CN101997102A - Lithium ion battery diaphragm and manufacturing method thereof - Google Patents
Lithium ion battery diaphragm and manufacturing method thereof Download PDFInfo
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- CN101997102A CN101997102A CN2009101896576A CN200910189657A CN101997102A CN 101997102 A CN101997102 A CN 101997102A CN 2009101896576 A CN2009101896576 A CN 2009101896576A CN 200910189657 A CN200910189657 A CN 200910189657A CN 101997102 A CN101997102 A CN 101997102A
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Abstract
The invention discloses a lithium ion battery diaphragm and a manufacturing method thereof. The diaphragm comprises composite microporous membranes in layers B, A and B, wherein the layer A is polyethylene, or copolymer of polyethylene and 0-50% of other olefins, or copolymer of polyethylene and 0-50% of other polyolefin, and the layer B is polyvinylidene fluoride or copolymer of hexafluoropropylene-vinylidene fluoride; the diaphragm is extruded and bidirectionally stretched by the three layers B, A and B, wherein the layer A and the layer B are made through a thermally induced phase separation method; and the stretching strength of the diaphragm is 120-170 MPa. The lithium ion battery diaphragm provided by the invention has the advantages of low pore closing temperature, high diaphragm breaking temperature and high mechanical strength, and can effectively improve the safety performance of the lithium ion battery using the diaphragm.
Description
[technical field]
The present invention relates to a kind of lithium ion battery, particularly relate to a kind of lithium ion battery separator and manufacture method thereof.
[background technology]
Lithium ion battery separator is a kind of little porous material, and material itself is an insulator, rises to separate positive/negative plate in battery, prevents the effect of internal short-circuit, and micropore sees through electrolyte simultaneously, guarantees that ionic conduction forms current circuit.So, lithium ion battery separator is except needing specific micropore, it is had outside the good ion permeability, what pay special attention to is its safety in utilization in battery, prevents that promptly positive/negative plate from directly contacting the formation internal short-circuit, requires barrier film that higher mechanical strength is arranged, good chemical stability, shrinkage is little, and the closed pore effect is arranged under the high temperature, characteristics such as molten broken temperature height.
Existing lithium ion battery separator mainly contains the polyethylene monofilm, polypropylene monofilm, or polypropylene, polyethylene/polyacrylic three layers of composite membrane.Poly fusing point is between 125 ℃-140 ℃, and polyacrylic fusing point is between 160 ℃-170 ℃.Because the polypropylene material fusing point is higher, so contain the barrier film of polypropylene material better high temperature safety is arranged, show that shrinkage is littler relatively, the broken film temperature height.But barrier film also must have the closed pore effect to ensure battery security, so list is that material just has the too high defective of closed pore temperature with dystectic polypropylene, polypropylene, polyethylene/polyacrylic three layers of composite membrane are just better in the high temperature safe sex expression.But existing polypropylene, polyethylene/polyacrylic three layers of composite membrane are to cause the mode that forms micropore between the crystalline region amorphous area to make barrier film by the hard elastics presoma simple tension to the highly crystalline orientation, mechanical strength is lower, battery winding short circuit ratio height influences production efficiency in the use.
Recently there are many researchs to concentrate on the polyethylene monofilm the dystectic resin of coating and improve its high temperature safety.Propose the porous layer of coating one deck poly on barrier film as patent CN200580051172, thereby form incorporate composite membrane,, the broken film temperature of barrier film is reached more than 250 ℃ because its coating composition fusing point is very high.Patent CN200480034190 proposes the surface coated fluororesin and makes through hole, also can improve the resistance to elevated temperatures of barrier film.But coating process is bigger to coating layer thickness evenness control difficulty on the one hand, and the coating processing speed is slower, is generally several meters/minutes, influences production efficiency, is difficult for heavy industrialization.Though coating high-melting-point material can improve the broken film temperature of barrier film on the other hand, because can causing the part in hole, stops up coating fluid, barrier film internal resistance meeting is increased.For this reason, usually use porosity big, the fast barrier film of air permeability is as matrix, even there is the part micropore blocked like this, still there is the abundant micropore can conducting ion, and can not make the internal resistance increase too big, but use porosity excessive, the too fast barrier film matrix of air permeability can make the mechanical strength variation of barrier film.
[summary of the invention]
The technical problem that the present invention solves is the problem that lithium ion battery separator closed pore broken film temperature is not suitable for and mechanical strength is low in the prior art, and the spy provides a kind of lithium ion battery new types of diaphragm.
The present invention also provides the preparation method of lithium ion battery new types of diaphragm.
The invention provides a kind of lithium ion battery separator, comprise the B/A/B three-layer composite microporous membrane, wherein, described A layer is the copolymer of other alkene of polyethylene or ethene and 0-50% or other polyolefinic mixtures of polyethylene and 0-50%; Described B layer is the copolymer of Kynoar or hexafluoropropylene-vinylidene; Described barrier film forms through the three-layer co-extruded pressure of B/A/B, biaxial tension, and wherein, A layer, B layer are made by thermally induced phase separation; The hot strength of described barrier film is at 120-170Mpa.
The present invention also provides the preparation method of this lithium ion battery separator, may further comprise the steps:
Step a, polymer and the diluent blend in extruder that the A layer is used are extruded, the polymer that the B layer is used, diluent and inorganic filler blend in extruder are extruded, pass through in die head compoundly with three layers of B/A/B then, chilling obtains composite sheet after the co-extrusion; Wherein, the used polymer of A layer is the copolymer of other alkene of polyethylene or ethene and 0-50% or other polyolefinic mixtures of polyethylene and 0-50%, and the used polymer of B layer is the copolymer of Kynoar or hexafluoropropylene-vinylidene;
Step b, will composite sheet become film through after the biaxial tension;
Step c, the film that step b is obtained pass through the eluting solvent wash-out, and dry;
Steps d, the film thermal finalization that step c is obtained.
Lithium ion battery separator provided by the invention has adopted the B/A/B three-layer composite microporous membrane, wherein the A layer adopts and contains the copolymer of polyethylene or ethene or contain polyethylene mixture, the low characteristics of poly closed pore temperature have been utilized, compound poly microporous barrier can make diaphragm closed pore temperature in 125 ℃-135 ℃ scope; And the B layer adopts the copolymer of Kynoar or hexafluoropropylene-vinylidene, on the one hand be that to utilize it be that a kind of fusing point is than higher crystalline polymer, after the stretched orientation, melt strength is improved, make the broken film temperature of barrier film can reach 170 ℃, the barrier film hot strength can reach more than the 120MPa simultaneously.Be that to utilize it be a kind of polarity macromolecule on the other hand, better with respect to non-polar high polymer barrier films such as polyethylene polypropylene to the adhesion of battery positive/negative plate, it is tightr that barrier film and pole piece are fitted, prevented from that material and Li dendrite pierce through barrier film in the generation of the gap of barrier film and negative plate, effectively reduced self-discharge of battery.
[description of drawings]
Lithium ion battery separator internal resistance and the closed pore broken film temperature tester structural representation of Fig. 1 for using among the present invention.
Lithium ion battery separator internal resistance and the closed pore broken film temperature tester modular construction schematic diagram of Fig. 2 for using among the present invention.
Lithium ion battery separator internal resistance and the closed pore broken film temperature tester modular construction schematic diagram of Fig. 3 for using among the present invention
[embodiment]
Describe lithium ion battery separator provided by the invention and preparation method thereof in detail below in conjunction with specific embodiment.
The invention provides a kind of lithium ion battery separator, comprise the B/A/B three-layer composite microporous membrane, wherein, described A layer is the copolymer of other alkene of polyethylene or ethene and 0-50% or other polyolefinic mixtures of polyethylene and 0-50%; Described B layer is the copolymer of Kynoar or hexafluoropropylene-vinylidene; Described barrier film forms through the three-layer co-extruded pressure of B/A/B, biaxial tension, and wherein, A layer, B layer are made by thermally induced phase separation; The hot strength of described barrier film is 120-170Mpa.The hot strength of barrier film is used the standard method of test test of GB/T1040.3-2006.
The polymer that described A layer is selected from contains a large amount of polyethylene compositions, is to utilize its fusing point lower, and lower closed pore temperature can be provided.One or more of copolymer that it can select low density polyethylene (LDPE), medium density polyethylene, high density polyethylene (HDPE), ultra-high molecular weight polyethylene or contain a large amount of polyethylene part.For consideration to barrier film intensity and processability, preferred high density polyethylene (HDPE), its fusing point is 132 ℃～136 ℃, molecular weight is 1 * 10
5～1 * 10
6Further preferred, molecular weight is 1 * 10
5-1 * 10
6High density polyethylene (HDPE) and molecular weight be 4 * 10
3-1 * 10
4The mixture of low density polyethylene (LDPE), the fusing point of described low density polyethylene (LDPE) is that the mass percent that 125 ℃～128 ℃, content account for mixture is 5%～20%, with further reduction closed pore temperature.
The polymer poly vinylidene that described B layer is selected from or the copolymer of hexafluoropropylene-vinylidene not only can improve the broken film temperature of barrier film, and can reduce self-discharge of battery with polyethylene, polyacrylic barrier film relatively merely.For to the taking all factors into consideration of processability, mechanical strength and broken film temperature, the molecular weight of the copolymer of described Kynoar, hexafluoropropylene-vinylidene is preferably 2.0 * 10
5-5 * 10
5, fusing point is 145 ℃-170 ℃.
Described B layer is 1 with the thickness ratio of described A layer: 2-1: 4.The gross thickness of described B/A/B three-layer composite microporous membrane is 20-50um, and the thickness of described B layer is 4-8um, and too thick then cost is too high, and too thin then being difficult to processes evenly.
Other alkene in the copolymer of other alkene of described ethene and 0-50% are one or more in propylene, 1-butylene, 4-methyl-1-pentene, the 1-hexene.Other polyolefin in the polyolefinic mixture of other of described polyethylene and 0-50% are to contain in the polymer of ethene, propylene, 1-butylene, 4-methyl-1-pentene, 1-hexene one or more.
Described lithium ion battery separator also comprises the application of described barrier film in lithium ion battery.
The present invention also provides the preparation method of described lithium ion battery separator, may further comprise the steps:
Step a, polymer and the diluent blend in extruder that the A layer is used are extruded, the polymer that the B layer is used, diluent and inorganic filler blend in extruder are extruded, pass through in die head compoundly with three layers of B/A/B then, chilling obtains composite sheet after the co-extrusion; Wherein, the used polymer of A layer is the copolymer of other alkene of polyethylene or ethene and 0-50% or other polyolefinic mixtures of polyethylene and 0-50%, and the used polymer of B layer is the copolymer of Kynoar or hexafluoropropylene-vinylidene;
Step b, will composite sheet become film through after the biaxial tension;
Step c, the film that step b is obtained pass through the eluting solvent wash-out, and dry;
Steps d, the film thermal finalization that step c is obtained.
The preparation method of above-mentioned barrier film, in step a, the polyethylene of A layer or contain the relatively easy fusion plastification of poly resin, so can adopt directly from double screw extruder charge door pan feeding, the mode of side direction feeding diluent, also can adopt earlier polyethylene or contain poly resin and after diluent fully mixes molten expanding, again the mode that adds from spout.The polyethylene of A layer or contain poly resin and can select the double screw extruder of draw ratio more than 40 for use, melting mixing between 190 ℃～250 ℃.The Kynoar of B layer or the copolymer of hexafluoropropylene-vinylidene, because certain polarity is arranged, the resin melting viscosity is bigger, with respect to the polyethylene of A layer or contain poly resin and will more be difficult to mixing, so need select the stronger double screw extruder of mixing ability for use, can select the double screw extruder of draw ratio more than 60 for use, melting mixing between 200 ℃～250 ℃.Before adding extruder, must in blender, heat up simultaneously and stir fast, fully can add extruder after swelling even the dissolving with diluent and inorganic filler, can be in homogenizer 90 ℃ of stirrings 2～10 hours.
Among the above-mentioned steps a, used diluent is the difficult solvent flashing of higher boiling point that good intermiscibility is arranged with A layer and B layer under the high temperature, plays two kinds of effects of plasticising and pore-forming.Therefore, described diluent is selected from a kind of in nonane, decane, atoleine, the dioctyl phthalate (DOP).
Among the step a, in the polymer and diluent that the A layer is used, the percentage of diluent accounts for 50%-80wt%, and then the barrier film porosity is too low very little for content, and content is processing and forming difficulty then too much.In polymer that the B layer is used and diluent and the inorganic filler, the percentage of diluent accounts for 30%～60wt%, and the percentage of inorganic filler accounts for 5%～20%.Mainly between 0.1～0.6um, porosity is 30%～50% to the pore-size distribution of A layer.The inorganic filler that the B layer is used, effect mainly have been porosity and the apertures that increase to stretch forms, and it can be the oxide etc. of elements such as siliceous, calcium, aluminium, germanium, zirconium, and particle diameter is that 10～100nm is the best; Specifically can be selected from and be nano-calcium carbonate or nano silicon.
Mainly between 0.5～1.5um, porosity is 50%～80% to the pore-size distribution of A layer.The aperture and the porosity of B layer are bigger than A layer, can reduce membrane surface ionic conduction resistance like this, can also guarantee that the diluent of A layer in step c can be by wash-out is complete fully.
Chilling speed among the step a is preferably in per minute more than 50 ℃, can make the microcosmic phase-splitting finer and closely woven like this, helps to form many and fine and closely woven micropore.
Among the step b, biaxial tension can be a step drawing, also can be synchro-draw.Step drawing is compared with synchro-draw can realize relatively large stretching ratio, makes barrier film that bigger mechanical strength be arranged; Synchro-draw stretches with respect to distributing, and the more approaching circle of the micropore of formation helps the conduction of ion, so both respectively have characteristics.During step drawing, the stretching ratio of longitudinal stretching is 3～6 times, preheat temperature is 115～125 ℃, and draft temperature is 110～120 ℃, and setting temperature is 115～125 ℃, preheat temperature will be higher than draft temperature makes the abundant preheating of diaphragm, draft temperature can not be too low, otherwise the fluororesin necking phenomenon can be very serious, and setting temperature is high as far as possible, and vertical draw the distance between horizontal the drawing short as far as possible, keep vertical pulling-on piece temperature to prevent cooling as far as possible; The preheat temperature of cross directional stretch is 120～130 ℃, and draft temperature is 115～125 ℃, and setting temperature is 120～130 ℃, and stretching ratio is 5～8 times.During synchro-draw, preheat temperature is 120～130 ℃, and draft temperature is 115～125 ℃, and setting temperature is 120～130 ℃, and each direction of stretching ratio is 2～4 times, and multiplying power is easily disconnected film during greater than 4 times.
Among the step c, described eluting solvent is the good solvent of diluent described in the step a, and the poor solvent of polymer is selected from a kind of in alkane, halogenated hydrocarbons, the ketone.
In the steps d, described thermal finalization is in order to reduce the film contraction distortion, is to be 120～130 ℃ in preheat temperature, and draft temperature is 115～125 ℃, setting temperature is under 120～130 ℃ of conditions film to be carried out 1～2 times little multiplying power cross directional stretch, and heat-setting time is preferably in 0.5～5min.In type-approval process,, can also do 5%～10% retraction in the typing section in order further to reduce to shrink.
The following example is to further explanation of the present invention and explanation, and the present invention is not constituted any limitation.
Embodiment 1
High density polyethylene (HDPE) (weight average molecular weight 2.5 * 10 with 27 (weight %)
5, 133 ℃ of fusing points) and the low density polyethylene (LDPE) (weight average molecular weight 5.5 * 10 of 3 (weight %)
3, 125 ℃ of fusing points) add double screw extruder A (diameter 75mm, L/D=60, strong mixed milling type), with measuring pump side to the atoleine that pumps into 70 (weight %) (kinematic viscosity 90cst/40 ℃), melting mixing is modulated into solution A under 200 ℃, 200 rev/mins condition again.
PVDF (weight average molecular weight 3.5 * 10 with 40 (weight %)
5, 163 ℃ of fusing points), the DOP (kinematic viscosity 70cst/40 ℃) of 50 (weight %), add after stirred tank mixes swelling 8h with the nano-calcium carbonate calcium powder (particle diameter 50nm) of 10 (weight %), add double screw extruder B (diameter 75mm, L/D=68, strong mixed milling type), melting mixing is modulated into solution B under 220 ℃, 200 rev/mins condition.
B/A/B in T pattern head is three-layer co-extruded with two kinds of solution, and three layers thickness ratio is 1: 3: 1, is traction casting sheet on 15 ℃ the slab roller in surface temperature, obtains the sheet that thickness is 0.8mm.
Sheet is carried out the substep biaxial tension, stretching ratio for vertical * horizontal=4 * 5 times, wherein vertically draw 123 ℃ of preheat temperatures, 118 ℃ of draft temperatures, 123 ℃ of setting temperatures; Horizontal 127 ℃ of the preheat temperatures of drawing, 122 ℃ of draft temperatures, 125 ℃ of setting temperatures.The film that obtains after the stretching is clean, dry with butanone.
Then with film 125 ℃ of preheat temperatures, 122 ℃ of draft temperatures, 125 ℃ of thermal finalization 1min of setting temperature stretch 1.6 times, the retraction 6%.Obtain the three-layer composite microporous membrane A1 of thick 25um.
PVDF among the embodiment 1 is become weight average molecular weight 2.5 * 10
5, 158 ℃ of fusing points, other are identical with embodiment 1, obtain three-layer composite microporous membrane A2.
PVDF among the embodiment 1 is become the copolymer of PVDF-HFP, weight average molecular weight 2.0 * 10
5, 155 ℃ of fusing points, other are identical with embodiment 1, obtain three-layer composite microporous membrane A3.
Embodiment 4
The resin of B layer among the embodiment 1 is not added nano-calcium carbonate, use PVDF (weight average molecular weight 3.5 * 10 40 (weight %)
5, 163 ℃ of fusing points), the DOP (kinematic viscosity 70cst/40 ℃) of 60 (weight %), other are identical with embodiment 1, obtain three-layer composite microporous membrane A4.
Low density polyethylene (LDPE) with the high density polyethylene (HDPE) and 3 (weight %) of 27 (weight %) in the raw material of solution A among the embodiment 1, become the high density polyethylene (HDPE) of 30 (weight %), do not add low density polyethylene (LDPE), other are identical with embodiment 1, obtain three-layer composite microporous membrane A5.
B/A/B threeply degree ratio among the embodiment 1 is become 1: 2: 1, and other are identical with embodiment 1, obtain three-layer composite microporous membrane A6.
Casting sheet thickness among the embodiment 1 is become 0.5mm, and the substep biaxial tension changes synchronous bidirectional into and stretches, stretching ratio for vertical * horizontal=3.5 * 3.5 times, wherein preheat temperature is 127 ℃, 122 ℃ of draft temperatures, 125 ℃ of setting temperatures, other are identical with embodiment 1, obtain three-layer composite microporous membrane A7.
Comparative Examples 1
High density polyethylene (HDPE) (weight average molecular weight 2.5 * 10 with 30 (weight %)
5, 133 ℃ of fusing points) add double screw extruder (diameter 75mm, L/D=60, strong mixed milling type), with measuring pump side to the atoleine that pumps into 70 (weight %) (kinematic viscosity 90cst/40 ℃), melting mixing is modulated into solution under 200 ℃, 200 rev/mins condition again.
By T pattern head, is cooling casting sheet on 15 ℃ the slab roller with solution in surface temperature, obtains the sheet of thickness 0.8mm.
Sheet is carried out the substep biaxial tension, stretching ratio for vertical * horizontal=4 * 5 times, wherein vertically draw 123 ℃ of preheat temperatures, 118 ℃ of draft temperatures, 123 ℃ of setting temperatures; Horizontal 127 ℃ of the preheat temperatures of drawing, 122 ℃ of draft temperatures, 125 ℃ of setting temperatures.The film that obtains after the stretching is clean, dry with heptane.
Then with film 125 ℃ of preheat temperatures, 122 ℃ of draft temperatures, 125 ℃ of thermal finalization 1min of setting temperature stretch 1.6 times, the retraction 5%.Obtain the individual layer PE film D1 of thick 25um.
Comparative Examples 2
High density polyethylene (HDPE) (weight average molecular weight 2.5 * 10 with 30 (weight %)
5, 133 ℃ of fusing points) add double screw extruder (diameter 75mm, L/D=60, strong mixed milling type), with measuring pump side to the atoleine that pumps into 70 (weight %) (kinematic viscosity 90cst/40 ℃), melting mixing is modulated into solution under 200 ℃, 200 rev/mins condition again.
By T pattern head, is cooling casting sheet on 15 ℃ the slab roller with solution in surface temperature, obtains the sheet of thickness 0.5mm.
Sheet is carried out the substep biaxial tension, stretching ratio for vertical * horizontal=4 * 5 times, wherein vertically draw 123 ℃ of preheat temperatures, 118 ℃ of draft temperatures, 123 ℃ of setting temperatures; Horizontal 127 ℃ of the preheat temperatures of drawing, 122 ℃ of draft temperatures, 125 ℃ of setting temperatures.The film that obtains after the stretching is clean, dry with heptane.
Then with film 125 ℃ of preheat temperatures, 122 ℃ of draft temperatures, 125 ℃ of thermal finalization 1min of setting temperature stretch 1.6 times, the retraction 5%.Obtain the individual layer PE film of thick 16um.
PVDF (weight average molecular weight 3.5 * 10 with 5 (weight %)
5, 163 ℃ of fusing points) become solution with the acetone of 95 (weight %) in stirrer for mixing, add again and account for total solution weight than 5 ‰ toluene, be mixed into the coating fluid of transparent homogeneous.Again with the individual layer PE film immersion that obtains in coating fluid, the PE film is taken out make the acetone volatilization then, make the toluene volatilization 90 ℃ of bakings again, obtain both sides and all be coated with PVDF, gross thickness is the film D2 of 25um.
Comparative Examples 3
The atoleine that the formula rate that the atoleine of the high density polyethylene (HDPE) and 70 (weight %) of 30 (weight %) in the comparative example 2 is modulated into solution changes the high density polyethylene (HDPE) and 80 (weight %) of 20 (weight %) into is modulated into solution.Other are identical with comparative example 2, obtain barrier film D3.
Method of testing
1, air permeability: use the standard of GB5402-2003, with the test of GURLEY Permeability gauge.
2, porosity: use standard and the method test of ASTM D2873.
3, pore-size distribution: use the mercury injection method test.
4, diluent residual quantity: take by weighing the barrier film of 10g, weight is accurate to 1mg, and note is m1.With scissors barrier film is shredded into tiny fragment, clean 5min with analytically pure hexane in ultrasonic cleaner then, treat to take by weighing barrier film weight once more after solvent fully volatilizees, weight is accurate to 1mg, and note is m2.Diluent residual quantity computing formula is (m1-m2)/m1 * 100%.
5, shrinkage: use standard and the method test of GB12027-2004.
6, hot strength: use standard and the method for testing test of GB/T1040.3-2006.
7, closed pore broken film temperature: Fig. 1 shows the testing apparatus figure of closed pore broken film temperature.With two thickness nickel foil (A, B) that is 10um, with a slice nickel foil A, be labeled as the 9 square parts that on slide 2, stay each 10mm of length and width, cover simultaneously fixedly (see figure 2) with insulating tape 8 (dash area among the figure).On the ceramic wafer 4 that is connected with thermocouple 3, another nickel foil of load B, be labeled as 10 (see figure 3)s, the lithium fluoroborate (solvent is isobutyl carbonate propylene glycol ester/ethylene carbonate ester/gamma-butyrolacton=1/1/2) that uses 1mol/l is as electrolyte, with placed on it with 2 hours test barrier film sample 1 of above-mentioned electrolyte dipping, the slide that nickel foil A is arranged is sticked in load thereon, and then load silicon rubber 5.It is arranged on the electric hot plate 7, applies with hydraulic press 6 under the pressure state of 1.5MPa, temperature is warmed up to 200 ℃ from 25 ℃ with the speed of 15 ℃/min.Exchanging 1V, measuring resistance changes under the condition of 1kHz.The resistance of barrier film is as barrier film resistance during with 25 ℃, and the temperature when reaching 1000 Ω with resistance is as closed pore temperature, reaches temperature when resistance falls after rise to 1000 Ω again after the closed pore state as broken film temperature.Electrode interface is labeled as 11 in the drawings.
The test result that obtains according to above-mentioned method of testing is recorded in the table 1.
Table 1 test result
Annotate: in embodiment 1-7, pore-size distribution is because there is difference in the two-layer aperture of A, B so be divided into two parts, and what the aperture was little is the A layer, and what the aperture was big is the B layer.Wherein embodiment 4 is not owing to add nanometer calcium carbonate, and the aperture of B layer is obviously little than other embodiment.In Comparative Examples 1, has only the PE layer; Among the Comparative Examples 2-3, the small-bore is the PE layer, and the large aperture is the PVDF layer of coating.
From the test result of top table 1 as can be seen, the broken film temperature of the barrier film of embodiment 1-7 preparation is all greater than 169 ℃, the broken film temperature of the barrier film of making apparently higher than Comparative Examples 1-3; And the MD hot strength of the barrier film of embodiment 1-7 and TD hot strength obviously are better than the barrier film of Comparative Examples especially; And the porosity of the barrier film of embodiment 1-7 preparation is higher.Therefore, lithium ion battery separator closed pore temperature provided by the invention is low, the broken film temperature height, and the mechanical strength height can effectively improve the security performance of the lithium ion battery that uses barrier film of the present invention.
Self discharge relatively
Making the three layers of barrier film of B/A/B that obtain with embodiment 1 is made into the battery note and makes battery A, be made into the battery note with three layers of barrier film of PP/PE/PP of 25um and make battery B, battery A, B all are charged to the state of 3.85V, place a period of time after, contrast its self discharge by its voltage drop relatively.Battery production method is as follows:
With cobalt acid lithium powder, acetylene black conductive agent powder, polyvinylidene fluoride and N-methyl pyrrolidone (NMP) according to 100: 3: 2: 40 weight ratio is evenly mixed, be modulated into anode sizing agent, this slurry is coated on the plus plate current-collecting body aluminium foil, dry then, compressing tablet, be cut into the anode pole piece of 485 * 44mm, this positive plate contains 6.9g cobalt acid lithium powder.
With graphite, electric conduction of carbon fiber agent, polytetrafluoroethylene and deionized water according to 100: 1.5: 3: 135 weight ratio is mixed, be modulated into cathode size, this slurry is coated on the negative current collector Copper Foil, dry then, compressing tablet, be cut into the cathode pole piece of 477 * 44mm, contain 3.2g graphite on this negative plate.
With LiPF6 is lithium salts, with its volume ratio that is dissolved into EC and EMC is in 1: 1 the solvent, to make its concentration reach 1mol/L, obtains nonaqueous electrolytic solution.
With the overlapping rectangular cell electricity core that is wound into of the above-mentioned positive plate of making, negative plate and barrier film, be inserted in 5 * 34 * 50mm rectangular cell shell, inject electrolyte and also seal, ageing in a conventional manner then, seal, obtain LP053450 type square lithium ion secondary battery.The design capacity of this battery is 1C=900mAh.
Table 2 self discharge compare test result
| Initial voltage (V) | After 15 days (V) | After 30 days (V) | After 45 days (V) | After 60 days (V) | |
| Battery A | 3.850 | 3.844 | 3.838 | 3.834 | 3.832 |
| Battery B | 3.850 | 3.847 | 3.846 | 3.845 | 3.845 |
From the test result of top table 2 as can be seen, will be significantly littler than the self discharge with the lithium ion battery of three layers of barrier film of PP/PE/PP with the self discharge of the lithium ion battery of barrier film of the present invention, battery performance be better.
Claims (15)
1. a lithium ion battery separator comprises the B/A/B three-layer composite microporous membrane, and wherein, described A layer is the copolymer of other alkene of polyethylene or ethene and 0-50% or other polyolefinic mixtures of polyethylene and 0-50%; Described B layer is the copolymer of Kynoar or hexafluoropropylene-vinylidene; Described barrier film forms through the three-layer co-extruded pressure of B/A/B, biaxial tension, and wherein, A layer, B layer are made by thermally induced phase separation; The hot strength 120-170Mpa of described barrier film.
2. lithium ion battery separator according to claim 1, wherein, described A layer is a high density polyethylene (HDPE), and its fusing point is 132 ℃～136 ℃, and molecular weight is 1 * 10
5-1 * 10
6
3. lithium ion battery separator according to claim 1, wherein, described A layer is that molecular weight is 1 * 10
5-1 * 10
6High density polyethylene (HDPE) and molecular weight be 4 * 10
3-1 * 10
4The mixture of low density polyethylene (LDPE), the fusing point of described low density polyethylene (LDPE) is that the mass percent that 125 ℃～128 ℃, content account for mixture is 5%-20%.
4. lithium ion battery separator according to claim 1, wherein, the molecular weight of the copolymer of described Kynoar and hexafluoropropylene-vinylidene is 2.0 * 10
5-5 * 10
5, fusing point is 145 ℃-170 ℃.
5. lithium ion battery separator according to claim 1, wherein, described B layer is 1 with the thickness ratio of described A layer: 2-1: 4.
6. lithium ion battery separator according to claim 1, wherein, the gross thickness of described B/A/B three-layer composite microporous membrane is 20-50um, the thickness of described B layer is 4-8um.
7. lithium ion battery separator according to claim 1, wherein, other alkene in the copolymer of other alkene of described ethene and 0-50% are one or more in propylene, 1-butylene, 4-methyl-1-pentene, the 1-hexene.
8. lithium ion battery separator according to claim 1, wherein, other polyolefin in the polyolefinic mixture of other of described polyethylene and 0-50% are to contain in the polymer of ethene, propylene, 1-butylene, 4-methyl-1-pentene, 1-hexene one or more.
9. one kind as any application of described lithium ion battery separator in lithium ion battery among the claim 1-8.
10. the preparation method of a lithium ion battery separator may further comprise the steps:
Step a, polymer and the diluent blend in extruder that the A layer is used are extruded, the polymer that the B layer is used, diluent and inorganic filler blend in extruder are extruded, pass through in die head compoundly with three layers of B/A/B then, chilling obtains composite sheet after the co-extrusion; Wherein, the used polymer of A layer is the copolymer of other alkene of polyethylene or ethene and 0-50% or other polyolefinic mixtures of polyethylene and 0-50%, and the used polymer of B layer is the copolymer of Kynoar or hexafluoropropylene-vinylidene;
Step b, will composite sheet become film through after the biaxial tension;
Step c, the film that step b is obtained pass through the eluting solvent wash-out, and dry;
Steps d, the film thermal finalization that step c is obtained.
11. the preparation method of lithium ion battery separator according to claim 10, wherein, among the step a, described inorganic filler is nano-calcium carbonate or nano silicon.
12. the preparation method of lithium ion battery separator according to claim 10, wherein, among the step a, described diluent is selected from a kind of in nonane, decane, atoleine, the dioctyl phthalate.
13. the preparation method of lithium ion battery separator according to claim 10, wherein, among the step a, in the polymer and diluent that the A layer is used, the percentage of diluent accounts for 50wt%-80wt%; In polymer that the B layer is used and diluent and the inorganic filler, the percentage of diluent accounts for 30wt%～60wt%, and the percentage of inorganic filler accounts for 5wt%～20wt%.
14. the preparation method of lithium ion battery separator according to claim 10, wherein, among the step b, biaxial tension is synchro-draw, and draft temperature is 115-125 ℃, and each direction of stretching ratio is 2～4 times.
15. the preparation method of lithium ion battery separator according to claim 10, wherein, among the step b, biaxial tension is a step drawing, and the stretching ratio of longitudinal stretching is 3～6 times, and draft temperature is 110～120 ℃; The stretching ratio of cross directional stretch is 5～8 times, and draft temperature is 115～125 ℃.
The preparation method of 16 lithium ion battery separators according to claim 10, wherein, in the steps d, described thermal finalization is under 120-130 ℃ of condition film to be carried out 1-2 stretching doubly, the time is 0.5-5min.
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