CN102199320A - Polymer composition for forming battery isolating membrane - Google Patents
Polymer composition for forming battery isolating membrane Download PDFInfo
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- CN102199320A CN102199320A CN2010106140055A CN201010614005A CN102199320A CN 102199320 A CN102199320 A CN 102199320A CN 2010106140055 A CN2010106140055 A CN 2010106140055A CN 201010614005 A CN201010614005 A CN 201010614005A CN 102199320 A CN102199320 A CN 102199320A
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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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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 excellent comprehensive performances, 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 to cut off electric current to guarantee cell safety at the battery operated ionic channel of closing when abnormal conditions occurring.
Battery isolating film is called battery diaphragm again, and its salient features comprises broken temperature of thickness, voidage, aperture, pore size distribution, intensity, closed pore temperature and film or the like.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 bigger external stress effect, and barrier film itself can guarantee not rupture of membranes, the maximum stretching force that can bear when keeping the integrity of barrier film; Owing to only separate with barrier film between positive and negative pole material, and positive and negative pole material is irregular, therefore irregular electrode materials can pierce through battery isolating film again, 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 danger such as for example explode, require the micropore in this barrier film that the fusion closure takes place after temperature rises to certain degree, pass through with isolated ion.Therefore, this area is called closed pore temperature with the micropore generation fusion closure of battery isolating film with the temperature that isolated ion passes through.
The broken temperature of the film of battery isolating film is meant that after reaching described closed pore temperature the temperature of barrier film continues to rise and breaks until barrier film fusing takes place, and this area is called the broken temperature of film with the temperature of barrier film generation fusion fracture.
Therefore guarantee to have enough temperature ranges between the broken temperature of the closed pore temperature of this area requirement battery isolating film and film, so that battery isolating film can have enough temperature buffer spaces when occurrence temperature inertia rose after temperature reaches the closed pore temperature of barrier film, film rupture does not take place.Difference between broken temperature of the film of existing battery isolating film and the closed pore temperature is generally 30-40 ℃.But,, need further to promote the broken temperature of film of battery isolating film and the difference between the closed pore temperature from security consideration.
In addition, for battery isolating film, can between the two poles of the earth, move to form electric current by barrier film swimmingly owing to need guarantee ion, therefore need have certain voidage, but the rising of voidage can cause the strength degradation of barrier film inevitably, thereby influences the reliability of battery.In addition, the wetting property of known electrolytes is relevant with aperture and pore size distribution: usually, be not under the very large situation in the aperture, pore size distribution is even more, and then the wetting property of electrolytic solution is just good more.Wetting property directly influences the resistance of ion migration, and wetting property is good more, and then ion is just more little by the resistance that barrier film moves, and the internal resistance of battery is just more little, and the current density of battery just has bigger raising leeway, and the cycle performance of battery is also good more.
Porosity, aperture, pore size distribution and the tensile strength of final battery isolating film depend on multiple factor, for example are used to make the manufacturing process of the 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 weight %
6Ultrahigh molecular weight polyethylene(UHMWPE) and the median size of the 5-15 weight % titanium oxide microparticle filler that is the 0.001-1 micron constitute.A better example of the prior art document is mentioned ultrahigh molecular weight polyethylene(UHMWPE), the low molecular weight polyethylene of 1-90 weight % and the titanium dioxide of 1-90 weight % that its battery isolating film contains 1-90 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 difference) 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 that is used to make 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.Shown in its table 1, CN 1954447A proves that the barrier film that its technical scheme makes has porosity and average 1 micron pore size of 51-74%.
Though CN 1954447A makes battery isolating film and can meet the demands substantially, the performance of this barrier film, especially mean pore size and pore size distribution still have room for improvement, so that further improve its electrolytic solution wetting property as battery isolating film.
Therefore, a goal of the invention of the present invention provides 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 the closed pore temperature, thereby help improving its electrolytic solution wetting property, improve the current density of the battery contain this battery isolating film and help improving the work-ing life and the reliability of this battery as battery isolating film.
Summary of the invention
A goal of the invention of the present invention provides 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 the closed pore temperature, thereby help improving its electrolytic solution wetting property, improve the current density of the battery contain this battery isolating film and help improving the work-ing life and the reliability of this battery as battery isolating film.
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 in the purposes that is used for preparing the lithium ion battery barrier film.
Description of drawings
Further specify the present invention below in conjunction with accompanying drawing, in the 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) is 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.
The ultrahigh molecular weight polyethylene(UHMWPE) that is suitable for 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, be preferably 0.96g/cm
3-1.2g/cm
3, 0.98g/cm more preferably
3-1.1g/cm
3
The high density polyethylene(HDPE) that is suitable for 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, be 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, then the porosity of the barrier film that forms with said composition can reduce, the aperture becomes that tensile strengths big, vertical and horizontal all can descend and percent thermal shrinkage becomes big.In addition, if the weight ratio of described ultrahigh molecular weight polyethylene(UHMWPE) and high density polyethylene(HDPE) less than 1: 1, then porosity descends, the aperture becomes big, transverse tensile strength reduces and percent thermal shrinkage becomes big.
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 the pore former that is suitable for 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 industry 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 the antioxidant that is suitable for 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 the butylated hydroxytoluene that is suitable for has, and for example 3,5-di-t-butyl-4-hydroxytoluene 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, this 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 cooling 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 high molecule micropore film through super-dry with structural shape.
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 finalizes the design after extraction and handle and the rolling film forming.
In another better example of the present invention, described method also is included in the extraction back film is carried out the tensile step.The ultra-high molecular weight PE microporous membrane of Sheng Chaning has the favorable mechanical performance in this way.
In a better example of the present invention, described film forming step comprise melt extrude, diaphragm moulding, two-way stretch, once side cut, extracting and washing, oven dry, secondary stretch, side cut, rolling and 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; Simultaneously also as can be seen, the battery isolating film of polymer composition formation of the present invention has bigger 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 soak into 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 the 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 about 40 ℃.
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 specify 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 be the mean value of 10 mensuration on the different measurement point.
3. transmitance
Adopt Gurley Gas permeability 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
Under the status adjustment environment, measure sample original length size;
Sample board is positioned on 120 ℃ ± 2 ℃ stainless rigid frames in the 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.
Calculating and test-results are represented
Size changing rate S presses formula and calculates:
L
0: the size of test back batten;
L
1: the size of batten before the 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 the stainless rigid frame, is positioned in the baking oven that is heated to preset temp two minutes, takes out the sample cooling, measures its gas permeation rate with aforesaid method again.The temperature that air penetrability was descended 5% o'clock is taken as closed pore temperature.
10. film breaks temperature
Whole film sample is fixed on the 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
With 120 gram density is 2 * 10
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 tertiary butyls-4-methylphenol and 2000 gram viscosity grades are No. 39 mineral oil (CAS8020-83-5, available from Lanzhou Petrochemical Company) add in the continous batching coppers, stir with 55 rev/mins speed, 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 is extruded with 200 rev/mins speed by twin screw extruder in the mixture of mineral oil and antioxidant more continuously; Miscellany is input in the 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 the mineral oil of the methylene dichloride belt surfaces that extraction obtains as extraction agent subsequently; Under 120 ℃ of conditions, will send into biaxial orientation stretching machine continuously and be drawn into film through the ribbon of extraction; Then adopt the dichloromethane extraction agent to extract the mineral oil of the film surface that obtains once more; Clean made film with pure water simultaneously; Under 120 ℃ of conditions, carried out heat setting type 15 minutes; With the speed rolling of film, obtain battery isolating film with 20 meters/minute.Measure this battery isolating film with aforesaid method, the result is as follows:
The Photomicrograph of above-mentioned battery isolating film as shown in Figure 1.
Embodiment 2
With 220 gram density is 2 * 10
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 tertiary butyls-4-methylphenol and 2200 gram viscosity grades are No. 39 mineral oil (CAS8020-83-5, available from Lanzhou Petrochemical Company) add in the continous batching coppers, stir with 50 rev/mins speed, 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 is extruded with 200 rev/mins speed by twin screw extruder in the mixture of mineral oil and antioxidant more continuously; Miscellany is input in the 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 the mineral oil of the methylene dichloride belt surfaces that extraction obtains as extraction agent subsequently; Under 120 ℃ of conditions, will send into biaxial orientation stretching machine continuously and be drawn into film through the ribbon of extraction; Then adopt the dichloromethane extraction agent to extract the mineral oil of the film surface that obtains once more; Clean made film with pure water simultaneously; Under 120 ℃ of conditions, carried out heat setting type 15 minutes; With the speed rolling of film, obtain battery isolating film with 20 meters/minute.Measure this battery isolating film with aforesaid method, the result is as follows:
Embodiment 3
With 520 gram density is 2 * 10
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 tertiary butyls-4-methylphenol and 3500 gram viscosity grades are No. 39 mineral oil (CAS8020-83-5, available from Lanzhou Petrochemical Company) add in the continous batching coppers, stir with 50 rev/mins speed, 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 is extruded with 200 rev/mins speed by twin screw extruder in the mixture of mineral oil and antioxidant more continuously; Miscellany is input in the 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 the mineral oil of the tetrachloromethane belt surfaces that extraction obtains as extraction agent subsequently; Under 120 ℃ of conditions, will send into biaxial orientation stretching machine continuously and be drawn into film through the ribbon of extraction; Then adopt the tetrachloromethane extraction agent to extract the mineral oil of the film surface that obtains once more; Clean made film with pure water simultaneously; Under 120 ℃ of conditions, carried out heat setting type 15 minutes; With the speed rolling of film, obtain battery isolating film with 20 meters/minute.Measure this battery isolating film with aforesaid method, the result is as follows:
Embodiment 4
With 520 gram density is 2 * 10
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 tertiary butyls-4-methylphenol and 3500 gram viscosity grades are No. 45 mineral oil (CAS8020-83-5, available from Lanzhou Petrochemical Company) add in the continous batching coppers, stir with 50 rev/mins speed, 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 is extruded with 200 rev/mins speed by twin screw extruder in the mixture of mineral oil and antioxidant more continuously; Miscellany is input in the 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 the mineral oil of the tetrachloromethane belt surfaces that extraction obtains as extraction agent subsequently; Under 120 ℃ of conditions, will send into biaxial orientation stretching machine continuously and be drawn into film through the ribbon of extraction; Then adopt the tetrachloromethane extraction agent to extract the mineral oil of the film surface that obtains once more; Clean made film with pure water simultaneously; Under 120 ℃ of conditions, carried out heat setting type 15 minutes; With the speed rolling of film, obtain battery isolating film with 20 meters/minute.Measure this battery isolating film with aforesaid method, the result is as follows:
Embodiment 5
With 520 gram density is 2 * 10
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 tertiary butyls-4-methylphenol, 0.5 gram 4, 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 mineral oil (CAS8020-83-5, available from Lanzhou Petrochemical Company) add in the continous batching coppers, stir with 50 rev/mins speed, 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 is extruded with 200 rev/mins speed by twin screw extruder in the mixture of mineral oil and antioxidant more continuously; Miscellany is input in the 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 the mineral oil of the methylene dichloride belt surfaces that extraction obtains as extraction agent subsequently; Under 120 ℃ of conditions, will send into biaxial orientation stretching machine continuously and be drawn into film through the ribbon of extraction; Then adopt the tetrachloromethane extraction agent to extract the mineral oil of the film surface that obtains once more; Clean made film with pure water simultaneously; Under 120 ℃ of conditions, carried out heat setting type 15 minutes; With the speed rolling of film, obtain battery isolating film with 20 meters/minute.Measure this battery isolating film with aforesaid method, the result is as follows:
Comparative example 1
With 2500 gram density is 2 * 10
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 tertiary butyls-4-methylphenol and 2000 gram viscosity grades are No. 39 mineral oil (CAS8020-83-5, available from Lanzhou Petrochemical Company) add in the continous batching coppers, stir with 55 rev/mins speed, 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 is extruded with 200 rev/mins speed by twin screw extruder in the mixture of mineral oil and antioxidant more continuously; Miscellany is input in the 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 the mineral oil of the methylene dichloride belt surfaces that extraction obtains as extraction agent subsequently; Under 120 ℃ of conditions, will send into biaxial orientation stretching machine continuously and be drawn into film through the ribbon of extraction; Then adopt the tetrachloromethane extraction agent to extract the mineral oil of the film surface that obtains once more; Clean made film with pure water simultaneously; Under 120 ℃ of conditions, carried out heat setting type 15 minutes; With the speed rolling of film, obtain battery isolating film with 20 meters/minute.Measure this battery isolating film with aforesaid method, the result is as follows:
Comparative example 2
With 100 gram density is 2 * 10
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 tertiary butyls-4-methylphenol and 2000 gram viscosity grades are No. 39 mineral oil (CAS8020-83-5, available from Lanzhou Petrochemical Company) add in the continous batching coppers, stir with 55 rev/mins speed, 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 is extruded with 200 rev/mins speed by twin screw extruder in the mixture of mineral oil and antioxidant more continuously; Miscellany is input in the 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 the mineral oil of the methylene dichloride belt surfaces that extraction obtains as extraction agent subsequently; Under 120 ℃ of conditions, will send into biaxial orientation stretching machine continuously and be drawn into film through the ribbon of extraction; Then adopt the dichloromethane extraction agent to extract the mineral oil of the film surface that obtains once more; Clean made film with pure water simultaneously; Under 120 ℃ of conditions, carried out heat setting type 15 minutes; With the speed rolling of film, obtain battery isolating film with 20 meters/minute.Measure this battery isolating film with aforesaid method, the 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 about 40 ℃, 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 (10)
1. polymer composition that is used to form battery isolating film, 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.
2. the polymer composition that is used to form battery isolating film as claimed in claim 1 is characterized in that the molecular weight of described ultrahigh molecular weight polyethylene(UHMWPE) is preferably 2.5 * 10
6-6.5 * 10
6, more preferably 3.5 * 10
6-5.5 * 10
6, be preferably 4.5 * 10
6-5.0 * 10
6
3. 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: 2-15, more preferably 1: 5-10.
4. 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.
5. the polymer composition that is used to form battery isolating film as claimed in claim 4 is characterized in that described C
6-15Alkane is selected from naphthalane, decane, undecane, dodecane; Described C
8-15Aliphatic carboxylic acid is selected from heptane, 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.
6. the polymer composition that is used to form battery isolating film as claimed in claim 1, it is characterized in that, weight by described ultrahigh molecular weight polyethylene(UHMWPE) and high density polyethylene(HDPE) is 100 parts, and it contains the pore former of 800-1800 weight part, better contains the pore former of 1000-1600 weight part.
7. the polymer composition that is used to form battery isolating film as claimed in claim 1, it is characterized in that described antioxidant is selected from 4,4-thiobis (6-tertiary butyl meta-cresol), 2,6 di tert butyl 4 methyl phenol, butylated hydroxytoluene, phosphorous acid ester, tertiarybutylhydroquinone.
8. the polymer composition that is used to form battery isolating film as claimed in claim 7 is characterized in that described butylated hydroxytoluene is selected from 3,5-di-t-butyl-4-hydroxytoluene or 2,6 ditertiary butyl p cresol.
9. the polymer composition that is used to form battery isolating film as claimed in claim 1, it is characterized in that, weight by described ultrahigh molecular weight polyethylene(UHMWPE) and high density polyethylene(HDPE) is 100 parts, it contain 0.8-18 part antioxidant, better contain 1.5-16 part antioxidant, better contain 2-12 part antioxidant.
As each described composition among the claim 1-9 in the purposes that is used for preparing the lithium ion battery barrier film.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102627796A (en) * | 2012-04-11 | 2012-08-08 | 中国科学院化学研究所 | Polyethylene composition for manufacturing lithium battery diaphragm |
| CN104987580A (en) * | 2015-08-06 | 2015-10-21 | 新乡市中科科技有限公司 | High-density polyethene micro porous membrane and preparation method therefor |
| 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 |
| WO2017206593A1 (en) * | 2016-06-01 | 2017-12-07 | 上海恩捷新材料科技股份有限公司 | High-wettability separator and preparation method therefor |
| 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 |
| CN109873107A (en) * | 2019-03-18 | 2019-06-11 | 泰顺永庆电力技术有限公司 | The preparation process of new energy lithium ion battery separator |
| CN109935756A (en) * | 2018-11-27 | 2019-06-25 | 万向一二三股份公司 | Preparation method of lithium ion battery composite diaphragm and lithium ion battery containing composite 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2010
- 2010-12-30 CN CN2010106140055A patent/CN102199320B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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| 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 |
| CN102627796A (en) * | 2012-04-11 | 2012-08-08 | 中国科学院化学研究所 | Polyethylene composition for manufacturing lithium battery diaphragm |
| CN104987580A (en) * | 2015-08-06 | 2015-10-21 | 新乡市中科科技有限公司 | High-density polyethene micro porous membrane and preparation method therefor |
| 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 |
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| CN107452919A (en) * | 2016-06-01 | 2017-12-08 | 上海恩捷新材料科技股份有限公司 | A kind of high wellability barrier film and its production and use |
| US11031654B2 (en) | 2016-06-01 | 2021-06-08 | Shanghai Energy New Materials Technology Co., Ltd. | High-wettability separator and preparation method 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 |
| WO2018209794A1 (en) * | 2017-05-15 | 2018-11-22 | 上海恩捷新材料科技股份有限公司 | Polymer composition for forming battery isolation membrane, battery isolation membrane and preparation method therefor |
| 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 |
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| CN109935756A (en) * | 2018-11-27 | 2019-06-25 | 万向一二三股份公司 | Preparation method of lithium ion battery composite diaphragm and lithium ion battery containing composite diaphragm |
| 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 |
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