CN102199320B - Polymer composition for forming battery isolating membrane - Google Patents
Polymer composition for forming battery isolating membrane Download PDFInfo
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- CN102199320B CN102199320B CN2010106140055A CN201010614005A CN102199320B CN 102199320 B CN102199320 B CN 102199320B CN 2010106140055 A CN2010106140055 A CN 2010106140055A CN 201010614005 A CN201010614005 A CN 201010614005A CN 102199320 B CN102199320 B CN 102199320B
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a polymer composition for forming a battery isolating membrane. The polymer composition comprises (a) a mixture of ultra high molecular weight polyethylene and high density polyethylene, (b) a pore-forming agent and (c) an antioxidant, wherein the molecular weight of the ultra high molecular weight polyethylene is 1.5*10<6>-7.5*10<6>, the density of the high density polyethylene is 0.945g/cm<3>, and the weight ratio of ultra high molecular weight polyethylene to high density polyethylene is 1: (1-20); based on 100 parts of weights of the ultra high molecular weight polyethylene and high density polyethylene, the quantity of the pore-forming agent is 500-2000 weight parts; and based on 100 parts of the weights of the ultra high molecular weight polyethylene and high density polyethylene, the quantity of the antioxidant is 0.5-20 parts.
Description
Technical field
The present invention relates to a kind of polymer composition that is used to form battery isolating film (especially lithium ion battery barrier film), the battery isolating film that forms with the present composition has good over-all properties, for example, the battery isolating film that forms with the present composition has low mean pore size, more uniform pore size distribution, the suitable broken temperature of closed pore temperature, film, good porosity and film toughness etc.
Background technology
Battery isolating film is one of main raw of battery, its effect is with the anode of inside battery and negative electrode separates in order to avoid short circuit, and ion can be moved swimmingly between the two poles of the earth by barrier film, form electric current, also at the battery operated ionic channel of closing when abnormal conditions occurring, cut off electric current to guarantee cell safety.
Battery isolating film is called again battery diaphragm, and its salient features comprises broken temperature of thickness, voidage, aperture, pore size distribution, intensity, closed pore temperature and film etc.The intensity of battery isolating film is mainly with tensile strength with pierce through intensity and characterize: tensile strength has characterized battery isolating film under larger external stress effect, and barrier film itself can guarantee not rupture of membranes, the maximum stretching force that can bear when keeping the isolation membrane integrity; Owing to only separating with barrier film between positive and negative pole material, and positive and negative pole material is irregular, and therefore irregular electrode materials can pierce through again battery isolating film, pierces through the anti-performance that pierces through of intensity characterizing battery barrier film.
An effect of battery isolating film is that ion can be moved between the two poles of the earth by barrier film swimmingly, forms electric current.But in order to prevent that battery from crossing thermogenesis such as danger such as blasts, require micropore in this barrier film that melting occurs after temperature rises to certain degree closed, pass through with isolated ion.Therefore, this area is called closed pore temperature with the micropore generation melting closure of battery isolating film with the temperature that isolated ion passes through.
The film of battery isolating film breaks temperature and refers to after reaching described closed pore temperature, and the temperature of barrier film continues to rise until the fusing of generation barrier film is broken, and the temperature that barrier film generation melting is ruptured in this area is called the broken temperature of film.
Therefore ensure enough temperature ranges between the broken temperature of the closed pore temperature of this area requirement battery isolating film and film, so that when occurrence temperature inertia rises after temperature reaches the closed pore temperature of barrier film, battery isolating film can have enough temperature buffer spaces, film rupture does not occur.Difference between the broken temperature of the film of existing battery isolating film and closed pore temperature is generally 30-40 ℃.But, from security consideration, need further to promote the broken temperature of film of battery isolating film and the difference between closed pore temperature.
In addition, for battery isolating film, guarantee ion can move swimmingly to form electric current by barrier film between the two poles of the earth therefore need to have certain voidage due to needs, but the rising of voidage inevitably can cause the strength degradation of barrier film, thereby affects the reliability of battery.In addition, the wetting property of known electrolytes is relevant with aperture and pore size distribution: usually, be not that in very large situation, pore size distribution is more even in the aperture, the wetting property of electrolytic solution is just better.Wetting property directly affects the resistance of ion migration, and wetting property is better, and ion is just less by the resistance that barrier film moves, and the internal resistance of battery is just less, and the current density of battery just has larger raising leeway, and the cycle performance of battery is also better.
Porosity, aperture, pore size distribution and the tensile strength of final battery isolating film depend on many factors, for example for the manufacture of the manufacturing process of material and the battery isolating film of battery isolating film, but depend primarily on its material.Be the battery isolating film that acquisition has gratifying porosity, aperture, pore size distribution and tensile strength, prior art has proposed various battery isolating film and manufacture method thereof.
For example, a kind of improved barrier film system that is applicable to lithium cell is disclosed as the CN 1954447A in PCT China national stage, it comprises that thickness is that 5-175 micron, porosity are the microporous membrane of 30-95%, and this microporous membrane is 1 * 10 by the minimum molecular-weight average of 85-95 % by weight
6Ultrahigh molecular weight polyethylene(UHMWPE) and the median size of the 5-15 % by weight titanium oxide microparticle filler that is the 0.001-1 micron consist of.A better example of the prior art document is mentioned ultrahigh molecular weight polyethylene(UHMWPE), the low molecular weight polyethylene of 1-90 % by weight and the titanium dioxide of 1-90 % by weight that its battery isolating film contains the 1-90 % by weight.And it is also mentioned in other embodiments, can with high density polyethylene(HDPE) or two or the mixture of three kind of ultrahigh molecular weight polyethylene(UHMWPE) (molecular weight is different) and high density polyethylene(HDPE) or other polyolefine, polyolefin copolymer or derivatives thereof replace ultrahigh molecular weight polyethylene(UHMWPE), and stable metal oxide filler replacement titanium dioxide filler that can other is suitable and performance improves.In other words, to mention the material for the manufacture of its battery isolating film can be following several to CN 1954447A:
(i) ultrahigh molecular weight polyethylene(UHMWPE), low molecular weight polyethylene and titanium oxide microparticle filler;
(ii) high density polyethylene(HDPE),, low molecular weight polyethylene and titanium oxide microparticle filler;
(iii) two or mixture, low molecular weight polyethylene and the titanium oxide microparticle filler of three kind of ultrahigh molecular weight polyethylene(UHMWPE) and high density polyethylene(HDPE);
(iv)....
In embodiment, CN 1954447A has implemented two groups of technical schemes, the i.e. combination of the combination of ultrahigh molecular weight polyethylene(UHMWPE) and titanium dioxide and ultrahigh molecular weight polyethylene(UHMWPE), low molecular weight polyethylene and titanium dioxide.As shown in its table 1, CN 1954447A proves that the barrier film that its technical scheme makes has the porosity of 51-74% and the aperture of average 1 micron.
Although CN 1954447A makes battery isolating film and can substantially meet the demands, the performance of this barrier film, especially mean pore size and pore size distribution still have room for improvement, in order to further improve it as the electrolytic solution wetting property of battery isolating film.
Therefore, a goal of the invention of the present invention is to provide a kind of polymer composition that is used to form battery isolating film, the battery isolating film that forms with this polymer composition has the broken temperature of film of improved battery isolating film and difference, improved intensity, mean pore size and the pore size distribution between closed pore temperature, thereby be conducive to improve it as the electrolytic solution wetting property of battery isolating film, improve the current density of the battery contain this battery isolating film and be conducive to improve work-ing life and the reliability of this battery.
Summary of the invention
A goal of the invention of the present invention is to provide a kind of polymer composition that is used to form battery isolating film, the battery isolating film that forms with this composition has the broken temperature of film of improved battery isolating film and difference, improved intensity, mean pore size and the pore size distribution between closed pore temperature, thereby be conducive to improve it as the electrolytic solution wetting property of battery isolating film, improve the current density of the battery contain this battery isolating film and be conducive to improve work-ing life and the reliability of this battery.
Therefore, one aspect of the present invention relates to a kind of polymer composition that is used to form battery isolating film, and it comprises:
(a) molecular weight is 1.5 * 10
6-7.5 * 10
6Ultrahigh molecular weight polyethylene(UHMWPE) and density be 0.945g/cm
3The mixture of above high density polyethylene(HDPE), the weight ratio of described ultrahigh molecular weight polyethylene(UHMWPE) and high density polyethylene(HDPE) is 1: 1-20;
(b) weight by described ultrahigh molecular weight polyethylene(UHMWPE) and high density polyethylene(HDPE) is 100 parts, the pore former of 500-2000 weight part; With
(c) weight by described ultrahigh molecular weight polyethylene(UHMWPE) and high density polyethylene(HDPE) is 100 parts, 0.5-20 part antioxidant.
Another aspect of the present invention relates to composition of the present invention for the preparation of the purposes in the lithium ion battery barrier film.
Description of drawings
Further illustrate the present invention below in conjunction with accompanying drawing, in accompanying drawing:
Fig. 1 is the Photomicrograph of the battery isolating film of polymer composition formation of the present invention;
Fig. 2 is the Photomicrograph of existing battery isolating film.
Embodiment
The polymer composition that the present invention is used to form battery isolating film comprises that molecular weight is 1.5 * 10
6-7.5 * 10
6Daltonian ultrahigh molecular weight polyethylene(UHMWPE).The molecular weight of this ultrahigh molecular weight polyethylene(UHMWPE) preferably 2.5 * 10
6-6.5 * 10
6Dalton, more preferably 3.5 * 10
6-5.5 * 10
6Dalton, be preferably 4.5 * 10
6-5.0 * 10
6Dalton.
Applicable ultrahigh molecular weight polyethylene(UHMWPE) is commercially available, and for example it can be available from PetroChina Company Limited.'s Lanzhou Petrochemical Company.
The polymer composition that the present invention is used to form battery isolating film also comprises high density polyethylene(HDPE).In an example of the present invention, described high density polyethylene(HDPE) is that density is 0.945g/cm
3Above high density polyethylene(HDPE).Press ASTM D 1248 and measure, the density of this high density polyethylene(HDPE) is preferably 0.945g/cm
3-1.3g/cm
3, 0.96g/cm preferably
3-1.2g/cm
3, 0.98g/cm more preferably
3-1.1g/cm
3
Applicable high density polyethylene(HDPE) also can be buied from the market, and for example it can be available from PetroChina Company Limited.'s Lanzhou Petrochemical Company.
The present invention is used to form in the polymer composition of battery isolating film, and the weight ratio of described ultrahigh molecular weight polyethylene(UHMWPE) and high density polyethylene(HDPE) is 1: 1-20, preferably 1: 2-15, more preferably 1: 5-10.If the weight ratio of described ultrahigh molecular weight polyethylene(UHMWPE) and high density polyethylene(HDPE) surpasses 1: 20, the porosity of the barrier film that forms with said composition can reduce, the aperture becomes that tensile strengths large, vertical and horizontal all can descend and percent thermal shrinkage becomes large.In addition, if the weight ratio of described ultrahigh molecular weight polyethylene(UHMWPE) and high density polyethylene(HDPE) less than 1: 1, porosity descends, the aperture becomes large, transverse tensile strength reduces and percent thermal shrinkage becomes large.
The present invention is used to form in the polymer composition of battery isolating film also can contain various additives.Weight by described ultrahigh molecular weight polyethylene(UHMWPE) and high density polyethylene(HDPE) is 100 parts, and described composition also contains the pore former of 500-2000 weight part.The indefiniteness example of applicable pore former has, for example:
Mineral oil is as CAS:8020-83-5,8042-47-5;
C
6-15Alkane is as naphthalane, decane, undecane, dodecane;
Lipid acid is as C
8-15Aliphatic carboxylic acid, for example heptane, capric acid, hendecoic acid, lauric acid;
Lipid acid alkane ester is as C
8-15Aliphatic carboxylic acid C
1-4Alkane ester, for example methyl caprate, ethyl decylate, capric acid propyl ester, the positive butyl ester of capric acid, hendecoic acid methyl esters, hendecoic acid ethyl ester, hendecoic acid propyl ester, the positive butyl ester of hendecoic acid, lauric acid methyl esters, lauric acid ethyl ester, lauric acid propyl ester, the positive butyl ester of lauric acid;
C
2-6Halogenated alkane is as ethylene dichloride, propylene dichloride, chlorofluoroethane, fluorine chloropropane.
Be preferably, described pore former is mineral oil CAS 8020-83-5 or CAS 8042-47-5, and it can be available from Lanzhou Petrochemical group of PetroChina Company Limited..
In a better example of the present invention, be 100 parts by the weight of described ultrahigh molecular weight polyethylene(UHMWPE) and high density polyethylene(HDPE), described composition contains the pore former of 800-1800 weight part, better contains the pore former of 1000-1600 weight part.
Weight by described ultrahigh molecular weight polyethylene(UHMWPE) and high density polyethylene(HDPE) is 100 parts, and the present invention is used to form in the polymer composition of battery isolating film and also contains 0.5-20 part antioxidant.The effect of antioxidant is to prevent the heat drop level of polyethylene composition or oxidation degradation.
The indefiniteness example of applicable antioxidant has, and for example 4,4-thiobis (6-tertiary butyl meta-cresol), 2,6 di tert butyl 4 methyl phenol, butylated hydroxytoluene, phosphorous acid ester, tertiarybutylhydroquinone etc.
The indefiniteness example of applicable butylated hydroxytoluene has, for example BHT or 2,6 ditertiary butyl p cresol.
In a better example of the present invention, weight by described ultrahigh molecular weight polyethylene(UHMWPE) and high density polyethylene(HDPE) is 100 parts, contain in the described polymer composition that is used to form battery isolating film 0.8-18 part antioxidant, better contain 1.5-16 part antioxidant, better contain 2-12 part antioxidant.
Can adopt any ordinary method known in the art to make battery isolating film with the present composition.In a better example of the present invention, adopt thermic (TIPS) method that is separated to make barrier film, the method comprises the steps:
(a) at high temperature polymer composition is dissolved in and forms homogeneous phase liquid in the solvent of high boiling point, low volatility;
(b) cooling down makes solution produce liquid-solid phase and separates or liquid-liquid phase separation, film forming subsequently;
(c) with volatile reagent, described high boiling solvent is extracted, obtain the porous membranes with structural shape through super-dry.
In another better example of the present invention, described method comprises the step that the film that forms is carried out unidirectional or two-way stretch before also being included in solvent extraction, and carries out heat treatment and rolling film forming after extraction.
In another better example of the present invention, described method also is included in the rear step that film is stretched of extraction.The ultra-high molecular weight PE microporous membrane of producing in this way has good mechanical property.
In a better example of the present invention, described film forming step comprise melt extrude, diaphragm moulding, two-way stretch, trimming, extracting and washing, oven dry, secondary stretch, trimming, a rolling and the step such as cut.
Fig. 2 is the Photomicrograph of existing commercially available battery isolating film.Fig. 1 is the Photomicrograph of the battery isolating film that forms with polymer composition of the present invention, and relatively as seen these two Photomicrographs, have more uniform pore size distribution with the battery isolating film of polymer composition formation of the present invention; Also can find out simultaneously, the battery isolating film that polymer composition of the present invention forms has larger useful area and the passage that lithium ion passes through of being convenient to.
The battery isolating film that forms with the present composition has mean pore size and the pore size distribution uniformly between the 0.36-0.5 micron, and this battery isolating film of result can well infiltrate with electrolytic solution, thereby reduces the internal resistance of cell, improves the cycle performance of battery.In addition, the battery isolating film that forms with the present composition can reasonably be controlled at the porosity of barrier film between 45-50%, thereby has advantageously taken into account the requirement of barrier film intensity.
In addition, the temperature difference of the broken temperature of the closed pore temperature of the barrier film that makes with the present composition and film is more than 50 ℃, and therefore the temperature difference of the broken temperature of the closed pore temperature of existing battery isolating film and film can make the battery with greater security with the barrier film of present composition formation 40 ℃ of left and right.
At last, the barrier film that makes with the present composition pierce through intensity between the 510-550 gram, thereby make this film have higher intensity, different electrodes is had higher adaptability, and has the work-ing life of prolongation.
The present composition is suitable for making the barrier film of lithium ion battery.
Further illustrate the present invention below in conjunction with embodiment.
Embodiment
Test method and equipment
1. thickness
Adopt Marl, Germany THICKNESS GAUGE FOR THE MEASUREMENT OF THIN FOILS (1216+1301) to measure (mensuration of GBT+6672-2001+ plastics film and sheet thickness+mechanical measurement method)
2. resistance
Adopt volt ohm-milliammeter to record on two points of 10cm at barrier film, the result of employing is the mean value that on different measurement point, 10 times are measured.
3. transmitance
Adopt Gurley permeating degree tester 4110 to measure according to GB/T1037 plastics film and the permeable steam test method of sheet material.
4. percentage of open area
Adopt the full-automatic mercury injection apparatus of health tower PoreMaster-33 to measure.
5. aperture
Adopt UV-3200 giant-screen sweep type ultraviolet-visible pectrophotometer to measure.
6. shrinking percentage
Measure sample original length size under the status adjustment environment;
Sample board is positioned on 120 ℃ ± 2 ℃ stainless rigid frames in baking oven, heats after 5 minutes and take out, be cooled to test ambient temperature;
Specimen length size after experiment with measuring under the status adjustment environment.
The calculation and test result represents
Size changing rate S presses formula and calculates:
L
0: the size of batten after test;
L
1: the size of batten before test.
7. pierce through intensity
Adopt the Shanghai skill QJ210A universal testing machine that inclines to expose intensity according to GB/T 2679.7 cardboards and measure.
8. tensile strength
Adopt the Shanghai skill QJ210A universal testing machine that inclines to measure according to the stretching standard method of test of ASTM d882-2002 plastic tab.
9. closed pore temperature
Whole film sample is fixed on stainless rigid frame, is positioned in the baking oven that is heated to preset temp two minutes, takes out sample cooling, then measures its gas permeation rate with aforesaid method.The temperature that air penetrability is descended 5% time is taken as closed pore temperature.
10. film breaks temperature
Whole film sample is fixed on stainless rigid frame, is positioned in the baking oven that is heated to preset temp two minutes, takes out sample and observes its deform subsequently (for example shrinking).Temperature during with the highest deforming is as the broken temperature of its film.
Embodiment 1
Be 2 * 10 with 120 gram density
6High density polyethylene(HDPE) (available from PetroChina Company Limited.'s Lanzhou Petrochemical Company), 100 gram molecular weights be 2,000,000 ultrahigh molecular weight polyethylene(UHMWPE) (available from PetroChina Company Limited.'s Lanzhou Petrochemical Company), 1 gram antioxidant 2,6 tert-butyl-4-methyl-Phenols and 2000 gram viscosity grades are the mineral oil (CAS8020-83-5 of No. 39, available from Lanzhou Petrochemical Company) add in the continous batching coppers, stir with the speed of 55 rev/mins, raw material is mixed.
Miscellany is added twin screw extruder continuously; Under 120 ℃ of conditions, described ultrahigh molecular weight polyethylene(UHMWPE) and high density polyethylene(HDPE) continuous-dissolution in twin screw extruder in the mixture of mineral oil and antioxidant, then is extruded with the speed of 200 rev/mins by twin screw extruder continuously; Miscellany is input in slot die continuously; Miscellany is extruded into the curtain coating cooling roller by slot die, the curtain coating thing that becomes band under 80 ℃ of conditions.
Adopt subsequently the mineral oil of the methylene dichloride belt surfaces that extraction obtains as extraction agent; To send into continuously biaxial orientation stretching machine through the ribbon of extraction and be drawn into film under 120 ℃ of conditions; Then adopt the dichloromethane extraction agent again to extract the mineral oil of the film surface that obtains; Clean made film with pure water simultaneously; Under 120 ℃ of conditions, carried out heat setting type 15 minutes; With the speed rolling of film with 20 m/mins, obtain battery isolating film.Measure this battery isolating film with aforesaid method, result is as follows:
The Photomicrograph of above-mentioned battery isolating film as shown in Figure 1.
Embodiment 2
Be 2 * 10 with 220 gram density
6High density polyethylene(HDPE) (available from PetroChina Company Limited.'s Lanzhou Petrochemical Company), 100 gram molecular weights be 8,000,000 ultrahigh molecular weight polyethylene(UHMWPE) (available from PetroChina Company Limited.'s Lanzhou Petrochemical Company), 1.2 gram antioxidants 2,6 tert-butyl-4-methyl-Phenols and 2200 gram viscosity grades are the mineral oil (CAS8020-83-5 of No. 39, available from Lanzhou Petrochemical Company) add in the continous batching coppers, stir with the speed of 50 rev/mins, raw material is mixed.
Miscellany is added twin screw extruder continuously; Under 120 ℃ of conditions, described ultrahigh molecular weight polyethylene(UHMWPE) and high density polyethylene(HDPE) continuous-dissolution in twin screw extruder in the mixture of mineral oil and antioxidant, then is extruded with the speed of 200 rev/mins by twin screw extruder continuously; Miscellany is input in slot die continuously; Miscellany is extruded into the curtain coating cooling roller by slot die, the curtain coating thing that becomes band under 80 ℃ of conditions.
Adopt subsequently the mineral oil of the methylene dichloride belt surfaces that extraction obtains as extraction agent; To send into continuously biaxial orientation stretching machine through the ribbon of extraction and be drawn into film under 120 ℃ of conditions; Then adopt the dichloromethane extraction agent again to extract the mineral oil of the film surface that obtains; Clean made film with pure water simultaneously; Under 120 ℃ of conditions, carried out heat setting type 15 minutes; With the speed rolling of film with 20 m/mins, obtain battery isolating film.Measure this battery isolating film with aforesaid method, result is as follows:
Embodiment 3
Be 2 * 10 with 520 gram density
6High density polyethylene(HDPE) (available from PetroChina Company Limited.'s Lanzhou Petrochemical Company), 100 gram molecular weights be 3,000,000 ultrahigh molecular weight polyethylene(UHMWPE) (available from PetroChina Company Limited.'s Lanzhou Petrochemical Company), 1.5 gram antioxidants 2,6 tert-butyl-4-methyl-Phenols and 3500 gram viscosity grades are the mineral oil (CAS8020-83-5 of No. 39, available from Lanzhou Petrochemical Company) add in the continous batching coppers, stir with the speed of 50 rev/mins, raw material is mixed.
Miscellany is added twin screw extruder continuously; Under 120 ℃ of conditions, described ultrahigh molecular weight polyethylene(UHMWPE) and high density polyethylene(HDPE) continuous-dissolution in twin screw extruder in the mixture of mineral oil and antioxidant, then is extruded with the speed of 200 rev/mins by twin screw extruder continuously; Miscellany is input in slot die continuously; Miscellany is extruded into the curtain coating cooling roller by slot die, the curtain coating thing that becomes band under 80 ℃ of conditions.
Adopt subsequently the mineral oil of the tetrachloromethane belt surfaces that extraction obtains as extraction agent; To send into continuously biaxial orientation stretching machine through the ribbon of extraction and be drawn into film under 120 ℃ of conditions; Then adopt the tetrachloromethane extraction agent again to extract the mineral oil of the film surface that obtains; Clean made film with pure water simultaneously; Under 120 ℃ of conditions, carried out heat setting type 15 minutes; With the speed rolling of film with 20 m/mins, obtain battery isolating film.Measure this battery isolating film with aforesaid method, result is as follows:
Embodiment 4
Be 2 * 10 with 520 gram density
6High density polyethylene(HDPE) (available from PetroChina Company Limited.'s Lanzhou Petrochemical Company), 100 gram molecular weights be 3,000,000 ultrahigh molecular weight polyethylene(UHMWPE) (available from PetroChina Company Limited.'s Lanzhou Petrochemical Company), 1.5 gram antioxidants 2,6 tert-butyl-4-methyl-Phenols and 3500 gram viscosity grades are the mineral oil (CAS8020-83-5 of No. 45, available from Lanzhou Petrochemical Company) add in the continous batching coppers, stir with the speed of 50 rev/mins, raw material is mixed.
Miscellany is added twin screw extruder continuously; Under 120 ℃ of conditions, described ultrahigh molecular weight polyethylene(UHMWPE) and high density polyethylene(HDPE) continuous-dissolution in twin screw extruder in the mixture of mineral oil and antioxidant, then is extruded with the speed of 200 rev/mins by twin screw extruder continuously; Miscellany is input in slot die continuously; Miscellany is extruded into the curtain coating cooling roller by slot die, the curtain coating thing that becomes band under 80 ℃ of conditions.
Adopt subsequently the mineral oil of the tetrachloromethane belt surfaces that extraction obtains as extraction agent; To send into continuously biaxial orientation stretching machine through the ribbon of extraction and be drawn into film under 120 ℃ of conditions; Then adopt the tetrachloromethane extraction agent again to extract the mineral oil of the film surface that obtains; Clean made film with pure water simultaneously; Under 120 ℃ of conditions, carried out heat setting type 15 minutes; With the speed rolling of film with 20 m/mins, obtain battery isolating film.Measure this battery isolating film with aforesaid method, result is as follows:
Embodiment 5
Be 2 * 10 with 520 gram density
6High density polyethylene(HDPE) (available from PetroChina Company Limited.'s Lanzhou Petrochemical Company), 100 gram molecular weights be 3,000,000 ultrahigh molecular weight polyethylene(UHMWPE) (available from PetroChina Company Limited.'s Lanzhou Petrochemical Company), 0.5 gram 2,6 tert-butyl-4-methyl-Phenols, 0.5 gram 4, mineral oil (the CAS8020-83-5 that the blending oxidizing agent that 4-thiobis (phenol between the 6-tertiary butyl) and 0.5 gram phosphorous acid ester form and 3500 gram viscosity grades are No. 39, available from Lanzhou Petrochemical Company) add in the continous batching coppers, stir with the speed of 50 rev/mins, raw material is mixed.
Miscellany is added twin screw extruder continuously; Under 120 ℃ of conditions, described ultrahigh molecular weight polyethylene(UHMWPE) and high density polyethylene(HDPE) continuous-dissolution in twin screw extruder in the mixture of mineral oil and antioxidant, then is extruded with the speed of 200 rev/mins by twin screw extruder continuously; Miscellany is input in slot die continuously; Miscellany is extruded into the curtain coating cooling roller by slot die, the curtain coating thing that becomes band under 80 ℃ of conditions.
Adopt subsequently the mineral oil of the methylene dichloride belt surfaces that extraction obtains as extraction agent; To send into continuously biaxial orientation stretching machine through the ribbon of extraction and be drawn into film under 120 ℃ of conditions; Then adopt the tetrachloromethane extraction agent again to extract the mineral oil of the film surface that obtains; Clean made film with pure water simultaneously; Under 120 ℃ of conditions, carried out heat setting type 15 minutes; With the speed rolling of film with 20 m/mins, obtain battery isolating film.Measure this battery isolating film with aforesaid method, result is as follows:
Comparative example 1
Be 2 * 10 with 2500 gram density
6High density polyethylene(HDPE) (available from PetroChina Company Limited.'s Lanzhou Petrochemical Company), 100 gram molecular weights be 2,000,000 ultrahigh molecular weight polyethylene(UHMWPE) (available from PetroChina Company Limited.'s Lanzhou Petrochemical Company), 1 gram antioxidant 2,6 tert-butyl-4-methyl-Phenols and 2000 gram viscosity grades are the mineral oil (CAS8020-83-5 of No. 39, available from Lanzhou Petrochemical Company) add in the continous batching coppers, stir with the speed of 55 rev/mins, raw material is mixed.
Miscellany is added twin screw extruder continuously; Under 120 ℃ of conditions, described ultrahigh molecular weight polyethylene(UHMWPE) and high density polyethylene(HDPE) continuous-dissolution in twin screw extruder in the mixture of mineral oil and antioxidant, then is extruded with the speed of 200 rev/mins by twin screw extruder continuously; Miscellany is input in slot die continuously; Miscellany is extruded into the curtain coating cooling roller by slot die, the curtain coating thing that becomes band under 80 ℃ of conditions.
Adopt subsequently the mineral oil of the methylene dichloride belt surfaces that extraction obtains as extraction agent; To send into continuously biaxial orientation stretching machine through the ribbon of extraction and be drawn into film under 120 ℃ of conditions; Then adopt the tetrachloromethane extraction agent again to extract the mineral oil of the film surface that obtains; Clean made film with pure water simultaneously; Under 120 ℃ of conditions, carried out heat setting type 15 minutes; With the speed rolling of film with 20 m/mins, obtain battery isolating film.Measure this battery isolating film with aforesaid method, result is as follows:
Comparative example 2
Be 2 * 10 with 100 gram density
6High density polyethylene(HDPE) (available from PetroChina Company Limited.'s Lanzhou Petrochemical Company), 500 gram molecular weights be 2,000,000 ultrahigh molecular weight polyethylene(UHMWPE) (available from PetroChina Company Limited.'s Lanzhou Petrochemical Company), 1 gram antioxidant 2,6 tert-butyl-4-methyl-Phenols and 2000 gram viscosity grades are the mineral oil (CAS8020-83-5 of No. 39, available from Lanzhou Petrochemical Company) add in the continous batching coppers, stir with the speed of 55 rev/mins, raw material is mixed.
Miscellany is added twin screw extruder continuously; Under 120 ℃ of conditions, described ultrahigh molecular weight polyethylene(UHMWPE) and high density polyethylene(HDPE) continuous-dissolution in twin screw extruder in the mixture of mineral oil and antioxidant, then is extruded with the speed of 200 rev/mins by twin screw extruder continuously; Miscellany is input in slot die continuously; Miscellany is extruded into the curtain coating cooling roller by slot die, the curtain coating thing that becomes band under 80 ℃ of conditions; Adopt subsequently the mineral oil of the methylene dichloride belt surfaces that extraction obtains as extraction agent; To send into continuously biaxial orientation stretching machine through the ribbon of extraction and be drawn into film under 120 ℃ of conditions; Then adopt the dichloromethane extraction agent again to extract the mineral oil of the film surface that obtains; Clean made film with pure water simultaneously; Under 120 ℃ of conditions, carried out heat setting type 15 minutes; With the speed rolling of film with 20 m/mins, obtain battery isolating film.Measure this battery isolating film with aforesaid method, result is as follows:
By above test-results as seen, when the content of composition middle-high density polyethylene and ultrahigh molecular weight polyethylene(UHMWPE) compares within the scope of the invention, the aperture of the barrier film that makes is between the 0.4-0.48 micron, and when this content range is outside scope of the present invention, its mean pore size between the 0.8-0.9 micron, the mean pore size of the barrier film that makes apparently higher than the present composition.
In addition; when the content of composition middle-high density polyethylene and ultrahigh molecular weight polyethylene(UHMWPE) compares within the scope of the invention; the temperature difference of the broken temperature of the closed pore temperature of the barrier film that makes and film is more than 50 ℃; and when this content range is outside scope of the present invention; the temperature difference interval of the broken temperature of its closed pore temperature and film obviously reduces; be 40 ℃ of left and right, be unfavorable for the safeguard protection performance of barrier film.
In addition, the barrier film that makes with the present composition pierce through intensity between the 510-550 gram, and the barrier film that the comparative example composition makes pierce through the highest 460 grams that are no more than of intensity, and no matter be vertically or transverse tensile strength all has obvious decline.
Claims (15)
1. polymer composition that is used to form battery isolating film, the mean pore size of described battery isolating film is that 0.36-0.5 micron, porosity are 45-50%, described polymer composition comprises:
(a) molecular weight is 1.5 * 10
6-5.0 * 10
6Ultrahigh molecular weight polyethylene(UHMWPE) and density be 0.945g/cm
3The mixture of above high density polyethylene(HDPE), the weight ratio of described ultrahigh molecular weight polyethylene(UHMWPE) and high density polyethylene(HDPE) is 1:1-10;
(b) weight by described ultrahigh molecular weight polyethylene(UHMWPE) and high density polyethylene(HDPE) is 100 parts, the pore former of 500-1600 weight part; With
(c) weight by described ultrahigh molecular weight polyethylene(UHMWPE) and high density polyethylene(HDPE) is 100 parts, 0.5-20 part antioxidant.
2. the polymer composition that is used to form battery isolating film as claimed in claim 1, the molecular weight that it is characterized in that described ultrahigh molecular weight polyethylene(UHMWPE) is 2.5 * 10
6-5.0 * 10
6
3. the polymer composition that is used to form battery isolating film as claimed in claim 2, the molecular weight that it is characterized in that described ultrahigh molecular weight polyethylene(UHMWPE) is 3.5 * 10
6-5.0 * 10
6
4. the polymer composition that is used to form battery isolating film as claimed in claim 3, the molecular weight that it is characterized in that described ultrahigh molecular weight polyethylene(UHMWPE) is 4.5 * 10
6-5.0 * 10
6
5. the polymer composition that is used to form battery isolating film as claimed in claim 1, the weight ratio that it is characterized in that described ultrahigh molecular weight polyethylene(UHMWPE) and high density polyethylene(HDPE) is 1:2-10.
6. the polymer composition that is used to form battery isolating film as claimed in claim 5, the weight ratio that it is characterized in that described ultrahigh molecular weight polyethylene(UHMWPE) and high density polyethylene(HDPE) is 1:5-10.
7. the polymer composition that is used to form battery isolating film as claimed in claim 1, is characterized in that described pore former is selected from mineral oil, C
6-15Alkane, C
8-15Aliphatic carboxylic acid, C
8-15Aliphatic carboxylic acid C
1-4Alkane ester and C
2-6Halogenated alkane.
8. the polymer composition that is used to form battery isolating film as claimed in claim 7, is characterized in that described C
6-15Alkane is selected from heptane, naphthalane, decane, undecane, dodecane; Described C
8-15Aliphatic carboxylic acid is selected from capric acid, hendecoic acid, lauric acid; Described C
8-15Aliphatic carboxylic acid C
1-4The alkane ester is selected from methyl caprate, ethyl decylate, capric acid propyl ester, the positive butyl ester of capric acid, hendecoic acid methyl esters, hendecoic acid ethyl ester, hendecoic acid propyl ester, the positive butyl ester of hendecoic acid, lauric acid methyl esters, lauric acid ethyl ester, lauric acid propyl ester, the positive butyl ester of lauric acid; Described C
2-6Halogenated alkane is selected from ethylene dichloride, propylene dichloride, chlorofluoroethane, fluorine chloropropane.
9. the polymer composition that is used to form battery isolating film as claimed in claim 1, is characterized in that, is 100 parts by the weight of described ultrahigh molecular weight polyethylene(UHMWPE) and high density polyethylene(HDPE), and it contains the pore former of 800-1600 weight part.
10. the polymer composition that is used to form battery isolating film as claimed in claim 1, is characterized in that described antioxidant is selected from 4,4-thiobis (6-tertiary butyl meta-cresol), butylated hydroxytoluene, phosphorous acid ester, tertiarybutylhydroquinone.
11. the polymer composition that is used to form battery isolating film as claimed in claim 10 is characterized in that described butylated hydroxytoluene is BHT.
12. the polymer composition that is used to form battery isolating film as claimed in claim 1 is characterized in that, is 100 parts by the weight of described ultrahigh molecular weight polyethylene(UHMWPE) and high density polyethylene(HDPE), it contains 0.8-18 part antioxidant.
13. the polymer composition that is used to form battery isolating film as claimed in claim 12 is characterized in that, is 100 parts by the weight of described ultrahigh molecular weight polyethylene(UHMWPE) and high density polyethylene(HDPE), it contains 1.5-16 part antioxidant.
14. the polymer composition that is used to form battery isolating film as claimed in claim 12 is characterized in that, is 100 parts by the weight of described ultrahigh molecular weight polyethylene(UHMWPE) and high density polyethylene(HDPE), it contains 2-12 part antioxidant.
15. composition as described in any one in claim 1-14 is for the preparation of the purposes in the lithium ion battery barrier film.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102627796B (en) * | 2012-04-11 | 2015-06-03 | 中国科学院化学研究所 | Polyethylene composition for manufacturing lithium battery diaphragm |
| CN104987580B (en) * | 2015-08-06 | 2017-07-11 | 新乡市中科科技有限公司 | High density polyethylene (HDPE) micro-porous film and preparation method thereof |
| CN107452919B (en) * | 2016-06-01 | 2020-08-28 | 上海恩捷新材料科技有限公司 | High-wettability isolating membrane and preparation method and application thereof |
| CN107200901A (en) * | 2017-05-15 | 2017-09-26 | 上海恩捷新材料科技股份有限公司 | Form polymer composition, battery isolating film and the preparation method of battery isolating film |
| CN108232091A (en) * | 2018-01-10 | 2018-06-29 | 上海恩捷新材料科技股份有限公司 | Battery isolating film preparation method |
| CN108636131A (en) * | 2018-05-04 | 2018-10-12 | 上海恩捷新材料科技股份有限公司 | Hydrophilized porous membrane and preparation method thereof |
| CN109935756B (en) * | 2018-11-27 | 2022-05-13 | 万向一二三股份公司 | Preparation method of lithium ion battery composite diaphragm and lithium ion battery containing composite diaphragm |
| CN109873107B (en) * | 2019-03-18 | 2022-09-20 | 锂通新能源科技(沧州)有限公司 | Preparation process of new energy lithium ion battery diaphragm |
| CN110838566A (en) * | 2019-11-06 | 2020-02-25 | 江苏厚生新能源科技有限公司 | Preparation method of multilayer polyethylene diaphragm |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101272907A (en) * | 2005-09-28 | 2008-09-24 | 东燃化学株式会社 | Process for producing microporous polyethylene film and separator for cell |
| WO2010108148A1 (en) * | 2009-03-19 | 2010-09-23 | Amtek Research International | Freestanding, heat resistant microporous film for use in energy storage devices |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101272907A (en) * | 2005-09-28 | 2008-09-24 | 东燃化学株式会社 | Process for producing microporous polyethylene film and separator for cell |
| WO2010108148A1 (en) * | 2009-03-19 | 2010-09-23 | Amtek Research International | Freestanding, heat resistant microporous film for use in energy storage devices |
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