, extrude after melting mixing at the temperature of 250 DEG C ~ 290 DEG C through twin screw extruder, be cut into particle, the particle obtained is dried to moisture content again lower than after 200ppm, to drop in single screw extrusion machine melting mixing at the temperature of 250 DEG C ~ 290 DEG C again to extrude, the cold drum being 20 DEG C ~ 40 DEG C through temperature cools and is cast into the sheet that thickness is 0.2 ~ 0.3mm; First after sheet being carried out longitudinal stretching 2 ~ 6 times at the temperature of 90 DEG C ~ 135 DEG C again, by the drying tunnel preheating that temperature is 90 DEG C ~ 135 DEG C, synchronous longitudinal stretching 2 ~ 6 times and cross directional stretch 2 ~ 3.5 times at the temperature of 90 DEG C ~ 135 DEG C again, last heat setting type process at the temperature of 120 DEG C ~ 150 DEG C, i.e. obtained 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 DEG C, 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 DEG C, 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 DEG C, 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 DEG C, heat-drawn wire is 60 DEG C (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 DEG C, heat-drawn wire is 65 DEG C (testing standard is ASTMD648, 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 DEG C, heat-drawn wire is 75 DEG C (testing standard is ASTMD648, 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 DEG C ~ 190 DEG C, and heat-drawn wire is 54 DEG C (testing standard is ASTMD648, 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 DEG C, and heat-drawn wire is 54.5 DEG C (testing standard is ASTMD648, and condition is 1.82MPa); The density of poly-ten two-1,12-bis-acyl hexanediamines (being called for short PA612) is 1.06g/cm 3, fusing point is within the scope of 218 ~ 222 DEG C, and heat-drawn wire is 62 DEG C (testing standard is ASTMD648, 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 DEG C, and heat-drawn wire is 40 DEG C (testing standard is ASTMD648, 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 DEG C, and heat-drawn wire is 58 DEG C (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 DEG C, and heat-drawn wire is 50.5 DEG C (testing standard is ASTMD648, 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 DEG C, heat-drawn wire is 135 DEG C (testing standard is ASTMD648, and condition is 1.82MPa), melting index be 6g/10min(testing standard is ASTMD1238, condition is 300 DEG C, 1.2kg); The fusing point of poly(4-methyl-1-pentene) (be called for short PMP) within the scope of 238 ~ 242 DEG C, heat-drawn wire is 80 DEG C (testing standard is ASTMD648, condition is 0.45MPa), melting index be 215g/10min(testing standard is ASTMD1238, condition is 260 DEG C, 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 features and beneficial effect:
(1) polymer A, polymer B, compatilizer and pore former mix by the present invention by a certain percentage, by twin screw extruder extruding pelletization, dry, extrude through twin screw extruder again, after cold founding sheet, first carry out longitudinal stretching, then two-way stretch, obtain serondary lithium battery polyester micro-pore septum; 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 uses polyester material, make the barrier film that obtains be less than 10% at the percent thermal shrinkage of 160 DEG C; Indulge lateral performance through synchronous bidirectional stretching metacneme more even, its tensile strength is all greater than 35MPa; The ventilation property of room temperature lower diaphragm plate can reach 500s/100mL; Breach existing with the restriction of polyolefine material, can only solving and adopt the technical barrier of dry process using polyester material as serondary lithium battery micro-pore septum base material;
(3) adopt the present invention, barrier film production technique is simple, and high-temperature hot shrinking percentage is little, barrier film in length and breadth to more even, good permeability (as shown in table 1); Can be used for lithium ion battery or the lithium cell of 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., it is especially mentioned that 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 is intended 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 number given in table 1 at different conditions drying, extrude after 280 DEG C of melting mixings through twin screw extruder and be cut into particle, after the particle obtained is dried to moisture content 200ppm again, drop into single screw extrusion machine melting mixing under 280 DEG C of conditions again to extrude, the sheet that thickness is 0.2 ~ 0.3mm is cast into through the cold drum cooling of 20 DEG C ~ 40 DEG C, after first carrying out longitudinal stretching 2 times under 120 DEG C of conditions, again by the drying tunnel preheating of 135 DEG C, synchronous bidirectional stretching is carried out under 135 DEG C of conditions, longitudinal stretching 2 times and cross directional stretch 2.5 times, heat setting type process at 135 DEG C again, obtain polyester micro-pore septum.
Embodiment 2-1,2-2:
After each component materials with certain proportion number given in table 1 at different conditions drying, extrude after 275 DEG C of melting mixings through twin screw extruder and be cut into particle, after the particle obtained is dried to moisture content 200ppm again, drop into single screw extrusion machine melting mixing under 275 DEG C of conditions again to extrude, the sheet that thickness is 0.2 ~ 0.3mm is cast into through the cold drum cooling of 20 DEG C ~ 40 DEG C, after first carrying out longitudinal stretching 2 times under 100 DEG C of conditions, by the drying tunnel preheating of 110 DEG C, synchronous bidirectional stretching is carried out under 110 DEG C of conditions, longitudinal stretching 2 times and cross directional stretch 3 times, heat setting type process at 145 DEG C again, obtain polyester micro-pore septum.
Embodiment 3-1,3-2:
After each component materials with certain proportion number given in table 1 at different conditions drying, extrude after 285 DEG C of melting mixings through twin screw extruder and be cut into particle, after the particle obtained is dried to moisture content 200ppm again, drop into single screw extrusion machine melting mixing under 285 DEG C of conditions again to extrude, the sheet that thickness is 0.2 ~ 0.3mm is cast into through the cold drum cooling of 20 DEG C ~ 40 DEG C, after first carrying out longitudinal stretching 2 times under 105 DEG C of conditions, by the drying tunnel preheating of 115 DEG C, synchronous bidirectional stretching is carried out under 115 DEG C of conditions, longitudinal stretching 2 times and cross directional stretch 2.8 times, heat setting type process at 150 DEG C again, obtain polyester micro-pore septum.
Embodiment 4-1,4-2:
After each component materials with certain proportion number given in table 1 at different conditions drying, extrude after 280 DEG C of melting mixings through twin screw extruder and be cut into particle, after the particle obtained is dried to moisture content 200ppm again, drop into single screw extrusion machine melting mixing under 280 DEG C of conditions again to extrude, the sheet that thickness is 0.2 ~ 0.3mm is cast into through the cold drum cooling of 20 DEG C ~ 40 DEG C, after first carrying out longitudinal stretching 2 times under 100 DEG C of conditions, by the drying tunnel preheating of 105 DEG C, synchronous bidirectional stretching is carried out under 105 DEG C of conditions, longitudinal stretching 2.2 times and cross directional stretch 2.5 times, heat setting type process at 145 DEG C again, obtain polyester micro-pore septum.
Embodiment 5-1,5-2:
After each component materials with certain proportion number given in table 1 at different conditions drying, extrude after 275 DEG C of melting mixings through twin screw extruder and be cut into particle, after the particle obtained is dried to moisture content 200ppm again, drop into single screw extrusion machine melting mixing under 275 DEG C of conditions again to extrude, the sheet that thickness is 0.2 ~ 0.3mm is cast into through the cold drum cooling of 20 DEG C ~ 40 DEG C, after first carrying out longitudinal stretching 2 times under 90 DEG C of conditions, by the drying tunnel preheating of 90 DEG C, synchronous bidirectional stretching is carried out under 90 DEG C of conditions, longitudinal stretching 3 times and cross directional stretch 2.5 times, heat setting type process at 120 DEG C again, obtain polyester micro-pore septum.
Embodiment 6-1,6-2:
After each component materials with certain proportion number given in table 1 at different conditions drying, extrude after 260 DEG C of melting mixings through twin screw extruder and be cut into particle, after the particle obtained is dried to moisture content 200ppm again, drop into single screw extrusion machine melting mixing under 260 DEG C of conditions again to extrude, the sheet that thickness is 0.2 ~ 0.3mm is cast into through the cold drum cooling of 20 DEG C ~ 40 DEG C, after first carrying out longitudinal stretching 2 times under 90 DEG C of conditions, by the drying tunnel preheating of 95 DEG C, synchronous bidirectional stretching is carried out under 95 DEG C of conditions, longitudinal stretching 2.5 times and cross directional stretch 2.5 times, heat setting type process at 120 DEG C again, obtain polyester micro-pore septum.
Embodiment 7-1,7-2:
After each component materials with certain proportion number given in table 1 at different conditions drying, extrude after 270 DEG C of melting mixings through twin screw extruder and be cut into particle, after the particle obtained is dried to moisture content 200ppm again, drop into single screw extrusion machine melting mixing under 270 DEG C of conditions again to extrude, the sheet that thickness is 0.2 ~ 0.3mm is cast into through the cold drum cooling of 20 DEG C ~ 40 DEG C, after first carrying out longitudinal stretching 2 times under 105 DEG C of conditions, by the drying tunnel preheating of 115 DEG C, synchronous bidirectional stretching is carried out under 115 DEG C of conditions, longitudinal stretching 2 times and cross directional stretch 2.8 times, heat setting type process at 125 DEG C again, obtain polyester micro-pore septum.
Embodiment 8-1,8-2:
By continued 1(1) in given each component materials with certain proportion number at different conditions after drying, extrude after 265 DEG C of melting mixings through twin screw extruder and be cut into particle, after the particle obtained is dried to moisture content 200ppm again, drop into single screw extrusion machine melting mixing under 265 DEG C of conditions again to extrude, the sheet that thickness is 0.2 ~ 0.3mm is cast into through the cold drum cooling of 20 DEG C ~ 40 DEG C, after first carrying out longitudinal stretching 2 times under 100 DEG C of conditions, by the drying tunnel preheating of 110 DEG C, synchronous bidirectional stretching is carried out under 110 DEG C of conditions, longitudinal stretching 2.2 times and cross directional stretch 2.5 times, heat setting type process at 135 DEG C again, obtain polyester micro-pore septum.
Embodiment 9-1,9-2:
By continued 1(1) in given each component materials with certain proportion number at different conditions after drying, extrude after 275 DEG C of melting mixings through twin screw extruder and be cut into particle, after the particle obtained is dried to moisture content 200ppm again, drop into single screw extrusion machine melting mixing under 275 DEG C of conditions again to extrude, the sheet that thickness is 0.2 ~ 0.3mm is cast into through the cold drum cooling of 20 DEG C ~ 40 DEG C, after first carrying out longitudinal stretching 2 times under 100 DEG C of conditions, by the drying tunnel preheating of 105 DEG C, synchronous bidirectional stretching is carried out under 105 DEG C of conditions, longitudinal stretching 2.5 times and cross directional stretch 2.5 times, heat setting type process at 135 DEG C again, obtain polyester micro-pore septum.
Embodiment 10-1,10-2:
By continued 1(1) in given each component materials with certain proportion number at different conditions after drying, extrude after 270 DEG C of melting mixings through twin screw extruder and be cut into particle, after the particle obtained is dried to moisture content 200ppm again, drop into single screw extrusion machine melting mixing under 270 DEG C of conditions again to extrude, the sheet that thickness is 0.2 ~ 0.3mm is cast into through the cold drum cooling of 20 DEG C ~ 40 DEG C, after first carrying out longitudinal stretching 2 times under 100 DEG C of conditions, by the drying tunnel preheating of 105 DEG C, synchronous bidirectional stretching is carried out under 105 DEG C of conditions, longitudinal stretching 2.3 times and cross directional stretch 2.8 times, heat setting type process at 145 DEG C again, obtain polyester micro-pore septum.
Embodiment 11-1,11-2:
By continued 1(1) in given each component materials with certain proportion number at different conditions after drying, extrude after 265 DEG C of melting mixings through twin screw extruder and be cut into particle, after the particle obtained is dried to moisture content 200ppm again, drop into single screw extrusion machine melting mixing under 265 DEG C of conditions again to extrude, the sheet that thickness is 0.2 ~ 0.3mm is cast into through the cold drum cooling of 20 DEG C ~ 40 DEG C, after first carrying out longitudinal stretching 2 times under 95 DEG C of conditions, by the drying tunnel preheating of 100 DEG C, synchronous bidirectional stretching is carried out under 100 DEG C of conditions, longitudinal stretching 2 times and cross directional stretch 3 times, heat setting type process at 140 DEG C again, obtain polyester micro-pore septum.
Embodiment 12-1,12-2:
By continued 1(1) in given each component materials with certain proportion number at different conditions after drying, extrude after 265 DEG C of melting mixings through twin screw extruder and be cut into particle, after the particle obtained is dried to moisture content 200ppm again, drop into single screw extrusion machine melting mixing under 265 DEG C of conditions again to extrude, the sheet that thickness is 0.2 ~ 0.3mm is cast into through the cold drum cooling of 20 DEG C ~ 40 DEG C, after first carrying out longitudinal stretching 2 times under 100 DEG C of conditions, by the drying tunnel preheating of 105 DEG C, synchronous bidirectional stretching is carried out under 105 DEG C of conditions, longitudinal stretching 2.5 times and cross directional stretch 2.5 times, heat setting type process at 145 DEG C again, obtain polyester micro-pore septum.
Embodiment 13-1,13-2:
By continued 1(2) in given each component materials with certain proportion number at different conditions after drying, extrude after 275 DEG C of melting mixings through twin screw extruder and be cut into particle, after the particle obtained is dried to moisture content 200ppm again, drop into single screw extrusion machine melting mixing under 275 DEG C of conditions again to extrude, the sheet that thickness is 0.2 ~ 0.3mm is cast into through the cold drum cooling of 20 DEG C ~ 40 DEG C, after first carrying out longitudinal stretching 2.5 times under 120 DEG C of conditions, by the drying tunnel preheating of 125 DEG C, synchronous bidirectional stretching is carried out under 125 DEG C of conditions, longitudinal stretching 2.5 times and cross directional stretch 2.5 times, heat setting type process at 150 DEG C again, obtain polyester micro-pore septum.
Embodiment 14-1,14-2:
By continued 1(2) in given each component materials with certain proportion number at different conditions after drying, extrude after 275 DEG C of melting mixings through twin screw extruder and be cut into particle, after the particle obtained is dried to moisture content 200ppm again, drop into single screw extrusion machine melting mixing under 275 DEG C of conditions again to extrude, the sheet that thickness is 0.2 ~ 0.3mm is cast into through the cold drum cooling of 20 DEG C ~ 40 DEG C, after first carrying out longitudinal stretching 2.3 times under 110 DEG C of conditions, by the drying tunnel preheating of 120 DEG C, synchronous bidirectional stretching is carried out under 120 DEG C of conditions, longitudinal stretching 2.5 times and cross directional stretch 2.8 times, heat setting type process at 150 DEG C again, obtain polyester micro-pore septum.
Embodiment 15-1,15-2:
By continued 1(2) in given each component materials with certain proportion number at different conditions after drying, extrude after 280 DEG C of melting mixings through twin screw extruder and be cut into particle, after the particle obtained is dried to moisture content 200ppm again, drop into single screw extrusion machine melting mixing under 280 DEG C of conditions again to extrude, the sheet that thickness is 0.2 ~ 0.3mm is cast into through the cold drum cooling of 20 DEG C ~ 40 DEG C, after first carrying out longitudinal stretching 3 times under 130 DEG C of conditions, by the drying tunnel preheating of 135 DEG C, synchronous bidirectional stretching is carried out under 135 DEG C of conditions, longitudinal stretching 2.5 times and cross directional stretch 2 times, heat setting type process at 145 DEG C 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 by 40 ~ 79% polymer A, 15 ~ 30% polymer B, 5 ~ 15% compatilizers and 1 ~ 15% pore former percent mass when component form;
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 (being 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 (be called for short PA610), any one in 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-ten two-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) (abbreviation PMP).
Described compatilizer is maleic anhydride grafted polyethylene (being called for short PE-g-MAH); Preferably for percentage of grafting is 1.03MAH%(MAH and maleic anhydride, the massfraction of the maleic anhydride of grafting in the polyethylene particles of MAH% representation unit quality), melting index be 1.0g/10min(testing standard is ASTMD1238, condition is 190 DEG C, 2.16kg), density is 0.94g/cm 3, fusing point 130 ~ 135 DEG C maleic anhydride grafted polyethylene;
Described pore former is particle diameter be 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 DEG C, 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 DEG C, 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 DEG C, 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 DEG C, heat-drawn wire is 60 DEG C (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 DEG C, heat-drawn wire is 65 DEG C (testing standard is ASTMD648, 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 DEG C, heat-drawn wire is 75 DEG C (testing standard is ASTMD648, 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 DEG C ~ 190 DEG C, and heat-drawn wire is 54 DEG C (testing standard is ASTMD648, 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 DEG C, and heat-drawn wire is 54.5 DEG C (testing standard is ASTMD648, and condition is 1.82MPa); The density of poly-ten two-1,12-bis-acyl hexanediamines (being called for short PA612) is 1.06g/cm 3, fusing point is within the scope of 218 ~ 222 DEG C, and heat-drawn wire is 62 DEG C (testing standard is ASTMD648, 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 DEG C, and heat-drawn wire is 40 DEG C (testing standard is ASTMD648, 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 DEG C, and heat-drawn wire is 58 DEG C (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 DEG C, and heat-drawn wire is 50.5 DEG C (testing standard is ASTMD648, 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 DEG C, heat-drawn wire is 135 DEG C (testing standard is ASTMD648, and condition is 1.82MPa), melting index be 6g/10min(testing standard is ASTMD1238, condition is 300 DEG C, 1.2kg); The fusing point of poly(4-methyl-1-pentene) (be called for short PMP) within the scope of 238 ~ 242 DEG C, heat-drawn wire is 80 DEG C (testing standard is ASTMD648, condition is 0.45MPa), melting index be 215g/10min(testing standard is ASTMD1238, condition is 260 DEG C, 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 serondary lithium battery preparation method of polyester micro-pore septum, is characterized in that comprising the following steps:
A, batching and pre-treatment:
By 40 ~ 79% polymer A, 15 ~ 30% polymer B, 5 ~ 15% compatilizers and 1 ~ 15% pore former percent mass when 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 at 160 DEG C of dryings 4 hours, polybutylene terephthalate at 120 DEG C of dryings 8 hours, polybutylene terephthalate in 120 DEG C of dryings 8 hours, Poly(Trimethylene Terephthalate) 120 DEG C of dryings 8 hours, for subsequent use;
Described polymer B is polyhexamethylene sebacamide (be called for short PA610), any one in 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-ten two-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) (abbreviation PMP).And by described polyhexamethylene sebacamide 90 DEG C of dryings 12 hours, polycaprolactam was 100 DEG C of dryings 10 hours, polyhexamethylene adipamide was 90 DEG C of dryings 5 hours, nylon 1010 at 95 DEG C dry 5 hours, poly-11 lactan at 85 DEG C dry 7 hours, nylon 12 at 85 DEG C dry 5 hours, poly-ten two-1, 12-bis-acyl hexanediamine at 105 DEG C dry 12 hours, polyenanthoamide at 90 DEG C dry 6 hours, poly-13 lactan at 80 DEG C dry 6 hours, bisphenol A polycarbonate was 120 DEG C of dryings 6 hours, poly(4-methyl-1-pentene) was 80 DEG C of dryings 5 hours, for subsequent use,
Described compatilizer is maleic anhydride grafted polyethylene (being called for short PE-g-MAH); Preferably for percentage of grafting is 1.03MAH%(MAH and maleic anhydride, the massfraction of the maleic anhydride of grafting in the polyethylene particles of MAH% representation unit quality), melting index be 1.0g/10min(testing standard is ASTMD1238, condition is 190 DEG C, 2.16kg), density is 0.94g/cm 3, fusing point 130 ~ 135 DEG C maleic anhydride grafted polyethylene;
Described pore former is particle diameter be 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, extrude after melting mixing at the temperature of 240 DEG C ~ 320 DEG C through twin screw extruder, be cut into particle, the particle obtained is dried to moisture content again lower than after 200ppm, to drop in single screw extrusion machine melting mixing at the temperature of 240 DEG C ~ 320 DEG C again to extrude, the cold drum being 10 DEG C ~ 60 DEG C through temperature cools and is cast into the sheet that thickness is 0.2 ~ 0.3mm; First after sheet being carried out longitudinal stretching 2 ~ 8 times at the temperature of 80 DEG C ~ 150 DEG C again, by the drying tunnel preheating that temperature is 80 DEG C ~ 150 DEG C, synchronous longitudinal stretching 2 ~ 6 times and cross directional stretch 1.5 ~ 8 times at the temperature of 80 DEG C ~ 150 DEG C again, last heat setting type process at the temperature of 120 DEG C ~ 150 DEG C, i.e. obtained 0.01 ~ 0.05mm polyester micro-pore septum.
Embodiment 30:
The serondary lithium battery preparation method of polyester micro-pore septum, prepare serondary lithium battery polyester micro-pore septum described in step b to replace with: polymer A, polymer B, compatilizer and pore former are mixed through high-speed mixer, extrude after melting mixing at the temperature of 240 DEG C through twin screw extruder, be cut into particle, the particle obtained is dried to moisture content again lower than after 200ppm, to drop in single screw extrusion machine melting mixing at the temperature of 240 DEG C again to extrude, the cold drum being 10 DEG C through temperature cools and is cast into the sheet that thickness is 0.2mm; First after sheet being carried out longitudinal stretching 2 times at the temperature of 80 DEG C again, by the drying tunnel preheating that temperature is 80 DEG C, synchronous longitudinal stretching 2 times and cross directional stretch 1.5 times at the temperature of 80 DEG C again, finally heat setting type process at the temperature of 120 DEG C, i.e. obtained 0.01 ~ 0.05mm polyester micro-pore septum.Arbitrary in the other the same as in Example 23 ~ 29, omit.
Embodiment 31:
The serondary lithium battery preparation method of polyester micro-pore septum, prepare serondary lithium battery polyester micro-pore septum described in step b to replace with: polymer A, polymer B, compatilizer and pore former are mixed through high-speed mixer, extrude after melting mixing at the temperature of 320 DEG C through twin screw extruder, be cut into particle, the particle obtained is dried to moisture content again lower than after 200ppm, to drop in single screw extrusion machine melting mixing at the temperature of 320 DEG C again to extrude, the cold drum being 60 DEG C through temperature cools and is cast into the sheet that thickness is 0.3mm; First after sheet being carried out longitudinal stretching 8 times at the temperature of 150 DEG C again, by the drying tunnel preheating that temperature is 150 DEG C, synchronous longitudinal stretching 6 times and cross directional stretch 8 times at the temperature of 150 DEG C again, finally heat setting type process at the temperature of 150 DEG C, i.e. obtained 0.01 ~ 0.05mm polyester micro-pore septum.Arbitrary in the other the same as in Example 23 ~ 29, omit.
Embodiment 32:
The serondary lithium battery preparation method of polyester micro-pore septum, prepare serondary lithium battery polyester micro-pore septum described in step b to replace with: polymer A, polymer B, compatilizer and pore former are mixed through high-speed mixer, extrude after melting mixing at the temperature of 280 DEG C through twin screw extruder, be cut into particle, the particle obtained is dried to moisture content again lower than after 200ppm, to drop in single screw extrusion machine melting mixing at the temperature of 280 DEG C again to extrude, the cold drum being 40 DEG C through temperature cools and is cast into the sheet that thickness is 0.25mm; First after sheet being carried out longitudinal stretching 5 times at the temperature of 120 DEG C again, by the drying tunnel preheating that temperature is 120 DEG C, synchronous longitudinal stretching 4 times and cross directional stretch 5 times at the temperature of 120 DEG C again, finally heat setting type process at the temperature of 130 DEG C, i.e. obtained 0.01 ~ 0.05mm polyester micro-pore septum.Arbitrary in the other the same as in Example 23 ~ 29, omit.
Embodiment 33:
The serondary lithium battery preparation method of polyester micro-pore septum, prepare serondary lithium battery polyester micro-pore septum described in step b to replace with: by polymer A, polymer B, compatilizer and pore former mix through high-speed mixer, extrude after melting mixing at the temperature of 250 DEG C ~ 290 DEG C through twin screw extruder, be cut into particle, the particle obtained is dried to moisture content again lower than after 200ppm, to drop in single screw extrusion machine melting mixing at the temperature of 250 DEG C ~ 290 DEG C again to extrude, the cold drum being 20 DEG C ~ 40 DEG C through temperature cools and is cast into the sheet that thickness is 0.2 ~ 0.3mm, first after sheet being carried out longitudinal stretching 2 ~ 6 times at the temperature of 90 DEG C ~ 135 DEG C again, by the drying tunnel preheating that temperature is 90 DEG C ~ 135 DEG C, synchronous longitudinal stretching 2 ~ 6 times and cross directional stretch 2 ~ 3.5 times at the temperature of 90 DEG C ~ 135 DEG C again, last heat setting type process at the temperature of 120 DEG C ~ 150 DEG C, i.e. obtained 0.01 ~ 0.05mm polyester micro-pore septum.Arbitrary in the other the same as in Example 23 ~ 29, omit.
Embodiment 34:
The serondary lithium battery preparation method of polyester micro-pore septum, prepare serondary lithium battery polyester micro-pore septum described in step b to replace with: polymer A, polymer B, compatilizer and pore former are mixed through high-speed mixer, extrude after melting mixing at the temperature of 290 DEG C through twin screw extruder, be cut into particle, the particle obtained is dried to moisture content again lower than after 200ppm, to drop in single screw extrusion machine melting mixing at the temperature of 290 DEG C again to extrude, the cold drum being 40 DEG C through temperature cools and is cast into the sheet that thickness is 0.3mm; First after sheet being carried out longitudinal stretching 6 times at the temperature of 135 DEG C again, by the drying tunnel preheating that temperature is 135 DEG C, synchronous longitudinal stretching 6 times and cross directional stretch 3.5 times at the temperature of 135 DEG C again, last heat setting type process at the temperature of 150 DEG C, i.e. obtained 0.01 ~ 0.05mm polyester micro-pore septum.Arbitrary in the other the same as in Example 23 ~ 29, omit.
Embodiment 35:
The serondary lithium battery preparation method of polyester micro-pore septum, prepare serondary lithium battery polyester micro-pore septum described in step b to replace with: polymer A, polymer B, compatilizer and pore former are mixed through high-speed mixer, extrude after melting mixing at the temperature of 250 DEG C through twin screw extruder, be cut into particle, the particle obtained is dried to moisture content again lower than after 200ppm, to drop in single screw extrusion machine melting mixing at the temperature of 250 DEG C again to extrude, the cold drum being 20 DEG C through temperature cools and is cast into the sheet that thickness is 0.2mm; First after sheet being carried out longitudinal stretching 2 times at the temperature of 90 DEG C again, by the drying tunnel preheating that temperature is 90 DEG C, synchronous longitudinal stretching 2 times and cross directional stretch 2 times at the temperature of 90 DEG C again, finally heat setting type process at the temperature of 120 DEG C, i.e. obtained 0.01 ~ 0.05mm polyester micro-pore septum.Arbitrary in the other the same as in Example 23 ~ 29, omit.
Embodiment 36:
The serondary lithium battery preparation method of polyester micro-pore septum, prepare serondary lithium battery polyester micro-pore septum described in step b to replace with: polymer A, polymer B, compatilizer and pore former are mixed through high-speed mixer, extrude after melting mixing at the temperature of 270 DEG C through twin screw extruder, be cut into particle, the particle obtained is dried to moisture content again lower than after 200ppm, to drop in single screw extrusion machine melting mixing at the temperature of 270 DEG C again to extrude, the cold drum being 30 DEG C through temperature cools and is cast into the sheet that thickness is 0.25mm; First after sheet being carried out longitudinal stretching 4 times at the temperature of 115 DEG C again, by the drying tunnel preheating that temperature is 115 DEG C, synchronous longitudinal stretching 4 times and cross directional stretch 2.8 times at the temperature of 115 DEG C again, last heat setting type process at the temperature of 135 DEG C, i.e. obtained 0.01 ~ 0.05mm polyester micro-pore septum.Arbitrary in the other the same as in Example 23 ~ 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 DEG C, 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 DEG C, 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 DEG C, 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 DEG C, heat-drawn wire is 60 DEG C (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 DEG C, heat-drawn wire is 65 DEG C (testing standard is ASTMD648, 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 DEG C, heat-drawn wire is 75 DEG C (testing standard is ASTMD648, 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 DEG C ~ 190 DEG C, and heat-drawn wire is 54 DEG C (testing standard is ASTMD648, 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 DEG C, and heat-drawn wire is 54.5 DEG C (testing standard is ASTMD648, and condition is 1.82MPa); The density of poly-ten two-1,12-bis-acyl hexanediamines (being called for short PA612) is 1.06g/cm 3, fusing point is within the scope of 218 ~ 222 DEG C, and heat-drawn wire is 62 DEG C (testing standard is ASTMD648, 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 DEG C, and heat-drawn wire is 40 DEG C (testing standard is ASTMD648, 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 DEG C, and heat-drawn wire is 58 DEG C (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 DEG C, and heat-drawn wire is 50.5 DEG C (testing standard is ASTMD648, 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 DEG C, heat-drawn wire is 135 DEG C (testing standard is ASTMD648, and condition is 1.82MPa), melting index be 6g/10min(testing standard is ASTMD1238, condition is 300 DEG C, 1.2kg); The fusing point of poly(4-methyl-1-pentene) (be called for short PMP) within the scope of 238 ~ 242 DEG C, heat-drawn wire is 80 DEG C (testing standard is ASTMD648, condition is 0.45MPa), melting index be 215g/10min(testing standard is ASTMD1238, condition is 260 DEG C, 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 adopted, do not indicate especially, be quality (weight) percentage (wt% is mass percent); In the ratio adopted, do not indicate especially, be quality (weight) ratio; Described weight part can be all kilogram or ton.
In above-described embodiment: the processing parameter (temperature, time, concentration etc.) in each step and each amounts of components numerical value etc. are scope, and any point is all applicable.
The concrete same prior art of technology contents described 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 described in content of the present invention and there is described good result.

Claims (10)

1. serondary lithium battery polyester micro-pore septum, it is characterized in that: (1) this barrier film by 40 ~ 79% polymer A, 15 ~ 30% polymer B, 5 ~ 15% compatilizers and 1 ~ 15% pore former percent mass when component form, membrane thicknesses is 0.01 ~ 0.05mm; And polymer A, polymer B, compatilizer and pore former are mixed (2), at 240 DEG C ~ 320 DEG C, pelletizing is melt extruded through twin screw extruder, be dried to moisture content again lower than after 200ppm, to drop in single screw extrusion machine melting mixing at the temperature of 240 DEG C ~ 320 DEG C again to extrude, the cold drum being 10 DEG C ~ 60 DEG C through temperature cools and is cast into the sheet that thickness is 0.2 ~ 0.3mm; First after sheet being carried out longitudinal stretching 2 ~ 8 times at the temperature of 80 DEG C ~ 150 DEG C again, by the drying tunnel preheating that temperature is 80 DEG C ~ 150 DEG C, synchronous longitudinal stretching 2 ~ 6 times and cross directional stretch 1.5 ~ 8 times at the temperature of 80 DEG C ~ 150 DEG C again, last heat setting type process at the temperature of 120 DEG C ~ 150 DEG C, i.e. obtained described polyester micro-pore septum;
Described polymer A is one or more the mixture in polyethylene terephthalate, polybutylene terephthalate, Poly(Trimethylene Terephthalate);
Described polymer B is any one in polyhexamethylene sebacamide, polycaprolactam, polyhexamethylene adipamide, nylon 1010, poly-11 lactan, nylon 12, poly-ten two-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;
The nano silicon of described pore former to be particle diameter be 40 ~ 80nm.
2. serondary lithium battery polyester micro-pore septum according to claim 1, it is characterized in that: the feature (2) in claim 1 replaces with: and polymer A, polymer B, compatilizer and pore former are mixed, at 250 DEG C ~ 290 DEG C, pelletizing is extruded after melting mixing through twin screw extruder, be dried to moisture content again lower than after 200ppm, to drop in single screw extrusion machine melting mixing at the temperature of 250 DEG C ~ 290 DEG C again to extrude, the cold drum being 20 DEG C ~ 40 DEG C through temperature cools and is cast into the sheet that thickness is 0.2 ~ 0.3mm; First after sheet being carried out longitudinal stretching 2 ~ 6 times at the temperature of 90 DEG C ~ 135 DEG C again, by the drying tunnel preheating that temperature is 90 DEG C ~ 135 DEG C, synchronous longitudinal stretching 2 ~ 6 times and cross directional stretch 2 ~ 3.5 times at the temperature of 90 DEG C ~ 135 DEG C again, last heat setting type process at the temperature of 120 DEG C ~ 150 DEG C, i.e. obtained described polyester micro-pore septum.
3., by the serondary lithium battery polyester micro-pore septum described in claim 1 or 2, it is characterized in that: the thickness of described barrier film is 0.02 ~ 0.03mm;
In described polymer A: the density of polyethylene terephthalate is 1.40g/cm 3, fusing point within the scope of 255 ~ 260 DEG C, 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 DEG C, 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 DEG C, 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 DEG C, heat-drawn wire is 60 DEG C; The density of polycaprolactam is 1.14g/cm 3, fusing point within the scope of 215 ~ 225 DEG C, heat-drawn wire is 65 DEG C; The density of polyhexamethylene adipamide is 1.15g/cm 3, fusing point is within the scope of 255 ~ 263 DEG C, heat-drawn wire is 75 DEG C; The density of poly-11 lactan is 1.05g/cm 3, fusing point is within the scope of 185 DEG C ~ 190 DEG C, and heat-drawn wire is 54 DEG C; The density of nylon 12 is 1.02g/cm 3, fusing point is within the scope of 173 ~ 180 DEG C, and heat-drawn wire is 54.5 DEG C; The density of poly-ten two-1,12-bis-acyl hexanediamines is 1.06g/cm 3, fusing point is within the scope of 218 ~ 222 DEG C, and heat-drawn wire is 62 DEG C; The density of nylon 1010 is 1.08g/cm 3, fusing point is within the scope of 200 ~ 210 DEG C, and heat-drawn wire is 40 DEG C; The density of polyenanthoamide is 1.11g/cm 3, fusing point is within the scope of 225 ~ 230 DEG C, and heat-drawn wire is 58 DEG C; The density of poly-13 lactan is 1.01g/cm 3, fusing point is within the scope of 180 ~ 183 DEG C, and heat-drawn wire is 50.5 DEG C; The density of bisphenol A polycarbonate is 1.20g/cm 3, fusing point within the scope of 247 ~ 254 DEG C, heat-drawn wire is 135 DEG C, melting index is 6g/10min; The fusing point of poly(4-methyl-1-pentene) within the scope of 238 ~ 242 DEG C, heat-drawn wire is 80 DEG C, melting index is 215g/10min.
4., by the serondary lithium battery polyester micro-pore septum described in claim 1 or 2, it is characterized in that: the thickness of described barrier film is 0.02 ~ 0.03mm;
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 serondary lithium battery preparation method of polyester micro-pore septum, is characterized in that comprising the following steps:
A, batching and pre-treatment:
By 40 ~ 79% polymer A, 15 ~ 30% polymer B, 5 ~ 15% compatilizers and 1 ~ 15% pore former percent mass when 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 at 160 DEG C of dryings 4 hours, polybutylene terephthalate at 120 DEG C of dryings 8 hours, polybutylene terephthalate in 120 DEG C of dryings 8 hours, Poly(Trimethylene Terephthalate) 120 DEG C of dryings 8 hours, for subsequent use;
Described polymer B is any one in polyhexamethylene sebacamide, polycaprolactam, polyhexamethylene adipamide, nylon 1010, poly-11 lactan, nylon 12, poly-ten two-1,12-bis-acyl hexanediamines, polyenanthoamide, poly-13 lactan, bisphenol A polycarbonate and poly(4-methyl-1-pentene), and by described polyhexamethylene sebacamide 90 DEG C of dryings 12 hours, polycaprolactam was 100 DEG C of dryings 10 hours, polyhexamethylene adipamide was 90 DEG C of dryings 5 hours, nylon 1010 at 95 DEG C dry 5 hours, poly-11 lactan at 85 DEG C dry 7 hours, nylon 12 at 85 DEG C dry 5 hours, poly-ten two-1, 12-bis-acyl hexanediamine at 105 DEG C dry 12 hours, polyenanthoamide at 90 DEG C dry 6 hours, poly-13 lactan at 80 DEG C dry 6 hours, bisphenol A polycarbonate was 120 DEG C of dryings 6 hours, poly(4-methyl-1-pentene) was 80 DEG C of dryings 5 hours, for subsequent use,
Described compatilizer is maleic anhydride grafted polyethylene;
The nano silicon of described pore former to be particle diameter be 40 ~ 80nm.
B, prepare serondary lithium battery polyester micro-pore septum:
Polymer A, polymer B, compatilizer and pore former are mixed, extrude after melting mixing at the temperature of 240 DEG C ~ 320 DEG C through twin screw extruder, be cut into particle, the particle obtained is dried to moisture content again lower than after 200ppm, to drop in single screw extrusion machine melting mixing at the temperature of 240 DEG C ~ 320 DEG C again to extrude, the cold drum being 10 DEG C ~ 60 DEG C through temperature cools and is cast into the sheet that thickness is 0.2 ~ 0.3mm; First after sheet being carried out longitudinal stretching 2 ~ 8 times at the temperature of 80 DEG C ~ 150 DEG C again, by the drying tunnel preheating that temperature is 80 DEG C ~ 150 DEG C, synchronous longitudinal stretching 2 ~ 6 times and cross directional stretch 1.5 ~ 8 times at the temperature of 80 DEG C ~ 150 DEG C again, last heat setting type process at the temperature of 120 DEG C ~ 150 DEG C, i.e. obtained 0.01 ~ 0.05mm polyester micro-pore septum.
6. by the preparation method of serondary lithium battery described in claim 5 with polyester micro-pore septum, it is characterized in that: prepare serondary lithium battery polyester micro-pore septum described in step b and replace with: by polymer A, polymer B, compatilizer and pore former mix, extrude after melting mixing at the temperature of 250 DEG C ~ 290 DEG C through twin screw extruder, be cut into particle, the particle obtained is dried to moisture content again lower than after 200ppm, to drop in single screw extrusion machine melting mixing at the temperature of 250 DEG C ~ 290 DEG C again to extrude, the cold drum being 20 DEG C ~ 40 DEG C through temperature cools and is cast into the sheet that thickness is 0.2 ~ 0.3mm, first after sheet being carried out longitudinal stretching 2 ~ 6 times at the temperature of 90 DEG C ~ 135 DEG C again, by the drying tunnel preheating that temperature is 90 DEG C ~ 135 DEG C, synchronous longitudinal stretching 2 ~ 6 times and cross directional stretch 2 ~ 3.5 times at the temperature of 90 DEG C ~ 135 DEG C again, last heat setting type process at the temperature of 120 DEG C ~ 150 DEG C, i.e. obtained 0.01 ~ 0.05mm polyester micro-pore septum.
7., by the serondary lithium battery preparation method of polyester micro-pore septum described in claim 5, it is characterized in that: the thickness of described barrier film is 0.02 ~ 0.03mm.
8., by the serondary lithium battery preparation method of polyester micro-pore septum described in claim 6, it is characterized in that: the thickness of described barrier film is 0.02 ~ 0.03mm.
9., by the serondary lithium battery preparation method of polyester micro-pore septum described in claim 5,6,7 or 8, 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 DEG C, 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 DEG C, 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 DEG C, 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 DEG C, heat-drawn wire is 60 DEG C; The density of polycaprolactam is 1.14g/cm 3, fusing point within the scope of 215 ~ 225 DEG C, heat-drawn wire is 65 DEG C; The density of polyhexamethylene adipamide is 1.15g/cm 3, fusing point is within the scope of 255 ~ 263 DEG C, heat-drawn wire is 75 DEG C; The density of poly-11 lactan is 1.05g/cm3, and fusing point is within the scope of 185 DEG C ~ 190 DEG C, and heat-drawn wire is 54 DEG C; The density of nylon 12 is 1.02g/cm3, and fusing point is within the scope of 173 ~ 180 DEG C, and heat-drawn wire is 54.5 DEG C; The density of poly-ten two-1,12-bis-acyl hexanediamines is 1.06g/cm3, and fusing point is within the scope of 218 ~ 222 DEG C, and heat-drawn wire is 62 DEG C; The density of nylon 1010 is 1.08g/cm3, and fusing point is within the scope of 200 ~ 210 DEG C, and heat-drawn wire is 40 DEG C; The density of polyenanthoamide is 1.11g/cm3, and fusing point is within the scope of 225 ~ 230 DEG C, and heat-drawn wire is 58 DEG C; The density of poly-13 lactan is 1.01g/cm3, and fusing point is within the scope of 180 ~ 183 DEG C, and heat-drawn wire is 50.5 DEG C; The density of bisphenol A polycarbonate is 1.20g/cm3, fusing point within the scope of 247 ~ 254 DEG C, heat-drawn wire is 135 DEG C, melting index is 6g/10min; The fusing point of poly(4-methyl-1-pentene) within the scope of 238 ~ 242 DEG C, heat-drawn wire is 80 DEG C, melting index is 215g/10min.
10. by the preparation method of serondary lithium battery described in claim 5,6,7 or 8 with 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).
CN201310740610.0A 2013-12-27 2013-12-27 Serondary lithium battery polyester micro-pore septum and preparation method thereof Active CN103724951B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310740610.0A CN103724951B (en) 2013-12-27 2013-12-27 Serondary lithium battery polyester micro-pore septum and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310740610.0A CN103724951B (en) 2013-12-27 2013-12-27 Serondary lithium battery polyester micro-pore septum and preparation method thereof

Publications (2)

Publication Number Publication Date
CN103724951A CN103724951A (en) 2014-04-16
CN103724951B true CN103724951B (en) 2016-01-20

Family

ID=50449264

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310740610.0A Active CN103724951B (en) 2013-12-27 2013-12-27 Serondary lithium battery polyester micro-pore septum and preparation method thereof

Country Status (1)

Country Link
CN (1) CN103724951B (en)

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105355817B (en) * 2015-12-14 2018-08-14 苏州锂盾储能材料技术有限公司 A kind of preparation method of lithium ion battery new types of diaphragm material
CN105514320B (en) * 2015-12-14 2019-03-19 苏州锂盾储能材料技术有限公司 A kind of preparation method of lithium ion battery high liquid-absorbing diaphragm material
CN105355814A (en) * 2015-12-14 2016-02-24 苏州锂盾储能材料技术有限公司 Preparation method of lithium-ion battery safe diaphragm material
CN105552280B (en) * 2016-03-07 2018-09-11 上海恩捷新材料科技股份有限公司 A kind of preparation method of lithium ion battery separator
CN110088194B (en) * 2016-12-27 2021-06-29 三井化学株式会社 Polyester sheet
CN108878745A (en) * 2017-05-12 2018-11-23 住友化学株式会社 Nonaqueous electrolytic solution secondary battery spacer porous layer and nonaqueous electrolytic solution secondary battery lamination spacer
CN108232090A (en) * 2018-01-08 2018-06-29 溧阳月泉电能源有限公司 Mixed raw material and its application of lithium ion secondary battery membrane are prepared again
CN109119574B (en) * 2018-08-15 2021-06-18 苏州大学 Porous lithium ion battery diaphragm based on cross-linked and linear polymer and preparation method and application thereof
CN109273646A (en) * 2018-09-28 2019-01-25 青岛大学 A method of preparing the lithium ion battery separator of polycarbonate cladding
CN109742300B (en) * 2018-12-28 2021-08-24 界首市天鸿新材料股份有限公司 Lithium battery diaphragm and preparation method thereof
CN109742295B (en) * 2018-12-28 2022-09-09 界首市天鸿新材料股份有限公司 Dry lithium battery diaphragm and preparation method thereof
CN110890505B (en) * 2019-12-02 2022-09-27 安徽金力新能源有限公司 Wet diaphragm and production system and production method thereof
CN113394512A (en) * 2021-05-20 2021-09-14 惠州锂威电子科技有限公司 Lithium ion battery diaphragm and preparation method thereof
CN114566757B (en) * 2021-12-31 2023-08-04 宁波长阳科技股份有限公司 Lithium ion battery diaphragm with high strength and high liquid absorption rate and preparation method thereof
CN115312970A (en) * 2022-08-15 2022-11-08 湖南创一工业新材料股份有限公司 Preparation method of high-strength PET battery diaphragm
CN116444959B (en) * 2022-12-30 2023-11-17 佛山华新恒丰聚酯包装有限公司 Plastic bottle and manufacturing method thereof

Citations (1)

* Cited by examiner, † Cited by third party
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

Patent Citations (1)

* Cited by examiner, † Cited by third party
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

Also Published As

Publication number Publication date
CN103724951A (en) 2014-04-16

Similar Documents

Publication Publication Date Title
CN103724951B (en) Serondary lithium battery polyester micro-pore septum and preparation method thereof
CN104466064B (en) A kind of preparation method of battery diaphragm
CN102931371B (en) Battery diaphragm preparation method
CN103407140B (en) Preparation method for PP/PE/PE three-layer compound microporous film
CN102501419B (en) Polyolefin multilayer micro-porous membrane and preparation method thereof
CN102064299A (en) Polyolefin multi-layer porous diaphragm for lithium ion battery and preparation method thereof
CN101981100B (en) Microporous film and method for producing the same
CN103811704B (en) A kind of preparation method of temp. resistance microporous film
CN109560235B (en) Novel preparation method of aramid fiber diaphragm of lithium ion battery
CN103633272B (en) A kind of preparation method of micro-pore septum and micro-pore septum
CN107732100A (en) A kind of three-layer co-extruded lithium ion battery separator and preparation method thereof
CN102064301A (en) Method for manufacturing porous multilayer composite diaphragm for lithium battery and diaphragm
CN202259507U (en) Polyester lithium ion battery diaphragm
CN103840113B (en) A kind of preparation method of the polyethylene separators for lithium battery
CN103717390A (en) Multilayer porous film, separator for nonaqueous electrolyte secondary batteries, and nonaqueous electrolyte secondary battery
CN103000850B (en) Preparation method of multilayer ceramic composite membrane for improving safety of secondary battery
CN105504565A (en) Graphene-containing conducting material used for 3D printing and preparation method of graphene-containing conducting material
CN105428574A (en) Lithium battery microporous membrane and preparation method thereof
CN107808943A (en) A kind of multi-layer polyolefin micro-pore septum and preparation method thereof
CN104393215A (en) Multilayer porous battery separator continuously varying with gradient in component proportion and preparation method thereof
CN106751043A (en) A kind of high intensity, amylene microporous barrier of poly- 4 methyl 1 of high thermal stability and preparation method thereof
CN106654121A (en) High-temperature-resisting multilayered micro-pore diaphragm and preparation method thereof
CN110945681A (en) Lithium battery diaphragm and preparation method thereof
CN103182818B (en) A kind of Merlon extrusion foaming composite board and preparation method thereof
CN103753726A (en) Method for preparing heat-conductive composite material

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant