CN105024028A - Preparation method of three-layer composite lithium battery membrane - Google Patents
Preparation method of three-layer composite lithium battery membrane Download PDFInfo
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- CN105024028A CN105024028A CN201510366133.5A CN201510366133A CN105024028A CN 105024028 A CN105024028 A CN 105024028A CN 201510366133 A CN201510366133 A CN 201510366133A CN 105024028 A CN105024028 A CN 105024028A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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- 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
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Abstract
The invention mainly discloses a preparation method of a three-layer composite lithium battery membrane, wherein a three-layer composite membrane is prepared through a multi-layer coextrusion method, and then a polyolefin microporous membrane is obtained through biaxial tension. The method has perfect equipment technology and simple technological process, and is easy to implement large-scale continuous production. The method comprises the following steps of molding a functional layer added with inorganic filling or the other pore-forming filling into a multi-layer composite microporous membrane precursor at one time by a plurality of (more than two) extruders through a polyolefin microporous membrane multi-cavity mold head, cooling through a chilling roller and obtaining a finished product through MDO (Machine Direction Oriented) and TDO (Transverse Direction Oriented) stretches. The microporous membrane obtained through the method has uniform pore size distribution, high production efficiency, free pollution and low cost, and is beneficial for large-scale production. In addition, the shock strength of the microporous membrane prepared through the method is greatly improved, the condition of insufficient strength of a uniaxial tension product can be avoided, and the security in battery application is improved.
Description
Technical field
The present invention relates to microporous barrier field, particularly relate to a kind of preparation method of Multi-layer composite polyolefine material microporous barrier, and the application of the microporous polyolefin film prepared by this method.
Background technology
From the thirties in last century, since the method appearance of film is prepared in biaxial tension, biaxially oriented film receives increasing concern with its distinctive performance.In biaxially oriented film production process, because polymer is subject to the stretching of longitudinal and transverse two directions, change the arrangement of molecule or segment, comparatively significantly, the impact strength of film and resist bending performance can be made to increase several times to tens times.The thermal coefficient of expansion of plastic material itself also can decrease.The domestic research about biaxial tension starts from the 1950's, and main body, to introduce, to absorb external sophisticated equipment and technology, brings the flourish of domestic biaxial stretching film.
In recent years, along with the fast development of lithium electrical travelling industry, domestic lithium electric separator production technology has also welcome a fast-developing period.Lithium electric separator mainly divides dry method, wet method two class by pore formation mechanism.Dry method barrier film mainly divides dry method simple tension again, based on wafer-separate moulding mechanism, and dry method biaxial tension, based on crystal transfer moulding mechanism.For now, dry method biaxial tension is mainly used in polypropylene crystalline structure transformation mechanism field.In the moulding mechanism field of wafer-separate, the main controlling difficulties of biaxial tension is mating of pore size distribution and size and apparatus and process, and equipment investment is large, and R&D costs are high.In addition, because the moulding mechanism of different materials and component is different, current technological process, is difficult to realize multilayer film simultaneously evenly shaping, and its pass and size distribution inequality, performance difference is large.The processing mode that common sandwich construction barrier film adopts the later stage to carry out applying usually adds functional layer.Its preparation process cannot realize one-shot forming, needs multiple working procedure just can complete, and therefore biaxial tension has no research report in the forming process of multi-layer co-extruded compound barrier film.
Summary of the invention
The present invention by the formula rate of adjustment functional layer, and selects suitable two drawing process to realize multilayer complex films one-shot forming, for the preparation of even structure, and the microporous polyolefin film of superior performance.The present invention mainly adopts multi-layer co-extruded method to prepare the composite membrane of three-decker, then experiences biaxial tension and obtain polyolefin microporous film.The method equipment and technology is perfect, and technological process is simple, easily realizes large-scale continuous production.The method will add functional layer and the microporous polyolefin film multi-cavity die head of inorganic filler or other pore-forming filler by multiple stage extruder (more than two), the composite microporous film precursor of one-step molded multilayer, after sharp cooling roll cooling, obtain finished product respectively through MDO, TDO twice stretching.The microporous barrier even aperture distribution obtained by the method, production efficiency is high, pollution-free, and cost is low, is beneficial to large-scale production.In addition the microporous barrier impact strength prepared by the method is significantly improved, and the situation of the undercapacity that simple tension product can be avoided to exist, improves the fail safe in battery applications.
The object of the present invention is to provide a kind of biaxial tension to prepare the method for Multi-layer composite high-performance microporous barrier, the microporous barrier prepared by the method possesses two-layer high strength, dystectic functional layer, for improving the security performance in battery use procedure.
Above-mentioned purpose of the present invention can be achieved by following technical solution:
A, filling mix: pore-forming filling and functional layer resin are carried out being mixed to get Resin A, wherein pore-forming filling weight accounting is 20 ~ 80%;
B, slab: the Resin A in step a is carried out fusion plastification from vistanex B through different extruder, A:B:A extrudes thickness proportion according to 10:80:10 ~ 20:60:20 and mixes through multi-chamber die head, flow out from narrow die lip mouth, after passing through-10 ~ 120 DEG C of sharp cooling roll coolings, obtain presoma sheet material;
C, first time stretch: by the precursor film prepared in step b, 80 ~ 160 DEG C of temperature, and carry out a longitudinal stretching (MDO) under stretching ratio 1.0 ~ 3.5 times;
D, second time stretch: by one-off drawing film in step c, at 80 ~ 160 DEG C of draft temperatures, and carry out secondary cross directional stretch (TDO) pore-forming under stretching ratio 1.0 ~ 2.5 times, obtain final microporous barrier;
E, thermal finalization: carried out by the microporous barrier of pore-forming in steps d two drawing (TDO2) to shape in the oven heat of 100 ~ 160 DEG C of temperature, stretching ratio is 0.5 ~ 2.0 times.
Pore-forming filling in described step a comprises: pore-forming filling is selected from the oxide of at least one in metal or semiconductor element, hydroxide, sulfide, nitride, carbide or its mixture.Wherein, metallic element is as Ca, Al, Si, Mg, Zn or Ba etc., and semiconductor element is as silicon, germanium, boron, selenium, tellurium or carbon etc.
Functional layer resin in described step a comprises: polyethylene, polypropylene, Kynoar (PVdF), polytetrafluoroethylene (PTFE), polyurethane, polymethylpentene (PMP), PETG (PET), Merlon (PC), polyester, polyvinyl alcohol (PVA), polyacrylonitrile (PAN), polyformaldehyde (PMO), polymethyl methacrylate (PMMA), polyoxyethylene (PEO) or cellulose, or its two or more mixture.
Pore-forming filling in described step a and functional layer mixed with resin, wherein, pore-forming filling preferred weight accounting is 30% ~ 70%.
Vistanex in described step b is preferably polypropylene, the polyolefine materials such as polyethylene.
The thickness proportion of extruding of the functional layer in described step b and polyolefin resin layer is: functional layer and polyolefin layer are combined as A-B-A three-decker, and the preferred thickness ratio of extruding of A:B:A is 15:70:15 ~ 20:60:20.
Sharp cooling roll temperature in described step b is preferably-10 ~ 120 DEG C;
MDO stretching ratio in described step c is preferably 1.5 ~ 3.0 times, and draft temperature is preferably 100 ~ 120 DEG C.
TDO stretching ratio in described steps d is preferably 1.5 ~ 2.0 times, and draft temperature is preferably 100 ~ 120 DEG C.
Setting temperature in described step e is preferably 120 ~ 150 DEG C, and TDO2 stretching ratio is preferably 0.8 ~ 1.5 times.
Beneficial effect describes: by the method, after optimizational function layer formula and later stage two drawing process, achieves the one-shot forming production model of multilayer complex films, greatly reduces operation number, reduce costs.And by the microporous barrier even aperture distribution that the method obtains, production efficiency is high, pollution-free, and cost is low, is beneficial to large-scale production.Preferable range of the present invention, hot strength and puncture strength are significantly due to one-component product.
Accompanying drawing explanation
Fig. 1 laminated diaphragm structure chart
1 and 3 is the functional layer that resin and pore-forming filling are mixed with; 2 is polyolefin micropore layer; 4 is microcellular structure in functional layer and distribution; 5 is microcellular structure on polyolefin micropore layer and distribution.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
In embodiment, the thickness of sample all with 16 μm for normative reference, other conditions are shown in technique scheme, and difference will be set forth in a particular embodiment.
Embodiment 1
By calcium carbonate (CaCO
3) powder adds in polypropylene according to the mass ratio of 40%, then with acrylic resin respectively by two extruders, extrude through three-layer co-extruded casting head, form the precursor film of A-B-A three-decker, A layer is CaCO
3with polypropylene mixed layer, B layer is polypropylene layer, and three layers are extruded thickness proportion is 10:80:10.Precursor film, through 90 DEG C of sharp cooling roll cooling formings, completes precursor film preparation process.Later stage completes the pore-forming type-approval process of precursor film by biaxial tension equipment.This precursor film is carried out under 100 DEG C of conditions the longitudinal stretching (MDO) of 2 times, under 140 DEG C of conditions, then complete the cross directional stretch (TDO) of 1.8 times, obtain microporous barrier.This microporous barrier obtains finished product through the secondary cross directional stretch (TDO2) of lower 0.95 times of 120 DEG C of conditions.
Embodiment 2
By calcium carbonate (CaCO
3) powder adds in polyester according to the mass ratio of 50%, then with acrylic resin respectively by two extruders, extrude through three-layer co-extruded casting head, form the precursor film of A-B-A three-decker, A layer is CaCO
3with polypropylene mixed layer, B layer is polypropylene layer, and three layers are extruded thickness proportion is 15:70:15.Precursor film, through 50 DEG C of sharp cooling roll cooling formings, completes precursor film preparation process.Later stage completes the pore-forming type-approval process of precursor film by biaxial tension equipment.This precursor film is carried out under 145 DEG C of conditions the longitudinal stretching (MDO) of 3 times, under 120 DEG C of conditions, then complete the cross directional stretch (TDO) of 1.5 times, obtain microporous barrier.This microporous barrier obtains finished product through the secondary cross directional stretch (TDO2) of lower 1.1 times of 140 DEG C of conditions.
Embodiment 3
By calcium carbonate (Al (OH)
3) powder adds in polypropylene according to the mass ratio of 60%, then with acrylic resin respectively by two extruders, extrude through three-layer co-extruded casting head, form the precursor film of A-B-A three-decker, A layer is CaCO
3with polypropylene mixed layer, B layer is polypropylene layer, and three layers are extruded thickness proportion is 20:60:20.Precursor film, through 70 DEG C of sharp cooling roll cooling formings, completes precursor film preparation process.Later stage completes the pore-forming type-approval process of precursor film by biaxial tension equipment.This precursor film is carried out under 120 DEG C of conditions the longitudinal stretching (MDO) of 2.5 times, under 140 DEG C of conditions, then complete the cross directional stretch (TDO) of 1.2 times, obtain microporous barrier.This microporous barrier obtains finished product through the secondary cross directional stretch (TDO2) of lower 1.2 times of 135 DEG C of conditions.
Embodiment 4
With virgin pp resin for basis material, use two extruders respectively, extrude through three-layer co-extruded casting head, form the precursor film of A-B-A three-decker, A layer is polypropylene layer, and B layer is also polypropylene layer, and three layers are extruded thickness proportion is 10:80:10.Precursor film, through 90 DEG C of sharp cooling roll cooling formings, completes precursor film preparation process.Later stage completes the pore-forming type-approval process of precursor film by biaxial tension equipment.This precursor film is carried out under 100 DEG C of conditions the longitudinal stretching (MDO) of 2 times, under 140 DEG C of conditions, then complete the cross directional stretch (TDO) of 1.8 times, obtain microporous barrier.This microporous barrier obtains finished product through the secondary cross directional stretch (TDO2) of lower 0.95 times of 120 DEG C of conditions.
The performance parameter of all embodiments is as table 1:
Table 1 embodiment properties of sample parameter
| Embodiment | MD hot strength kgf/cm 2 | Puncture strength/g | Porosity/% | Ventilative value/s |
| Embodiment 1 | 1850 | 445 | 38 | 254 |
| Embodiment 2 | 2843 | 561 | 43 | 336 |
| Embodiment 3 | 2232 | 412 | 34 | 412 |
| Embodiment 4 | 1552 | 320 | 36 | 305 |
Note: the hot strength in what " MD hot strength " represented sample test the is direction paralleled with draw direction.
As shown in Table 1, the basic material of functional layer, closely bound up with the performance of microporous barrier, the strength character of its material own is more useful, and the performance of final products is also better.Matrix resin in embodiment 2 is polyester, and gained microporous barrier intensity is significantly superior to embodiment 1 and embodiment 3 adopts polypropylene to be microporous barrier prepared by matrix resin.The microporous barrier that embodiment 4 is prepared for uniform resin polypropylene, contrast shows, a certain proportion of pore-forming material adds, and the introducing of specific function layer matrix resin, significantly can improve the performance of microporous barrier.
Embodiment 5
Adopt the preparation of embodiment 1 method, wherein process ratio, and test result is as shown in table 2.
Table 2
As shown in Table 2, the preferred technical scope of the present invention, has hot strength and the better technique effect of puncture strength, meanwhile, ensure that the porosity of micro-pore septum itself and ventilative value suitable with marketable product.
In addition, three layers of compound lithium battery diaphragm prepared within the present invention's preferred pore-forming filling accounting scope 20% ~ 80%, hot strength and puncture strength, technique effect is better.Especially, 30% ~ 70%, technique effect is more remarkable.For other functional layer resin and vistanex, there is similar technique effect.
Above-mentioned execution mode is only the preferred embodiment of the present invention; can not limit the scope of protection of the invention with this, change and the replacement of any unsubstantiality that those skilled in the art does on basis of the present invention all belong to the present invention's scope required for protection.
Claims (10)
1. a preparation method for three layers of compound lithium battery diaphragm, is characterized in that, comprises the following steps:
A, filling mix: pore-forming filling and functional layer resin are carried out being mixed to get Resin A, wherein pore-forming filling weight accounting is 20 ~ 80%;
B, slab: the Resin A in step a is carried out fusion plastification from vistanex B through different extruder, A:B:A extrudes thickness proportion according to 10:80:10 ~ 20:60:20 and mixes through multi-chamber die head, flow out from narrow die lip mouth, after passing through-10 ~ 120 DEG C of sharp cooling roll coolings, obtain presoma sheet material;
C, first time stretch: by the precursor film prepared in step b, 80 ~ 160 DEG C of temperature, and carry out a longitudinal stretching (MDO) under stretching ratio 1.0 ~ 3.5 times;
D, second time stretch: by one-off drawing film in step c, at 80 ~ 160 DEG C of draft temperatures, and carry out secondary cross directional stretch (TDO1) pore-forming under stretching ratio 1.0 ~ 2.5 times, obtain final microporous barrier;
E, thermal finalization: carried out by the microporous barrier of pore-forming in steps d two drawing (TDO2) to shape in the oven heat of 100 ~ 160 DEG C of temperature, stretching ratio is 0.5 ~ 2 times.
2. preparation method according to claim 1, it is characterized in that, described pore-forming filling preferred weight accounting is 30% ~ 70%.
3. preparation method according to claim 1, it is characterized in that, described pore-forming filling is selected from least one oxide, hydroxide, sulfide, nitride, carbide or its mixture in metal or semiconductor element.
4. preparation method according to claim 3, it is characterized in that, described metallic element is selected from Ca, Al, Si, Mg, Zn or Ba, and described semiconductor element is selected from silicon, germanium, boron, selenium, tellurium or carbon.
5. preparation method according to claim 1, it is characterized in that, described functional layer resin is selected from polyethylene, polypropylene, Kynoar (PVdF), polytetrafluoroethylene (PTFE), polyurethane, polymethylpentene (PMP), PETG (PET), Merlon (PC), polyester, polyvinyl alcohol (PVA), polyacrylonitrile (PAN), polyformaldehyde (PMO), polymethyl methacrylate (PMMA), polyoxyethylene (PEO) or cellulose, or its two or more mixture.
6. preparation method according to claim 1 or 2, is characterized in that, the sharp cooling roll temperature in described step b is preferably-10 ~ 120 DEG C.
7. preparation method according to claim 1 or 2, is characterized in that, the MDO stretching ratio in described step c is preferably 1.5 ~ 3.0 times, and draft temperature is preferably 100 ~ 120 DEG C.
8. preparation method according to claim 1 or 2, is characterized in that, the TDO stretching ratio in described steps d is preferably 1.5 ~ 2.0 times, and draft temperature is preferably 100 ~ 120 DEG C.
9. preparation method according to claim 1 or 2, is characterized in that, the setting temperature in described step e is preferably 120 ~ 150 DEG C, and TDO2 stretching ratio is preferably 0.8 ~ 1.5 times.
10. three layers of compound lithium battery diaphragm, is characterized in that, described battery diaphragm method according to the arbitrary claim of claim 1-9 prepares.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109968622A (en) * | 2019-03-25 | 2019-07-05 | 成都新柯力化工科技有限公司 | A kind of method that clean type Screw Extrusion prepares lithium battery polymer dielectric film |
| CN110744840A (en) * | 2019-10-10 | 2020-02-04 | 深圳中兴新材技术股份有限公司 | Preparation method of dry-method single-drawing multilayer diaphragm, battery diaphragm and application of battery diaphragm |
| CN112004592A (en) * | 2018-03-02 | 2020-11-27 | 赛尔格有限责任公司 | Microporous membranes, battery separators, and methods of making and using the same |
| CN112886067A (en) * | 2021-02-01 | 2021-06-01 | 上海恩捷新材料科技有限公司 | Preparation method of synchronous substrate-supported solid composite electrolyte membrane |
| CN115347322A (en) * | 2022-08-30 | 2022-11-15 | 新乡市中科膜材料科技有限公司 | Preparation method and application of porous polyolefin composite membrane |
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| US20110064990A1 (en) * | 2008-05-02 | 2011-03-17 | Treofan Germany GmbH & Co.. KG | Micro-porous multi-layer membrane film based on polypropylene for batteries with a cut-off function |
| CN101997102A (en) * | 2009-08-26 | 2011-03-30 | 比亚迪股份有限公司 | Lithium ion battery diaphragm and manufacturing method thereof |
| CN102738427A (en) * | 2012-07-19 | 2012-10-17 | 河南义腾新能源科技有限公司 | Inorganic composite microporous membrane serving as lithium ion battery diaphragm and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20110064990A1 (en) * | 2008-05-02 | 2011-03-17 | Treofan Germany GmbH & Co.. KG | Micro-porous multi-layer membrane film based on polypropylene for batteries with a cut-off function |
| CN101997102A (en) * | 2009-08-26 | 2011-03-30 | 比亚迪股份有限公司 | Lithium ion battery diaphragm and manufacturing method thereof |
| CN102738427A (en) * | 2012-07-19 | 2012-10-17 | 河南义腾新能源科技有限公司 | Inorganic composite microporous membrane serving as lithium ion battery diaphragm and preparation method thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112004592A (en) * | 2018-03-02 | 2020-11-27 | 赛尔格有限责任公司 | Microporous membranes, battery separators, and methods of making and using the same |
| CN109968622A (en) * | 2019-03-25 | 2019-07-05 | 成都新柯力化工科技有限公司 | A kind of method that clean type Screw Extrusion prepares lithium battery polymer dielectric film |
| CN110744840A (en) * | 2019-10-10 | 2020-02-04 | 深圳中兴新材技术股份有限公司 | Preparation method of dry-method single-drawing multilayer diaphragm, battery diaphragm and application of battery diaphragm |
| CN112886067A (en) * | 2021-02-01 | 2021-06-01 | 上海恩捷新材料科技有限公司 | Preparation method of synchronous substrate-supported solid composite electrolyte membrane |
| CN112886067B (en) * | 2021-02-01 | 2022-04-26 | 上海恩捷新材料科技有限公司 | Preparation method of synchronous substrate-supported solid composite electrolyte membrane |
| CN115347322A (en) * | 2022-08-30 | 2022-11-15 | 新乡市中科膜材料科技有限公司 | Preparation method and application of porous polyolefin composite membrane |
| CN115347322B (en) * | 2022-08-30 | 2024-02-02 | 新乡市中科膜材料科技有限公司 | Preparation method and application of porous polyolefin composite membrane |
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