CN107331822A - A kind of three-layer co-extruded lithium ion battery separator of polypropylene, polyethylene/polypropylene and preparation method thereof - Google Patents
A kind of three-layer co-extruded lithium ion battery separator of polypropylene, polyethylene/polypropylene and preparation method thereof Download PDFInfo
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M50/411—Organic material
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The present invention relates to a kind of three-layer co-extruded lithium battery diaphragm of polypropylene, polyethylene/polypropylene, it is A1/B/A2Three-decker, wherein, top layer A1、A2It is the loose structure of COPP formation；Intermediate layer B is the loose structure of high density polyethylene (HDPE) formation；Its preparation method is：By high density polyethylene (HDPE) and COPP difference fusion plastification, then synchronously it is coextruded from three layers of compound casting head of three die cavities and draws film forming, obtained with A1/B/A2The coextrusion casting film of three-decker；Made annealing treatment successively again, longitudinal cold stretch, hot-stretch, the three-layer co-extruded lithium ion battery separator of polypropylene, polyethylene/polypropylene is obtained after thermal finalization.Lithium battery diaphragm of the present invention has the higher fusion temperature of the relatively low closed pore temperature in intermediate layer and top layer, improves the melt integrity and battery security of the extreme high-temperature condition lower diaphragm plate of lithium battery；There is the intermediate layer of low melt index and the top layer of high fusion index simultaneously, good intermediate layer intensity and top layer plasticizing uniformity is had concurrently.
Description
Technical field
The invention belongs to lithium ion battery separator technical field, and in particular to a kind of polypropylene (PP)/polyethylene (PE)/poly-
Propylene (PP) three-layer co-extruded lithium ion battery separator and preparation method thereof.
Background technology
Barrier film is to determine lithium battery inner boundary structure, internal resistance, capacity, the crucial material of cycle performance, particularly security performance
Material.Overcharge/cross put or other extreme conditions under, lithium battery interior temperature can it is very fast rise.When internal temperature of battery close to every
During film pore-forming material fusing point, pore-forming material can soften and occur closed pore behavior, so as to block ion to transmit to form open circuit, play peace
The effect of full guard.But the barrier film of individual layer material is identical with fusion temperature due to closed pore temperature, barrier film while closed pore by
Drastically raised in temperature, reaction, so as to cause battery plus-negative plate directly to contact, causes short-circuit and quick-fried not as good as rupture of membranes is easily caused
It is fried.
To solve the problem of closed pore temperature is identical with fusion temperature, researcher is combined using dissimilar materials to barrier film
To obtain the higher barrier film fusing point temperature difference.Such as in patent US5952120, Celgard is entered using PE microporous barriers and PP microporous barriers
Row hot pressing is combined, and obtains the compound sandwich constructions of PE/PP, is ensureing the same of PE low temperature closed pore (130~140 DEG C of fusion temperature)
When, PP films are not ruptured due to higher fusion temperature (~150 DEG C).But, it is this to form ex situ compound again after microporous barrier
Thickness of multilayer film prepared by complex technique is larger；While the pore structure in order to not damage barrier film, hot combined temp is relatively low, PE/PP
Bonding it is insufficient, cause barrier film to occur layering behavior under the elevated condition of work of temperature.For the compound skill of non-laminar
Art, Tang haolin et al. (J Power Sources 2013,241,203) use PVDF-HFP (vinylidene-hexafluoros third
Alkene copolymer) it is combined with ePTFE (expanded PTFE) porous network, the PVDF-HFP/ePTFE composite diaphragm closed pores of preparation
Temperature is~150 DEG C, and because ePTFE forms continuous network structure, its fusion temperature (broken film temperature) reaches~350 DEG C.
But, this complex technique cost using porous network as matrix is too high, it is impossible to the need for meeting large-scale industrial production.
It is multi-layer co-extruded be high efficiency, at low cost obtain ultrathin film the mode of production, due to each layer higher than fusing temperature
It is coextruded under conditions of degree, Coating combination closely, is difficult layering under the conditions of applied at elevated temperature.ZL201410427455.1 is public
A kind of technology of preparing of PP/EVA/PVDC/EVA/PE five-layer co-squeezings film is opened, multilayer film, which uses to have, to be used to extrude different materials
Multiple layers of molds prepare, extruding layer is provided with multiple runners being connected with extruder.ZL201410497379.1 discloses one kind
The method that five-layer co-squeezing prepares Biaxially oriented polypropylene antifog film, each layer containing different additive in preparation, by 180~
250 DEG C of different temperatures are pooled to die head from each layer extruder and sent jointly, obtain five layers of compound casting films, and gross thickness is 17~49
μm.For the high lithium battery diaphragm of pore structure index request, because each component is in close temperature melt fluidity, knot
The difference of brilliant and crystalline transformation pore-forming property, the certain technical complexity of multi-layer co-extruded presentation.
ZL201510269976.3 is using two kinds of different polypropylene fusion co-extrusions of isotacticity more than 98%, melt index
Go out, obtain composite construction, the barrier film with good mechanical properties.ZL201410247897.8 discloses a kind of three-layer composite structure
COPP and HOPP is respectively adopted in microporous polypropylene membrane and preparation method thereof, surface layer and intermediate layer；Due to two kinds
Relatively, therefore, co-extrusion rheological characteristic is easier to solve for polypropylene fusing point and mobility；Its pore-forming uniformity is brilliant by adding β
Type nucleator and biaxial tension are solved.It is three-layer co-extruded that ZL201410292515 discloses a polypropylene, polyethylene/polypropylene
The preparation method of composite diaphragm, in preparation process, using the polypropylene and polyethylene of low melt index to the rheological characteristic of barrier film
Strengthened.ZL201510366657.4,201510366133.5 are using addition metal or semiconductor transformation in the resin of top layer
The method of compound, increases the pore-forming performance on top layer.But, in above-mentioned patent, in the addition of top layer or intermediate layer dissimilar materials
The stability of barrier film in use can be influenceed.
The content of the invention
The technical problems to be solved by the invention be for above-mentioned prior art exist deficiency and provide a kind of polypropylene/
Three-layer co-extruded lithium ion battery separator of polyethylene/polypropylene and preparation method thereof, takes into account synchronous curtain coating and synchro-draw pore-forming, nothing
Additive need to be relied on, you can obtain uniform compound, high hole membrane configuration.
The technical scheme that the present invention is used by solution the problem of set forth above for：
A kind of three-layer co-extruded lithium ion battery separator of polypropylene, polyethylene/polypropylene, it is A1/B/A2Three-decker, its
In, top layer A1、A2It is the loose structure of COPP (PP) formation；Intermediate layer B is many of high density polyethylene (HDPE) (PE) formation
Pore structure.
By such scheme, described A1/B/A2The gross thickness of three-decker is 9~50 μm.
By such scheme, described intermediate layer B thickness is top layer A1Or top layer A21~4 times of thickness, top layer A1、A2Thickness
Degree is equal or unequal.
By such scheme, the molecular weight of described COPP is 20~400,000, polyethylene (PE) block concentration 0.1~
2%, 230 DEG C of melt index are 2~8.
By such scheme, the molecular weight of described high density polyethylene (HDPE) is 40~600,000,190 DEG C of melt index be 0.1~
1。
The preparation method of the above-mentioned three-layer co-extruded lithium ion battery separator of polypropylene, polyethylene/polypropylene of the present invention, main step
It is rapid as follows：
(1) step is melted：High density polyethylene (HDPE) and COPP are separately added into two extruder fusion plastifications；
(2) casting step：The high density polyethylene (HDPE) and COPP of fusion plastification obtained by step (1) is synchronous from three layers
It is coextruded in three layers of compound casting head of coextrusion casting machine, and film forming is drawn under high drafting ratio, is obtained with A1/B/A2
The coextrusion casting film of three-decker；
(3) annealing steps：To there is A obtained by step (2)1/B/A2The coextrusion casting film of three-decker is made annealing treatment,
Naturally cool to room temperature；
(4) stretching step：Casting films to annealing obtained by step (3) carry out longitudinal cold stretch, hot-stretch, shape successively
Into porous membrane structure；
(5) heat setting step：Room temperature is cooled to after thermal finalization to perforated membrane obtained by step (4), polypropylene/poly- second is obtained
The three-layer co-extruded lithium ion battery separator of alkene/polypropylene.
By such scheme, in step (1), 50~75 DEG C of high density polyethylene (HDPE) extruder transportation section temperature, compression section temperature
140 DEG C~195 DEG C, 170 DEG C~195 DEG C of melt zone temperature, 170 DEG C~220 DEG C of metering section temperature, screw speed be 50~
300rpm；50~75 DEG C of COPP extruder transportation section temperature, 140 DEG C~225 DEG C of compression section temperature, melt zone temperature
170 DEG C~225 DEG C, 170 DEG C~215 DEG C of metering section temperature, screw speed be 50~300rpm.
By such scheme, in step (2), die head temperature is 190~215 DEG C, die orifice 2.0~3.0mm of aperture, casting roller speed
25~80m/min, 35~100 DEG C of chill-roll temperature.
By such scheme, in step (3), annealing temperature is 110~130 DEG C, 8~16h of annealing time position.
By such scheme, in step (4), cold drawing temperature is 30~50 DEG C, draw ratio is 1.2~1.5；Hot-stretch temperature
It is 1.5~3.0 for 120~150 DEG C, draw ratio.
By such scheme, in step (5), 125~140 DEG C of heat setting temperature, time 10s~5min.
Preferably, the present invention provides a kind of more detailed three-layer co-extruded lithium ion battery of polypropylene, polyethylene/polypropylene
The preparation method of barrier film, is comprised the following steps that：
(1) step is melted：High density polyethylene (HDPE) and COPP are separately added into two extruder fusion plastifications, its
In, 50~75 DEG C of high density polyethylene (HDPE) extruder transportation section temperature, 140 DEG C~195 DEG C of compression section temperature, melt zone temperature 170
DEG C~195 DEG C, 170 DEG C~220 DEG C of metering section temperature, screw speed be 50~300rpm；COPP extruder transportation section
50~75 DEG C of temperature, 140 DEG C~225 DEG C of compression section temperature, 170 DEG C~225 DEG C of melt zone temperature, 170 DEG C of metering section temperature~
215 DEG C, screw speed be 50~300rpm；
(2) casting step：The high density polyethylene (HDPE) and COPP of fusion plastification obtained by step (1) is synchronous from three types
It is coextruded in three layers of compound casting head of chamber and draws film forming under high drafting ratio, is obtained with A1/B/A2Three-decker
Coextrusion casting film, wherein, die head temperature be 190~215 DEG C, 2.0~3.0mm of die orifice aperture, 25~80m/ of casting roller speed
Min, 35~100 DEG C of chill-roll temperature；
(3) annealing steps：To there is A obtained by step (2)1/B/A2The coextrusion casting film of three-decker is made annealing treatment,
Annealing temperature is 110~130 DEG C, 8~16h of annealing time position, and room temperature is naturally cooled to afterwards；
(4) stretching step：Casting films to annealing obtained by step (3) carry out longitudinal cold stretch, hot-stretch successively, cold
To draw temperature be 30~50 DEG C, draw ratio is 1.2~1.5；Hot-drawn temperature is 120~150 DEG C, draw ratio is 1.5~3.0, is formed
Loose structure；
(5) heat setting step：To the perforated membrane of above-mentioned stretching in 125~140 DEG C of thermal finalization 10s~5min, cool down afterwards
To room temperature, the three-layer co-extruded lithium ion battery separator of polypropylene, polyethylene/polypropylene is obtained.
Compared with prior art, the beneficial effects of the invention are as follows：
First, the lithium battery diaphragm prepared by the present invention is that top layer is the three-layer composite structure that PP, intermediate layer are PE, is had
The higher fusion temperature of the relatively low closed pore temperature in intermediate layer and top layer, so as to improve the complete of the extreme hot conditions lower diaphragm plate of lithium battery
Whole property and battery security；Meanwhile, the top layer in intermediate layer and high fusion index with low melt index has good intensity concurrently
Uniformity is plastified with top layer.
Second, the present invention can not take into account synchronous curtain coating and synchro-draw for existing three-layer co-extruded Heterogeneous Composite lithium electric separator
Pore-forming, so as to rely on other additives of addition and obtain that uniform compound, there is provided one kind for the technological deficiency of high hole membrane configuration
Three-layer co-extruded lithium ion battery separator of polypropylene, polyethylene/polypropylene and preparation method thereof, utilizes COPP and polyethylene
Close temperature flowing and annealing crystallization between body, directly prepare the uniform compound, composite diaphragm of high pore structure, simultaneous
Synchronous curtain coating and synchro-draw pore-forming are turned round and look at, without relying on additive.
Embodiment
For a better understanding of the present invention, with reference to the embodiment content that the present invention is furture elucidated, but the present invention
Content is not limited solely to the following examples.
Embodiment 1
A kind of three-layer co-extruded lithium ion battery separator of polypropylene, polyethylene/polypropylene, its preparation method specific steps are such as
Under：
(1) step is melted：The high density polyethylene (HDPE) and molecular weight for being 0.3 by molecular weight 40~500,000,190 DEG C of melt index
20~300,000, PE block concentrations 0.5%, 230 DEG C of melt index are separately added into two extruder melting modelings for 4 COPP
Change；Wherein, 50~65 DEG C of high density polyethylene (HDPE) extruder transportation section temperature, 140 DEG C~180 DEG C of compression section temperature, melt zone temperature
170 DEG C~200 DEG C of degree, 170 DEG C~190 DEG C of metering section temperature, screw speed are 200rpm；COPP extruder transportation section
50~60 DEG C of temperature, 140 DEG C~175 DEG C of compression section temperature, 170 DEG C~210 DEG C of melt zone temperature, 170 DEG C of metering section temperature~
195 DEG C, screw speed be 250rpm；
(2) casting step：The high density polyethylene (HDPE) and COPP of fusion plastification obtained by step (1) is synchronous from three types
It is coextruded in three layers of compound casting head of chamber and draws film forming under high draw ratio, is obtained with A1/B/A2Three layers of structure
Coextrusion casting film, wherein, die head temperature is 200 DEG C, die orifice aperture 2.5mm, casting roller speed 70m/min, and chill-roll temperature is 40
℃；
(3) annealing steps：To there is A obtained by step (2)1/B/A2The three-layer co-extruded casting films of structure are made annealing treatment,
Annealing temperature is 125 DEG C, annealing time position 16h, and room temperature is naturally cooled to afterwards；
(4) stretching step：Casting films to annealing obtained by step (3) carry out longitudinal cold stretch, hot-stretch successively, cold
To draw temperature be 40 DEG C, the fast ratio of stretching is 1.4；Hot-drawn temperature is 140 DEG C, fast ratio of stretching is 2.0, formation porous membrane structure；
(5) heat setting step：To the perforated membrane obtained by step (4) in 130 DEG C of thermal finalization 10s~5min, it is cooled to afterwards
Room temperature, obtains the three-layer co-extruded lithium ion battery separator of polypropylene, polyethylene/polypropylene.
The three-layer co-extruded lithium ion battery separator gross thickness of polypropylene, polyethylene/polypropylene manufactured in the present embodiment is 20 μm,
Intermediate layer B thickness degree is 10 μm, top layer A1And A2Thickness is 5 μm.
Embodiment 2
A kind of three-layer co-extruded lithium ion battery separator of polypropylene, polyethylene/polypropylene, its preparation method specific steps are such as
Under：
(1) step is melted：It is 40~500,000,190 DEG C of high density polyethylene (HDPE) of melt index 0.1 and molecular weight 20 by molecular weight
~30 ten thousand, PE block concentrations 0.1%, 230 DEG C of melt index are separately added into two extruder melting modelings for 2 COPP
Change；Wherein, 60~75 DEG C of high density polyethylene (HDPE) extruder transportation section temperature, 140 DEG C~195 DEG C of compression section temperature, melt zone temperature
175 DEG C~195 DEG C of degree, 175 DEG C~215 DEG C of metering section temperature, screw speed are 50rpm；COPP extruder transportation section
60~75 DEG C of temperature, 140 DEG C~195 DEG C of compression section temperature, 170 DEG C~225 DEG C of melt zone temperature, 170 DEG C of metering section temperature~
215 DEG C, screw speed be 50rpm；
(2) casting step：The high density poly propylene and COPP of fusion plastification obtained by step (1) is synchronous from three types
It is coextruded in three layers of compound casting head of chamber and film forming is drawn under high magnification and is obtained with A1/B/A2Structure it is three-layer co-extruded
Casting films, wherein, die head temperature is 190 DEG C, die orifice aperture 2.0mm, casting roller speed 25m/min, 35 DEG C of chill-roll temperature position；
(3) annealing steps：To there is A obtained by step (2)1/B/A2The three-layer co-extruded casting films of structure are made annealing treatment,
Annealing temperature is 120 DEG C, annealing time position 18h, and room temperature is naturally cooled to afterwards；
(4) stretching step：Casting films to annealing obtained by step (3) carry out longitudinal cold stretch, hot-stretch successively, cold
To draw temperature be 30 DEG C, the fast ratio of stretching is 1.2；Hot-drawn temperature is 120 DEG C, fast ratio of stretching is 1.5, formation porous membrane structure；
(5) heat setting step：To the perforated membrane obtained by step (4) in 125 DEG C of thermal finalization 10s~5min, it is cooled to afterwards
Room temperature, obtains the three-layer co-extruded lithium ion battery separator of polypropylene, polyethylene/polypropylene.
The three-layer co-extruded lithium ion battery separator gross thickness of polypropylene, polyethylene/polypropylene manufactured in the present embodiment is 50 μm,
Intermediate layer B thickness degree is 30 μm, top layer A1And A2Thickness is 10 μm.
Embodiment 3
A kind of three-layer co-extruded lithium ion battery separator of polypropylene, polyethylene/polypropylene, its preparation method specific steps are such as
Under：
(1) step is melted：Be 50~600,000 by molecular weight, 190 DEG C of melt index be 1 high density polyethylene (HDPE) and molecular weight 30
~40 ten thousand, PE block concentrations 2%, 230 DEG C of melt index are that 8 COPPs are separately added into two extruder fusion plastifications；Its
In, 60~70 DEG C of high density polyethylene (HDPE) extruder transportation section temperature, 160 DEG C~190 DEG C of compression section temperature, melt zone temperature 170
DEG C~210 DEG C, 170 DEG C~195 DEG C of metering section temperature, screw speed be 300rpm；COPP extruder transportation section temperature
60~70 DEG C, 160 DEG C~220 DEG C of compression section temperature, 190 DEG C~215 DEG C of melt zone temperature, metering section temperature 190 DEG C~205
DEG C, screw speed be 300rpm；
(2) casting step：The high density polyethylene (HDPE) and COPP of fusion plastification obtained by step (1) is synchronous from three types
It is coextruded in three layers of compound casting head of chamber and film forming is drawn under high draw ratio and is obtained with A1/B/A2Three layers of structure are altogether
Casting films are squeezed, wherein, die head temperature is 215 DEG C, die orifice aperture 3.0mm, casting roller speed 80m/min, 80 DEG C of chill-roll temperature position；
(3) annealing steps：To there is A obtained by step (2)1/B/A2The three-layer co-extruded casting films of structure are made annealing treatment,
Annealing temperature is 130 DEG C, annealing time position 20h, and room temperature is naturally cooled to afterwards；
(4) stretching step：Casting films to annealing obtained by step (3) carry out longitudinal cold stretch, hot-stretch successively, cold
To draw temperature be 50 DEG C, the fast ratio of stretching is 1.5；Hot-drawn temperature is 150 DEG C, fast ratio of stretching is 3.0, formation loose structure；
(5) heat setting step：To the perforated membrane obtained by step (4) in 140 DEG C of thermal finalization 10s~5min, it is cooled to afterwards
Room temperature, obtains the three-layer co-extruded lithium ion battery separator of polypropylene, polyethylene/polypropylene.
The three-layer co-extruded lithium ion battery separator gross thickness of polypropylene, polyethylene/polypropylene manufactured in the present embodiment is 9 μm,
Intermediate layer B thickness degree is 3 μm, top layer A1And A2Thickness is 3 μm.
Embodiment 4
A kind of three-layer co-extruded lithium ion battery separator of polypropylene, polyethylene/polypropylene, its preparation method specific steps are such as
Under：
(1) step is melted：Be 50~600,000 by molecular weight, 190 DEG C of melt index be 0.7 high density polyethylene (HDPE) and molecular weight
30~400,000, PE block concentrations 1.5%, 230 DEG C of melt index are separately added into two extruder meltings for 5.8 COPP
Plasticizing；Wherein, 55~65 DEG C of high density polyethylene (HDPE) extruder transportation section temperature, 160 DEG C~185 DEG C of compression section temperature, melt zone
170 DEG C~210 DEG C of temperature, 170 DEG C~200 DEG C of metering section temperature, screw speed are 100rpm；COPP extruder is conveyed
55~70 DEG C of Duan Wendu, 150 DEG C~210 DEG C of compression section temperature, 170 DEG C~230 DEG C of melt zone temperature, 170 DEG C of metering section temperature
~210 DEG C, screw speed be 100rpm；
(2) casting step：The high density polyethylene (HDPE) and COPP of fusion plastification obtained by step (1) is synchronous from three types
It is coextruded in three layers of compound casting head of chamber and draws film forming under high draw ratio, is obtained with A1/B/A2Three layers of structure
Coextrusion casting film, wherein, die head temperature is 200 DEG C, die orifice aperture 2.4mm, casting roller speed 50m/min, chill-roll temperature position 70
℃；
(3) annealing steps：To there is A obtained by step (2)1/B/A2The three-layer co-extruded casting films of structure are made annealing treatment,
Annealing temperature is 125 DEG C, and annealing time 10s~5min is cooled to room temperature afterwards；
(4) stretching step：Casting films to annealing obtained by step (3) carry out longitudinal cold stretch, hot-stretch successively, cold
To draw temperature be 45 DEG C, the fast ratio of stretching is 1.3；Hot-drawn temperature is 120~150 DEG C, fast ratio of stretching is 2.5, formation porous membrane structure；
(5) heat setting step：To the perforated membrane obtained by step (4) in 135 DEG C of thermal finalization 10s~5min, it is cooled to afterwards
Room temperature, obtains the three-layer co-extruded lithium ion battery separator of polypropylene, polyethylene/polypropylene.
The three-layer co-extruded lithium ion battery separator gross thickness of polypropylene, polyethylene/polypropylene manufactured in the present embodiment is 30 μm,
Intermediate layer B thickness degree is 20 μm, top layer A1And A2Thickness is 5 μm.
The three-layer co-extruded barrier film of polypropylene, polyethylene/polypropylene prepared by embodiment 1~4 is used and newly thinks carefully omnipotent reality
Machine, Gurley Permeability gauges, health tower PoreMaster-60 mercury injection apparatuses are tested, its various aspects of performance is tested under the same conditions, its data
As a result it is as shown in table 1.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Porosity % | 42 | 39 | 45 | 43 |
| Air penetrability s/100mL | 346 | 593 | 325 | 457 |
| Puncture strength, gf | 678 | 743 | 585 | 646 |
| Longitudinal tensile strength, MPa | 148 | 165 | 136 | 143 |
| Shrinkage factor (90 DEG C, 2h) | 3 | 2.5 | 2.2 | 2.9 |
| Closed pore temperature, DEG C | 133 | 136 | 129 | 131 |
| Fusion temperature DEG C | 153 | 156 | 149 | 151 |
As shown in table 1, the prepared three-layer co-extruded barrier film porosity of polypropylene, polyethylene/polypropylene of the present invention is high, gas permeability
Good, puncture strength and longitudinal tensile strength, shrinkage factor are suitable, and higher with the relatively low closed pore temperature in intermediate layer and top layer
Fusion temperature, improves the melt integrity and battery security of the extreme high-temperature condition lower diaphragm plate of lithium battery.
Described above is only the preferred embodiment of the present invention, it is noted that come for one of ordinary skill in the art
Say, without departing from the concept of the premise of the invention, some modifications and variations can also be made, these belong to the present invention's
Protection domain.
Claims (10)
1. a kind of three-layer co-extruded lithium ion battery separator of polypropylene, polyethylene/polypropylene, it is characterised in that it is A1/B/A2Three layers
Structure, wherein, top layer A1、A2It is the loose structure of COPP formation；Intermediate layer B is many of high density polyethylene (HDPE) formation
Pore structure.
2. a kind of three-layer co-extruded lithium ion battery separator of polypropylene, polyethylene/polypropylene according to claim 1, it is special
Levy and be described A1/B/A2The gross thickness of three-decker is 9~50 μm.
3. a kind of three-layer co-extruded lithium ion battery separator of polypropylene, polyethylene/polypropylene according to claim 1, it is special
Levy and be that described intermediate layer B thickness is top layer A1Or top layer A21~4 times of thickness, top layer A1、A2Thickness it is equal or different.
4. a kind of three-layer co-extruded lithium ion battery separator of polypropylene, polyethylene/polypropylene according to claim 1, it is special
Levy and be that the molecular weight of described COPP is 20~400,000,0.1~2%, 230 DEG C of melt index of polyethylene block content
For 2~8.
5. a kind of three-layer co-extruded lithium ion battery separator of polypropylene, polyethylene/polypropylene according to claim 1, it is special
Levy be described high density polyethylene (HDPE) molecular weight be 40~600,000,190 DEG C of melt index be 0.1~1.
6. a kind of preparation method of the three-layer co-extruded lithium ion battery separator of polypropylene, polyethylene/polypropylene, it is characterised in that main
Step is as follows：
(1) step is melted：High density polyethylene (HDPE) and COPP are separately added into two extruder fusion plastifications；
(2) casting step：The high density polyethylene (HDPE) and COPP of fusion plastification obtained by step (1) is synchronous from three-layer co-extruded
It is coextruded in three layers of compound casting head of casting machine, and draws film forming, is obtained with A1/B/A2The coextrusion casting of three-decker
Film；
(3) annealing steps：To there is A obtained by step (2)1/B/A2The coextrusion casting film of three-decker is made annealing treatment, natural
It is cooled to room temperature；
(4) stretching step：Casting films to annealing obtained by step (3) carry out longitudinal cold stretch, hot-stretch successively, are formed many
Pore membrane structure；
(5) heat setting step：Room temperature is cooled to after thermal finalization to perforated membrane obtained by step (4), obtain polypropylene, polyethylene/
The three-layer co-extruded lithium ion battery separator of polypropylene.
7. a kind of preparation of three-layer co-extruded lithium ion battery separator of polypropylene, polyethylene/polypropylene according to claim 6
Method, it is characterised in that in step (1), 50~75 DEG C of high density polyethylene (HDPE) extruder transportation section temperature, 140 DEG C of compression section temperature
~195 DEG C, 170 DEG C~195 DEG C of melt zone temperature, 170 DEG C~220 DEG C of metering section temperature, screw speed be 50~300rpm；Altogether
Poly- 50~75 DEG C of polypropylene extruder transportation section temperature, 140 DEG C~225 DEG C of compression section temperature, melt zone temperature 170 DEG C~225
DEG C, 170 DEG C~215 DEG C of metering section temperature, screw speed be 50~300rpm.
8. a kind of preparation of three-layer co-extruded lithium ion battery separator of polypropylene, polyethylene/polypropylene according to claim 6
Method, it is characterised in that in step (2), die head temperature is 190~215 DEG C, die orifice 2.0~3.0mm of aperture, casting roller speed 25~
80m/min, 35~100 DEG C of chill-roll temperature.
9. a kind of preparation of three-layer co-extruded lithium ion battery separator of polypropylene, polyethylene/polypropylene according to claim 6
Method, it is characterised in that in step (3), annealing temperature is 110~130 DEG C, 8~16h of annealing time position；In step (5), heat is fixed
125~140 DEG C of type temperature, time 10s~5min.
10. a kind of system of three-layer co-extruded lithium ion battery separator of polypropylene, polyethylene/polypropylene according to claim 6
Preparation Method, it is characterised in that in step (4), cold drawing temperature is 30~50 DEG C, draw ratio is 1.2~1.5；Hot-stretch temperature is
120~150 DEG C, draw ratio be 1.5~3.0.
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Denomination of invention: Polypropylene / polyethylene / polypropylene three-layer coextrusion lithium ion battery diaphragm and its preparation method Effective date of registration: 20220622 Granted publication date: 20201020 Pledgee: Bank of China Limited Wuhan Jianghan sub branch Pledgor: HUIQIANG (WUHAN) NEW ENERGY MATERIAL TECHNOLOGY CO.,LTD. Registration number: Y2022420000176 |
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