CN1891443A - Method for making high-temperature-resistance polyolefin microporous membrane - Google Patents
Method for making high-temperature-resistance polyolefin microporous membrane Download PDFInfo
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- CN1891443A CN1891443A CN 200510035681 CN200510035681A CN1891443A CN 1891443 A CN1891443 A CN 1891443A CN 200510035681 CN200510035681 CN 200510035681 CN 200510035681 A CN200510035681 A CN 200510035681A CN 1891443 A CN1891443 A CN 1891443A
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- 229920000098 polyolefin Polymers 0.000 title claims abstract description 111
- 239000012982 microporous membrane Substances 0.000 title claims description 10
- 238000000034 method Methods 0.000 title abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 34
- 238000002844 melting Methods 0.000 claims abstract description 11
- 230000008018 melting Effects 0.000 claims abstract description 11
- 239000012528 membrane Substances 0.000 claims description 45
- 238000010438 heat treatment Methods 0.000 claims description 22
- 238000002360 preparation method Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 4
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 4
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 claims description 4
- 150000002170 ethers Chemical class 0.000 claims description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 5
- 238000001125 extrusion Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract description 2
- 239000010408 film Substances 0.000 abstract 5
- 230000009977 dual effect Effects 0.000 abstract 1
- 229920005672 polyolefin resin Polymers 0.000 abstract 1
- 239000010409 thin film Substances 0.000 abstract 1
- 230000035699 permeability Effects 0.000 description 16
- 238000003860 storage Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- 239000011347 resin Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 125000004836 hexamethylene group Chemical class [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Cell Separators (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
This invention relates to a manufacturing method for high temperature-proof polyolefin micro-porous films including: a, melting the polyolefin resin and a solvent to a uniform solution, b, extruding said solution out by the mold head of an extrusion machine to be cooled and cast on a roller to become a thick plate, c, stretching the thick plate in dual way to a thin film, d, washing off the solvent on the film, e, stereotyping the film laterally the second time to get the polyolefin porous film characterizing that said film is fixed in two ways vertically and horizontally in short time high temperature process and its high temperature performance is improved greatly.
Description
Technical field
The present invention relates to the preparation method of polyolefin micro porous polyolefin membrane, particularly relate to a kind of preparation method that can effectively improve the polyolefin micro porous polyolefin membrane of polyolefin micro porous polyolefin membrane high-temperature behavior, lithium ion battery internal resistance after high-temperature storage of being made by described polyolefin micro porous polyolefin membrane changes little, capacity restoration rate height.
Background technology
Polyolefin micro porous polyolefin membrane is a kind of film shape material that contains micropore, and it is widely used in the making of battery with nonaqueous electrolyte barrier film, capacitor diaphragm, various diffusion barrier, membrane for water treatment etc.
The preparation method of polyolefin micro porous polyolefin membrane comprises solvent method, stretching perforate method etc., generally adopts solvent method.Known solvent method is that polyolefin and solvent heating and melting are mixed into uniform solution, this solution is extruded through extruder die head, and sheet is cast in cooling on slab roller, sheet becomes film through biaxial tension, this film draws typing just to obtain polyolefin micro porous polyolefin membrane by secondary is horizontal through extractant wash-out solvent wherein then.
The high-temperature storage performance is an important performance of lithium ion battery, and it requires lithium ion battery internal resistance after high-temperature storage to change little, capacity restoration rate height.In order to improve the high-temperature storage performance of lithium ion battery, also must have the good high-temperature performance as the polyolefin micro porous polyolefin membrane of barrier film, promptly little, the permeability of percent thermal shrinkage changes little after high-temperature storage.Therefore, in the production process of solvent method, must do corresponding PROCESS FOR TREATMENT at the high-temperature behavior of improving polyolefin micro porous polyolefin membrane.Many processing methods of improving the polyolefin micro porous polyolefin membrane high-temperature behavior are arranged at present, as method at way, film surface cloth stabilization agent, can improve under the condition of high temperature long-time capacity deterioration of preserving the back battery, this method has a detailed description in the Japan Patent JP2004-204162 of Tonen and JP2004-204163 etc.; Also have the stretching shrink process one by one of both direction in length and breadth, can reduce the percent thermal shrinkage under the polyolefin micro porous polyolefin membrane high temperature, this method has a detailed description in the Japan Patent JP2003-119306 of Nitto.
Disclosed coating stabilization agents such as Japan Patent JP2004-204162, JP2004-204163 are to improve the method for polyolefin micro porous polyolefin membrane high-temperature behavior, its battery that makes can be 85 ℃ of capacity response rates that can also reach after storing 30 days more than 70%, but the electrochemical stability existing problems of organic stabilization agent of introducing when heavy-current discharge have after the reaction and stop up the hidden danger that barrier film causes permeability to descend; The method of Japan Patent JP2003-119306 relaxes internal stress in the polyolefin micro porous polyolefin membrane by the mode of shrinking again after stretching, to reduce polyolefin micro porous polyolefin membrane shrinkage factor at high temperature, contraction after this stretching is need be limited in the smaller scope, otherwise will influence the permeability and the mechanical strength of polyolefin micro porous polyolefin membrane greatly, from the combination property of polyolefin micro porous polyolefin membrane, this improved procedure also has problems.
Summary of the invention
The present invention aims to provide a kind of preparation method of improved polyolefin micro porous polyolefin membrane, not only have air permeability and good and mechanical strength with preparation, and high-temperature behavior is obviously improved, the high-temperature-resistance polyolefin microporous membrane that percent thermal shrinkage is little after high-temperature storage, the permeability variation is little, and make lithium ion battery internal resistance after high-temperature storage of making of this polyolefin micro porous polyolefin membrane change little, capacity restoration rate height.
For achieving the above object, the invention provides a kind of preparation method of polyolefin micro porous polyolefin membrane, it may further comprise the steps: a, vistanex is become uniform solution with the solvent melting mixing; B, described solution is extruded by the die head of extruder, and sheet is cast in cooling on slab roller; C, sheet is made film through biaxial tension; D, with described film eluting solvent; E, the film that obtains is obtained polyolefin micro porous polyolefin membrane after drawing typing through secondary is horizontal again, it is characterized in that, with described polyolefin micro porous polyolefin membrane in length and breadth two to fixing, 110 ℃-140 ℃ heat treatment 1-30 second, obtain the polyolefin micro porous polyolefin membrane that high-temperature behavior is obviously improved.
When described polyolefin micro porous polyolefin membrane is heat-treated, must be with polyolefin micro porous polyolefin membrane in length and breadth two to fixing, otherwise polyolefin micro porous polyolefin membrane two shrinks to meeting in length and breadth in heat treatment process, and permeability obviously descends.
Heat treated preferred temperature is 120 ℃-135 ℃, and heat treatment temperature is too low, does not have the effect that improves the polyolefin micro porous polyolefin membrane high-temperature behavior, and temperature is too high, polyolefin micro porous polyolefin membrane generation closed pore phenomenon, and permeability obviously descends.
The heat treated preferred time is 3-20 second, and heat treatment time is too short, does not have the effect that improves the polyolefin micro porous polyolefin membrane high-temperature behavior, and the time is oversize, and polyolefin micro porous polyolefin membrane also the closed pore phenomenon can take place, and permeability obviously descends.
Among the step a, the vistanex that is used to make micro-porous film can be one or more polyolefinic mixtures, preferably contains the extrahigh-molecular weight polyolefins resin.The extrahigh-molecular weight polyolefins resin can be polyolefinic single polymers or copolymers such as ethene, propylene, 1-butylene, 4-methyl-1-pentene, 1-hexene, or their mixture.The micro-porous film that obtains with these extrahigh-molecular weight polyolefins resins has characteristics such as high strength, high broken film temperature.The weight average molecular weight of extrahigh-molecular weight polyolefins resin should be 1 * 10
6～1 * 10
7, be higher than 1 * 10
7The time vistanex melt viscosity too big, be difficult to and the solvent melting mixing; Be lower than 1 * 10
6The time do not reach the purpose that improves film-strength and broken film temperature again.The weight of extrahigh-molecular weight polyolefins resin account for the resin total amount more than 20% for well, its preferred value is 30～90%.
The vistanex that except the extrahigh-molecular weight polyolefins resin, also should contain other, require from high strength micro-porous film, add the high density polyolefins resin, as polyolefinic single polymers or copolymers such as ethene, propylene, 1-butylene, 4-methyl-1-pentene, 1-hexenes, or their mixture effect is better.The weight average molecular weight of this resin should be 1 * 10
4～1 * 10
6, its preferred weight average molecular weight is 5 * 10
4～3 * 10
5
In order to reduce the closed pore temperature of micro-porous film, can add a small amount of low density polyolefin, as polyolefinic single polymers or copolymers such as ethene, propylene, 1-butylene, 4-methyl-1-pentene, 1-hexenes, or their mixture.Consider that adding low density polyolefin can reduce film strength, thus weight account for the resin total amount below 20% for well.
For making vistanex and solvent be easy to melting mixing, the solvent of the vistanex in step a can be a kind of in the aliphatic hydrocarbons such as nonane, decane, hendecane, dodecane, naphthalane, atoleine, preferably is difficult to the atoleine that volatilizees.The kinematic viscosity that atoleine is 40 ℃ should be chosen between 30～150cst, the low excessively melting mixing that is unfavorable for solvent and vistanex of viscosity, and viscosity is too high to be unfavorable for by the extractant wash-out.The content of solvent accounts for the 40～90% better of vistanex and solvent gross weight, and content is too low, and the micro-porous film void content that obtains is low, and permeability is poor, and content is too high, vistanex solution difficult forming.
The melting mixing method of vistanex among the step a and solvent can have multiple choices, can heat the pressurization stirring regular hour earlier in stirred tank and fully mix, and extrudes with single screw extrusion machine again; Also can add double screw extruder to vistanex earlier, add solvent by the side direction spout again, directly mix and extrude with double screw extruder.Generally more than vistanex mixture melting point 20～60 ℃ of melting temperatures.
Among the step b, polyolefin solution is extruded by the extruder die head, and sheet is cast in cooling on slab roller.In order to prevent that phase process from producing big phase region, after extruding, should cool off rapidly vistanex solution, and the temperature of slab roller should can also use water-bath, ice bath, cryosel bath etc. to accelerate cooling velocity below 30 ℃.
Among the step c, be the biaxial tension of longitudinal and transverse two directions to the biaxial tension of sheet, the total multiplying power of vertically and horizontally stretching is 10～100 times.Stretching ratio is too little, and the porosity of the micro-porous film that obtains is low, permeability is poor, and intensity is low; Stretching ratio is excessive, and stretcher can't meet the demands.Draft temperature is 90 ℃-140 ℃.
Eluting solvent in the steps d is to use the extractant eluting solvent, and described extractant can be a kind of in hydro carbons, chlorohydrocarbon, fluorinated hydrocarbons and the ethers, and the residual volume of solvent is below 1wt% behind the eluting solvent.Extractant can be hydro carbons such as pentane, hexane, heptane, decane, chlorohydrocarbons such as chloromethanes, carbon tetrachloride, and three fluoridize fluorinated hydrocarbons such as ethane, ethers such as ether, dioxane, the easy volatile solvent of ketones such as acetone, butanone.The residual volume of washing back solvent should be below 1wt%.
Among the step e, secondary is horizontal to draw typing not only can regulate mechanical performance, the permeability of film, and can improve the stability of film in long-term the use.The horizontal stretching ratio that draws typing of secondary is generally at 1.0-1.8 times, and temperature is 90 ℃-140 ℃.
Contribution of the present invention is that it has effectively improved the high-temperature behavior of polyolefin micro porous polyolefin membrane.The present invention is because when carrying out the high-temperature heat treatment of short time to polyolefin micro porous polyolefin membrane, and polyolefin micro porous polyolefin membrane has been carried out in length and breadth two to fixing, therefore obviously improved the high-temperature behavior of polyolefin micro porous polyolefin membrane.The polyolefin micro porous polyolefin membrane that finally obtains percent thermal shrinkage after high-temperature storage is little, permeability changes little.Lithium ion battery internal resistance after high-temperature storage of making of this polyolefin micro porous polyolefin membrane changes little, capacity restoration rate height.
The specific embodiment
The following example is to further explanation of the present invention and explanation, and the present invention is not constituted any limitation.
Embodiment 1
High density polyethylene (HDPE) (weight average molecular weight 2.7 * 10 with 27 (weight %)
5, 133 ℃ of fusing points), UHMWPE (ultra-high molecular weight polyethylene, the weight average molecular weight 1.0 * 10 of 3 (weight %)
6, 138 ℃ of fusing point fusing points) drop in the double screw extruder (diameter 78mm, L/D=48, strong mixed milling type), with the atoleine (kinematic viscosity 90cst/40 ℃) of measuring pump by side direction spout adding 70 (weight %), melting mixing is modulated into polyethylene solution under 200 ℃, 200 rev/mins condition.
Polyethylene solution by T pattern head (die lip opening degree 1.2mm, width of cloth 260mm), is extruded with the speed of 3m/min, is cooling casting sheet on 10 ℃ the slab roller in surface temperature, obtains the sheet of thickness 1.0mm.
Sheet is carried out progressively biaxial tension, stretching ratio for vertical * horizontal=5 * 7 times, wherein vertical 115 ℃ of the preheat temperatures, 100 ℃ of draft temperatures of drawing; Horizontal 125 ℃ of the preheat temperatures of drawing, 110 ℃ of draft temperatures.The film that obtains after the stretching is clean, dry with heptane.
Film carried out secondary is horizontal to draw typing, stretching ratio is 1.5 times, 110 ℃ of draft temperatures.
Then with the horizontal film two that obtains of typing that draws of secondary to fixing, heat-treat, 127 ℃ of heat treatment temperatures in 8 seconds processing times, finally obtain the polyolefin micro porous polyolefin membrane of thick 20um.
Embodiment 2
Heat treatment temperature is 130 ℃ in the heat treatment step, and in 5 seconds processing times, other step is with embodiment 1.
Embodiment 3
Heat treatment temperature is 125 ℃ in the heat treatment step, and in 12 seconds processing times, other step is with embodiment 1.
Comparative example 1
Do not carry out the heat treatment of final step, other step is with embodiment 1.
Comparative example 2
Fixed film is vertical in the heat treatment step, allows film cross-direction shrinkage 15%, and other step is with embodiment 1.
Comparative example 3
Heat treatment temperature is 140 ℃ in the heat treatment step, and other step is with embodiment 1.
Comparative example 4
Heat treatment time is 30 seconds in the heat treatment step, and other step is with embodiment 1.
The making of battery
The preparation of negative pole: get 059 graphite of 100 parts of weight, add 3 parts PVDF (Kynoar), add a certain amount of oxolane, mix.On the Copper Foil of 10 μ m, carry out slurry, dry then, be pressed into the negative plate that battery is used.
Anodal preparation: the LiCoO that gets 100 parts of weight
2, add 3 parts PVDF, add 4 parts of acetylene blacks again, mix at NMP (N-methyl pyrrolidone) solution.On the thick aluminium foil of 20 μ m, carry out slurry, dry then, be pressed into the anode pole piece that battery is used.
Electrolyte: in EC: EMC=1: 2 ratio is made solvent, adds a certain amount of LiPF
6(lithium hexafluoro phosphate) forms concentration is 1mol/1 electrolyte.
The different diaphragm paper that negative plate and positive plate and each embodiment obtain is separated by and is stacked, and reels, and injects electrolyte, makes battery.
The high-temperature behavior of the polyolefin micro porous polyolefin membrane that different technology conditions obtains (85 ℃, 16hr storage) is as table 1.
Table 1
| Gas permeability (s/100cc) before storing | Shrinkage factor after the storage | Store back gas permeability (s/100cc) | ||
| MD％ | TD％ | |||
| Embodiment 1 | 430 | 2.1 | 3.0 | 520 |
| Embodiment 2 | 450 | 1.9 | 2.7 | 510 |
| Embodiment 3 | 420 | 2.4 | 3.5 | 540 |
| Comparative example 1 | 410 | 5.5 | 8.7 | 800 |
| Comparative example 2 | 680 | 2.0 | 1.5 | 760 |
| Comparative example 3 | 1500 | 1.0 | 1.3 | 1600 |
| Comparative example 4 | 830 | 1.8 | 2.5 | 94O |
The high-temperature storage performance (85 ℃, 48hr) of the lithium ion battery that the polyolefin micro porous polyolefin membrane that obtains with different technology conditions is made is as table 2
Table 2
| Internal resistance (m Ω) before storing | Store back internal resistance (m Ω) | Store back capacity restoration rate (%) | |
| Embodiment 1 | 37 | 57 | 75 |
| Embodiment 2 | 39 | 56 | 77 |
| Embodiment 3 | 36 | 60 | 70 |
| Comparative example 1 | 36 | 120 | 45 |
Annotate: the polyolefin micro porous polyolefin membrane permeability that comparative example 2-4 obtains is poor, has not reached the requirement of making battery.
As seen embodiment and comparative example are contrasted, two to fixing, the polyolefin micro porous polyolefin membrane that the high-temperature heat treatment of short time obtains has not only kept high ventilation performance before the heat treatment by in length and breadth, and high-temperature behavior obviously improves, and little, the permeability of percent thermal shrinkage changes little after high-temperature storage.Lithium ion battery internal resistance after high-temperature storage of making of this polyolefin micro porous polyolefin membrane changes little, capacity restoration rate height.
Claims (7)
1, a kind of preparation method of high-temperature-resistance polyolefin microporous membrane, it may further comprise the steps: a, vistanex is become uniform solution with the solvent melting mixing; B, described solution is extruded by the die head of extruder, and sheet is cast in cooling on slab roller; C, sheet is made film through biaxial tension; D, with described film eluting solvent; E, the film that obtains is obtained polyolefin micro porous polyolefin membrane after drawing typing through secondary is horizontal again, it is characterized in that, with described polyolefin micro porous polyolefin membrane in length and breadth two to fixing, 110 ℃-140 ℃ heat treatment 1-30 second, obtain the polyolefin micro porous polyolefin membrane that high-temperature behavior is obviously improved.
2, the preparation method of high-temperature-resistance polyolefin microporous membrane as claimed in claim 1 is characterized in that, preferred heat treatment temperature is 120 ℃-135 ℃.
3, the preparation method of high-temperature-resistance polyolefin microporous membrane as claimed in claim 1 is characterized in that, preferred heat treatment time is 3-20 second.
4, the preparation method of high-temperature-resistance polyolefin microporous membrane as claimed in claim 1, it is characterized in that, the solvent of the vistanex in the step (a) can be a kind of in the aliphatic hydrocarbons such as nonane, decane, hendecane, dodecane, naphthalane, atoleine, and the content of solvent accounts for 40～90% of vistanex and solvent gross weight.
5, the preparation method of high-temperature-resistance polyolefin microporous membrane as claimed in claim 1, it is characterized in that, in the step (c), be the biaxial tension of longitudinal and transverse two directions to the biaxial tension of sheet, the total multiplying power of vertically and horizontally stretching is 10～100 times, and draft temperature is 90 ℃-140 ℃.
6, the preparation method of high-temperature-resistance polyolefin microporous membrane as claimed in claim 1, it is characterized in that, eluting solvent in the step (d) is to use the extractant eluting solvent, described extractant can be a kind of in hydro carbons, chlorohydrocarbon, fluorinated hydrocarbons and the ethers, and the residual volume of solvent is below 1wt% behind the eluting solvent.
7, the preparation method of high-temperature-resistance polyolefin microporous membrane as claimed in claim 1 is characterized in that, in the step (e), secondary is horizontal draw the stretching ratio of typing be 1.0-1.8 doubly, temperature is 90 ℃-140 ℃.
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|---|---|---|---|
| CNB2005100356816A CN100418741C (en) | 2005-06-30 | 2005-06-30 | Method for making high-temperature-resistance polyolefin microporous membrane |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100356816A CN100418741C (en) | 2005-06-30 | 2005-06-30 | Method for making high-temperature-resistance polyolefin microporous membrane |
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| CN100418741C CN100418741C (en) | 2008-09-17 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102152514A (en) * | 2010-12-25 | 2011-08-17 | 佛山塑料集团股份有限公司 | Method for preparing multiple layers of polyolefin microporous film |
| CN105835383A (en) * | 2016-05-12 | 2016-08-10 | 武汉纺织大学 | Manufacturing method for two-way-stretching nylon fiber porous film |
| CN106891557A (en) * | 2017-03-15 | 2017-06-27 | 中国科学技术大学 | A kind of polyolefine micro/nano-fibre film and preparation method thereof |
| CN111180645A (en) * | 2020-02-18 | 2020-05-19 | 江苏厚生新能源科技有限公司 | Polyolefin porous membrane and preparation method thereof |
| CN114784454A (en) * | 2022-06-17 | 2022-07-22 | 宁波长阳科技股份有限公司 | High-temperature-resistant polyolefin microporous membrane and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0301621A1 (en) * | 1987-07-23 | 1989-02-01 | Dsm N.V. | Process for the production of polymer Films of high interlaminar strength by biaxial ultrastretching and the use thereof |
| JPH107832A (en) * | 1996-04-26 | 1998-01-13 | Mitsui Petrochem Ind Ltd | High strength porous film of polypropylene and its production |
| US6245272B1 (en) * | 1999-02-19 | 2001-06-12 | Tonen Chemical Corporation | Polyolefin microporous film and method for preparing the same |
| JP2003119306A (en) * | 2001-10-11 | 2003-04-23 | Nitto Denko Corp | Low-shrinkable fine porous film and method for producing the same |
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2005
- 2005-06-30 CN CNB2005100356816A patent/CN100418741C/en active Active
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102152514A (en) * | 2010-12-25 | 2011-08-17 | 佛山塑料集团股份有限公司 | Method for preparing multiple layers of polyolefin microporous film |
| CN102152514B (en) * | 2010-12-25 | 2013-07-03 | 佛山市金辉高科光电材料有限公司 | Method for preparing multiple layers of polyolefin microporous film |
| CN105835383A (en) * | 2016-05-12 | 2016-08-10 | 武汉纺织大学 | Manufacturing method for two-way-stretching nylon fiber porous film |
| CN106891557A (en) * | 2017-03-15 | 2017-06-27 | 中国科学技术大学 | A kind of polyolefine micro/nano-fibre film and preparation method thereof |
| CN111180645A (en) * | 2020-02-18 | 2020-05-19 | 江苏厚生新能源科技有限公司 | Polyolefin porous membrane and preparation method thereof |
| CN111180645B (en) * | 2020-02-18 | 2021-07-13 | 江苏厚生新能源科技有限公司 | Polyolefin porous membrane and preparation method thereof |
| CN114784454A (en) * | 2022-06-17 | 2022-07-22 | 宁波长阳科技股份有限公司 | High-temperature-resistant polyolefin microporous membrane and preparation method thereof |
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| CN100418741C (en) | 2008-09-17 |
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