CN103137930A - Lithium ion battery diaphragm, preparation method of the lithium ion battery diaphragm, and lithium ion battery containing the lithium ion battery diaphragm - Google Patents
Lithium ion battery diaphragm, preparation method of the lithium ion battery diaphragm, and lithium ion battery containing the lithium ion battery diaphragm Download PDFInfo
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- CN103137930A CN103137930A CN2011103776665A CN201110377666A CN103137930A CN 103137930 A CN103137930 A CN 103137930A CN 2011103776665 A CN2011103776665 A CN 2011103776665A CN 201110377666 A CN201110377666 A CN 201110377666A CN 103137930 A CN103137930 A CN 103137930A
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Abstract
The invention provides a lithium ion battery diaphragm. The lithium ion battery diaphragm comprises a diaphragm base material and an organic polymer layer deposited on at least one surface of the diaphragm base material by a physical vapor deposition method. The invention also provides a preparation method of the lithium ion battery diaphragm, a device adopted by the preparation method, and a lithium ion battery containing the lithium ion battery diaphragm. A high rate of lithium ion transmission between positive and negative poles of the lithium ion battery containing the lithium ion battery diaphragm is kept, a risk of short circuit between the positive and negative poles is reduced, and a diaphragm heat shrinkage problem and battery safety are improved.
Description
Technical field
The invention belongs to the lithium ion battery field, relate to a kind of lithium ion battery separator and preparation method thereof, contain the lithium ion battery of this barrier film.
Background technology
In recent years, lithium ion battery is as the high-energy-density power supply, and its range of application is constantly expanded, and extensively is applied to the fields such as portable electron device, electric tool, electric automobile, energy-accumulating power station.Increasingly extensive along with lithium ion battery applications also had higher requirement to the combination property of lithium ion battery.Particularly electric automobile market shows the vigorous growth impetus, needs the lithium ion battery that charging and discharging currents is large, power is higher.Many compact electric apparatus also requirement can high-multiplying power discharge, and the low discharging current lithium ion battery is the demand of satisfying the market fully.The rate charge-discharge performance that improves lithium ion battery seems and is even more important.On the other hand, because lithium ion battery adopts inflammable organic electrolyte, overcharge when battery exists, internal short-circuit etc. can cause the battery even blast of catching fire when abnormal.The safety issue of lithium ion battery receives much concern always.
Lithium rechargeable battery comprises positive pole, negative pole, electrolyte and barrier film; The effect of barrier film is that the electronic conductance between the blocking-up both positive and negative polarity is avoided battery short circuit on the one hand, is the ionic conduction of keeping when battery discharges and recharges between both positive and negative polarity on the other hand.Ionic conduction between both positive and negative polarity is limited by the ionic conductivity of electrolyte itself on the one hand, depends on the other hand the barrier film characteristic.The barrier film characteristic that affects ionic conduction between both positive and negative polarity comprises porosity, pore-size distribution, imbibition ability, membrane thicknesses etc.Generally, the porosity, the reduction membrane thicknesses that improve barrier film can improve the ionic conduction between both positive and negative polarity, improve the high rate performance of battery; But above-mentioned way has increased the risk of both positive and negative polarity short circuit and thermal runaway.
At present, for the high rate performance of balance lithium ion battery and the contradiction between security performance, adopt the surface-coated technology to be coated with organic polymer or oxide-based ceramic nanoparticle or mixture both at the membrane surface of high porosity, low thickness more.This surface-coated technology adopts wet coating more, namely adopts solution or the suspension of organic polymer or nano particle, with technology such as roller coat, dip-coating, spraying, intaglio printings, organic polymer or nano particle is attached to membrane surface.The method is difficult to control to coating layer thickness and uniformity, and owing to relating to baking step, speed restriction is coated with the low also application of this technology of restriction greatly of membrane efficiency in addition.
Summary of the invention
The present invention is for solving the method complexity that is coated with organic polymer and organic polymer and the poor technical problem of base material adhesion of existing lithium ion battery separator, good and simple lithium ion battery of technique of a kind of polymer and base material adhesion and preparation method thereof is provided, contains the battery of this barrier film.
The invention provides a kind of lithium ion battery separator, this barrier film comprises that barrier film base material and physical vapour deposition (PVD) are in the organic polymer layers at least one surface of base material.
The present invention also provides a kind of preparation method of lithium ion battery separator, and the method is in substrate surface physical vapour deposition (PVD) one deck organic polymer layers.
The present invention also provides a kind of winding continuous coating equipment, vacuum control unit; Be in unwinding device, pretreating device, the first filming drum, the first physical vapor deposition device, the second plated film drum, the second physical vapor deposition device, wrap-up in the cavity of vacuum control unit;
Unwinding device and wrap-up lay respectively at the both sides of the first filming drum and the second plated film drum; Described the first physical vapor deposition device is positioned at the below of the first filming drum; Described the second physical vapor deposition device is positioned at the top of the second plated film drum;
Between described unwinding device and the first filming drum, pretreating device is set;
Between described unwinding device and pretreating device, between pretreating device and the first filming drum, between the first filming drum and the second plated film drum, be provided with deflector roll between the second plated film drum and wrap-up.
The present invention also provides a kind of lithium ion battery, and this battery comprises housing and is positioned at pole piece and the electrolyte of housing; Described pole piece comprises positive pole, negative pole and is in barrier film between positive and negative electrode, and described barrier film is barrier film of the present invention.
The present invention adopts the method for physical vapour deposition (PVD) organic polymer to be deposited on the surface of barrier film, and the method technical process is simple, pollution-free, consumptive material is few, the modification coating even compact that obtains, strong with the adhesion of matrix.The barrier film that adopts organic polymer to carry out finishing has kept the high porosity of barrier film base material and suitable closed pore temperature, has improved the imbibition ability of barrier film; Broken film temperature when fusing point can improve barrier film and is heated higher than the organic polymer of base material; On the other hand, owing to adopting the binding agent of polarity in positive and negative electrode, membrane surface adopts polar polymer, strengthen with the wettability of electrolyte, better to the adhesiveness of battery positive and negative electrode with respect to nonpolar PP, PE base material, make the applying between barrier film and positive and negative electrode tightr, prevent coming off of positive and negative electrode active material.
Description of drawings
Fig. 1 is winding continuous coating equipment schematic diagram of the present invention.
Embodiment
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, is not intended to limit the present invention.
The invention provides a kind of lithium ion battery separator, this barrier film comprises that barrier film base material and physical vapour deposition (PVD) are in the organic polymer layers at least one surface of base material.
Preferably, also contain solid electrolyte in described organic polymer layers.
Preferably, described barrier film also comprises the solid-state electrolyte layer that is positioned at the organic polymer layers surface.
Preferably, described barrier film also comprises the solid-state electrolyte layer between organic polymer layers and base material.
When having compatibility issue (oxidation-reduction potential of both positive and negative polarity is different) between solid electrolyte or organic polymer and both positive and negative polarity, can apply respectively different materials on barrier film base material two sides.Preferably, described barrier film also comprises solid-state electrolyte layer, and described organic polymer layers is positioned at a surface of base material, and described solid electrolyte layer is positioned at another surface of base material.
The barrier film that the present invention further adopts solid electrolyte to carry out finishing can make the higher lithium ion conduction speed of maintenance between lithium ion battery plus-negative plate, reduced simultaneously the risk of short circuit between both positive and negative polarity, the thermal contraction problem of having improved barrier film improves the security performance of battery.
Barrier film of the present invention, in order further to keep the high porosity of barrier film base material and suitable closed pore temperature, described organic polymer is PVDF-HFP(Kynoar-hexafluoropropylene), the PI(polyimides), the PU(polyamide), the PTFE(polytetrafluoroethylene), the PA(polyacrylate) the PVC(polyvinyl chloride), the PVDF(Kynoar) at least a.
Preferably, the lithium ion conductivity of described solid electrolyte is higher than 10
-8S
/Cm, electronic conductivity is lower than 10
-9S/cm.Higher ionic conductivity can provide except electrolyte more lithium ion conduction passage, replenishes under high magnification the lithium ion conduction by barrier film; Lower electronic conductivity has reduced the possibility of positive and negative electrode short circuit, the fail safe that has improved battery simultaneously.
According to barrier film provided by the present invention, in order further to reduce the short circuit of battery, preferably, described solid electrolyte is Li
xPO
yN
z, 2＜x＜4,3＜y＜5,0.1＜z＜0.9, LiNbO
3, Li
10GeP
2S
12, LiTaO
3, Li
xLa
(1/3-x)TaO
3, 0＜x＜3, Li
3PO
4, Li
xTi
y(PO
4)
3, 0＜x＜2,0＜y＜3, Li
xAl
yTi
z(PO
4)
3, 0＜x＜2,0＜y＜1,0＜z＜3, Li
2SiO
3, Li
2O, Li
2S, Li
2S-P
2S
5, Li
2S-SiS
2-P
2S
5, Li
xSi
yS
z, 0＜x＜3,0＜y＜2,0＜z＜4, Li
xP
yS
z, 0＜x＜3,0＜y＜3,0＜z＜7, LiBO
2, Li
3.6Si
0.6P
0.4O
4, Li
3At least a in N.
According to barrier film provided by the present invention, described base material has no particular limits, and can get final product for this area battery diaphragm commonly used, can be for example at least a in polyethylene, polypropylene or polyimides.
In order further to improve the lithium ion conduction speed between lithium ion battery government, preferably, the porosity of described base material is 20-70%.The thickness of described base material is the 8-35 micron.
In order to adapt to different batteries to the requirement of barrier film, preferably, the thickness of solid-state electrolyte layer is 10-500nm, and the thickness of organic polymer layers is 0.05-2 μ m.
The present invention also provides a kind of preparation method of lithium ion battery separator, and the method is in substrate surface physical vapour deposition (PVD) one deck organic polymer layers.
Preferably, also contain solid electrolyte in described organic polymer layer.
Preferably, also be included in the step of organic polymer layers surface physics gaseous phase deposition solid state dielectric substrate after substrate surface physical vapour deposition (PVD) organic polymer layers.
Preferably, also be included in the step of substrate surface physical vapour deposition (PVD) solid-state electrolyte layer before substrate surface physical vapour deposition (PVD) organic polymer layers.
Preferably, at a basic surface physics vapour deposition organic polymer layers, another surface physics gaseous phase deposition solid state dielectric substrate.
Described physical vapour deposition (PVD) is under vacuum condition, adopt physical method, material source (solid or liquid) surface is gasificated into gaseous atom, molecule or partial ionization becomes ion, and by low-pressure gas (or plasma) process, has the technology of the film of certain specific function in the matrix surface deposition.Described physical vapour deposition (PVD) is a kind of in magnetron sputtering, ion beam sputtering, pulsed laser deposition, ald and electron beam evaporation plating.
Physical gas phase deposition technology has following advantage: technical process is simple, pollution-free, consumptive material is few, film forming even compact, strong with the adhesion of matrix.Physical vapour deposition (PVD) also has outstanding characteristics to be: can carry out reactive deposition in specific atmosphere, for example Li
3PO
4At N
2Carry out sputter in atmosphere and can obtain the LiPON film, and LiPON is good solid electrolyte.The process that solid electrolyte is deposited on membrane surface as an example of magnetron sputtering deposition LiPON example describes: at first with the Li of suitable dimension
3PO
4Target is arranged in magnetron sputtering apparatus, and base material is fixed in filming equipment, vacuumizes that to reach vacuum degree be 5 * 10
-2Pa.Argon flow amount is 20sccm, and nitrogen flow is 120sccm, and sputtering power is 1000w, carries out plated film with the linear velocity of 80m/h, and the deposition regular hour namely gets the barrier film of finishing LiPON.
Described solid-state electrolyte layer is by the coating of solid state electrolysis raw material through obtaining after physical vapour deposition (PVD).Described solid state electrolysis raw material is LiNbO
3, LiTaO
3, Li
x2La
(1/3-x2)TaO
3, Li
3PO
4, Li
x3Ti
y3(PO
4)
3, Li
x4Al
y4Ti
z4(PO
4)
3, Li
2SiO
3, Li
2O, Li
2S, Li
2S-P
2S
5, Li
2S-SiS
2-P
2S
5, Li
x5Si
y5S
z5, Li
x6P
y6S
z6, LiBO
2, Li
3.6Si
0.6P
0.4O
4And Li
3At least a in N, wherein 2＜x1＜4,3＜y1＜5,0.1＜z1＜0.9; 0＜x2＜3; 0＜x3＜2,0＜y3＜3; 0＜x4＜2,0＜y4＜1,0＜z4＜3; 0＜x5＜3,0＜y5＜2,0＜z5＜4; 0＜x6＜3,0＜y6＜3,0＜z6＜7.
Physical gas-phase deposite method of the present invention is arranged in the equipment such as magnetron sputtering, pulsed laser deposition or ion beam sputtering, ald, electron beam evaporation plating for corresponding chemical being measured the solid state electrolysis raw material of ratio or target or coating materials that organic polymer is made, and deposition obtains in certain atmosphere.The present invention is take the method for the method of magnetron sputtering as example, and additive method is also the common practise of this area, again repeats no more.
Magnetron sputtering, at first the target with suitable dimension is arranged in magnetron sputtering apparatus, and base material is fixed in filming equipment, vacuumizes that to reach vacuum degree be 5 * 10
-1Pa-5 * 10
-4(may pass into other reacting gass, O2, H2S etc.) sputtering power is 500-3000w, carries out plated film with the linear velocity of 20m/h-120m/h, and the deposition regular hour namely gets the barrier film of finishing.
Described base material adopts the PE(polyethylene), the PP(polypropylene) or the PI(polyimides) in one or more.Preparation technology adopts the film by dry method preparation technology of this area routine, and the base material preparation process is as follows: 1. the melting in extruder with raw material polyolefin or polyimides, the raw material of melting be by die head, is drawn into former film through sharp cooling roll is cooling; 160-300 ℃ of film head temperature; Touch interlabial gap 0.1-2.3mm, sharp cooling roll temperature: 10-30 ℃.Draw ratio 5-50; 2. above-mentioned former film is passed through preheat roll, preheat temperature is 50-120 ℃, and be 5min-10 hour warm-up time.3. drawing and forming carries out two-way or longitudinal stretching with the polyolefin after preheating or polyimide film under temperature field and stretching and pulling force field synergy.Draft temperature 30-30 ℃; Stretching ratio is 5-100; Rate of extension 3-200m/min; 4. thermal finalization is carried out continuously or batch (-type) thermal finalization the polyolefin after stretching or polyimide film; 5. cooling, the film process after thermal finalization is continuous or the batch (-type) cooling section is cooling, can obtain barrier film base material of the present invention.
Because base material PP, PE are that its surface tension of non-polar polymer is less and have static, for tack and the firmness that improves coating.Preferably, base material is carried out surface treatment, and described pre-treatment is the methods such as corona, glow discharge, ion beam bombardment, and this pre-treatment can be eliminated the static of substrate surface, improve the surface tension of base material, the adhesion of base material and overlay coating is greatly improved.
The present invention also provides a kind of winding continuous coating equipment, and this equipment comprises vacuum control unit; Be in unwinding device, pretreating device, the first filming drum, the first physical vapor deposition device, the second plated film drum, the second physical vapor deposition device, wrap-up in the cavity of vacuum control unit;
Unwinding device and wrap-up lay respectively at the both sides of the first filming drum and the second plated film drum; Described the first physical vapor deposition device is positioned at the below of the first filming drum; Described the second physical vapor deposition device is positioned at the top of the second plated film drum;
Between described unwinding device and the first filming drum, pretreating device is set;
Between described unwinding device and pretreating device, between pretreating device and the first filming drum, between the first filming drum and the second plated film drum, be provided with deflector roll between the second plated film drum and wrap-up.
Coating process comprises: the base material barrier film is fixed in unwinding device, by closing in wrap-up after pretreating device, physical vapor deposition device, after regulating certain vacuum degree and other filming parameters, open unwinding device and wrap-up, carry out continuous coating according to certain linear velocity, plated film finishes namely to get barrier film of the present invention.As described in Figure 1,1 is unwinding device, and 2 is pretreating device, and 3a is the first filming drum, and 4a is the first physical vapor deposition device, and 3b is the second plated film drum, and 4b is the second physical vapor deposition device, and 5 is wrap-up.
The present invention also provides a kind of lithium ion battery, and this battery comprises housing and is positioned at pole piece and the electrolyte of housing; Described pole piece comprises positive pole, negative pole and is in barrier film between positive and negative electrode, and described barrier film is barrier film of the present invention.
Below in conjunction with specific embodiment, the present invention is described in further detail.
Embodiment 1
(1) base material preparation:
High density polyethylene (HDPE) (Mw=250000, Mw/Mn=12) is made former film by double screw extruder, 220 ℃ of temperature, stretching ratio is 5, former film preheating, the time is 2h, temperature is 120 ℃.Then the wide film of width 400mm is carried out longitudinal stretching, stretching ratio is 25, and rate of extension is 37m/min, 120 ℃ of temperature.Namely getting porosity is 60%, and thickness is the barrier film base material of 16 μ m.
(2) finishing coating
The base material that is 16 μ m with the long 1000m thickness of wide 400mm is fixed in the unwinding device and wrap-up of winding continuous coating equipment, that the square PVDF-HFP target that the target that adopts is of a size of 400*80*2 is arranged on respectively in physical vapor deposition device a and physical vapor deposition device b, close the plated film cavity, be evacuated to 5 * 10
-2Pa; Then, regulate breather valve and pass into argon gas and nitrogen, wherein argon flow amount is 20sccm, and nitrogen flow is 120sccm, and sputtering power is 1500W, and linear velocity is 60m/h, and obtaining is the barrier film of the thick PVDF-HFP layer of surface deposition 400nm, is denoted as S1.
(3) making of battery
Adopt the barrier film of above-mentioned preparation to be placed in and make to such an extent that nominal capacity is that the 1050mAh model is 053450 rectangular cell through coiling, sheath body, fluid injection, seal, change into etc. between cobalt acid lithium positive electrode and graphite negative electrode, be denoted as A1.
Embodiment 2
Adopt the method identical with embodiment 1 to prepare barrier film base material, finishing coating and battery, the target that different is adopts is of a size of the square PTFE of the being target of 400*80*2, and target only is arranged on physical vapor deposition device a, sputtering power is 1500W, linear velocity is 40m/h, obtaining is the barrier film of the thick PTFE layer of surface deposition 500nm, is denoted as S2; The made battery is denoted as A2.
Embodiment 3
Adopt the method identical with embodiment 1 to prepare barrier film base material, finishing coating and battery, different is to adopt respectively different targets and filming parameter in physical vapor deposition device a and physical vapor deposition device b, wherein 4a adopts the square PVDF-HFP(of the being molecular weight 450,000 that is of a size of 400*80*2,175 ℃ of fusing points) target, sputtering power is 1500W; 4b adopts the square LiNbO that is of a size of 400*80*6
3Target, sputtering power are 1000W.Coating wire speed is 60m/h, and obtaining is a thick PVDF-HFP layer of surface deposition 200nm and the thick LiNbO of another surface deposition 50nm
3The barrier film of layer is denoted as S3; Battery manufacturing process septation surface deposition LiNbO
3One side of layer is corresponding anodal, the corresponding negative pole of a side of surface deposition PVDF-HFP layer, and the made battery is denoted as A3.
Embodiment 4
Adopt the method identical with embodiment 1 to prepare barrier film base material, finishing coating and battery.Difference is: target is Li
2S, Li
2The S thickness of coating is 100nm; And then with Li
2S changes square PVC target its surface sputter one deck organic polymer layers again that is of a size of 400*80*2 into, and sputtering power is 1500W, and linear velocity is 60m/h, and obtaining is the barrier film of the thick PVC layer of surface deposition 400nm, is denoted as S4; The made battery is denoted as A4.
Embodiment 5
Adopt the method identical with embodiment 1 to prepare barrier film base material, finishing coating and battery, the target that different is first adopts is of a size of the square PTFE(of the being target of 400*80*2, sputtering power is 1500W, linear velocity is 40m/h, obtaining is the barrier film of the thick PTFE layer of surface deposition 2000nm, then the PTFE target is changed into the square Li that is of a size of 400*80*6
2SiO
3Target is arranged in filming equipment, closes the plated film cavity, is evacuated to 5 * 10
-2Pa; Then, regulate breather valve and pass into argon gas and nitrogen, wherein argon flow amount is 20sccm, and oxygen flow is 120sccm, and the adjusting sputtering power is 1000W, carries out plated film with the linear velocity of 80m/h, obtains the thick Li of surface deposition 500nm
2SiO
3The barrier film of layer is denoted as S5; The made battery is denoted as A5.
Embodiment 6
Adopt the method identical with embodiment 1 to prepare barrier film base material, finishing coating and battery, the stretching ratio of different is base material is 30, and the porosity of the base material that obtains is 65%, and the barrier film after plated film is denoted as S6; The made battery is denoted as A6.
Embodiment 7
Adopt the method identical with embodiment 1 to prepare barrier film base material, finishing coating and battery, different is that target Li is installed respectively in physical vapor deposition device a and physical vapor deposition device b simultaneously
2S and P
2S
5Obtain barrier film S7, the battery of made is designated as A7.
Embodiment 8
Adopt the method identical with embodiment 1 to prepare barrier film base material, finishing coating and battery, different is that target is Li
3PO
4And do not pass into nitrogen; Then with Li
3PO
4Change the square PVDF(molecular weight 400,000 that is of a size of 400*80*2 into, 168 ℃ of fusing points) target its surface sputter one deck organic polymer layers again, sputtering power is 1500W, and linear velocity is 60m/h, and obtaining is the barrier film of the thick PVDF layer of surface deposition 400nm, is denoted as S8; The made battery is denoted as A8.
Embodiment 9
Adopt the method identical with embodiment 1 to prepare barrier film base material, finishing coating and battery, different is that PI(molecular weight 180,000,334 ℃ of fusing points are installed respectively in physical vapor deposition device a and physical vapor deposition device b simultaneously) target and LiLa
0.5TaO
3Target, sputtering power are 1500W.Coating wire speed is 60m/h, and obtaining is the thick PI of surface deposition 250nm and LiLa
0.5TaO
3The barrier film of mixed layer is denoted as S9; The made battery is denoted as A9.
Embodiment 10
Adopt the method identical with embodiment 1 to prepare barrier film base material, finishing coating and battery, different different be that PU target and LiBO are installed respectively in physical vapor deposition device a and physical vapor deposition device b simultaneously
2Target, sputtering power are 1000W.Coating wire speed is 60m/h, and obtaining is the thick PU of surface deposition 1100nm and LiBO
2The barrier film of mixed layer is denoted as S10; The made battery is denoted as A10.
Embodiment 11
Adopt the method identical with embodiment 1 to prepare barrier film base material, finishing coating and battery, different is to adopt respectively different targets and filming parameter in physical vapor deposition device a and physical vapor deposition device b, wherein, wherein 4a adopts the square PA of the being target that is of a size of 400*80*2, and sputtering power is 1500W; The square Li that is of a size of 400*80*6 is adopted in the 4b position
3.6Si
0.6P
0.4O
4Target, sputtering power are 1000W.Coating wire speed is 60m/h, and obtaining is the thick PA layer of surface deposition 1500nm and the thick Li of 200nm
3.6Si
0.6P
0.4O
4The barrier film of layer is denoted as S11; Battery manufacturing process septation surface deposition Li
3.6Si
0.6P
0.4O
4One side of layer is corresponding anodal, the corresponding negative pole of a side of surface deposition PA layer, and the made battery is denoted as A11.
Comparative Examples 1
(1) barrier film preparation:
High density polyethylene (HDPE) (Mw=250000, Mw/Mn=12) is made former film by double screw extruder, temperature 220, stretching ratio is 5, former film preheating, the time is 2h, temperature is 120 ℃.Then the wide film of width 400mm is carried out longitudinal stretching, stretching ratio is 25, and rate of extension is 37m/min, 120 ℃ of temperature.Namely getting porosity is 60%, and thickness is the barrier film of 16 μ m, is denoted as SS1.
(2) battery preparation
Adopting the barrier film of above-mentioned preparation to be placed in and making nominal capacity through coiling, sheath body, fluid injection, seal, change into etc. between cobalt acid lithium positive electrode and graphite negative electrode is that the 1050mAh model is 053450 rectangular cell, is denoted as DA1.
Comparative Examples 2
Adopt the method identical with Comparative Examples 1 to prepare barrier film base material and battery, the stretching ratio of different is base material is 30, and the porosity of the base material that obtains is 65%, and the barrier film after plated film is denoted as SS2; The made battery is denoted as DA2.
Comparative Examples 3
Adopt the method identical with embodiment 1 to prepare barrier film base material battery, different is that finishing coating is coated in membrane surface by coating method.
(1) barrier film preparation:
High density polyethylene (HDPE) (Mw=250000, Mw/Mn=12) is made former film by double screw extruder, temperature 220, stretching ratio is 5, former film preheating, the time is 2h, temperature is 120 ℃.Then the wide film of width 400mm is carried out longitudinal stretching, stretching ratio is 25, and rate of extension is 37m/min, 120 ℃ of temperature.Namely getting porosity is 60%, and thickness is the barrier film of 16 μ m.
(2) surface-coated
0.1KG PVDF-HFP is added in 10KG acetone, stir 1h in de-airing mixer, obtain slurry and be placed in coating apparatus.The base material that is 16 μ m with the long 1000m thickness of wide 400mm is fixed in the unwinding device and wrap-up of coating apparatus, with the linear velocity of 5 m/h, is coated with processing by the dip-coating mode, and because acetone is inflammable, the baking temperature of coating process is controlled in 40 ℃.Namely obtaining porosity after coating is completed is 47%, and thickness is the barrier film of 35 μ m, is denoted as SS3; The made battery is denoted as DA3.
Performance test
One, the barrier film in embodiment 1-11 and Comparative Examples 1-3 is carried out following test, the results are shown in Table 1.
1, porosity: use standard and the method for ASTM D2873 to test.
2, air permeability: use the standard of GB4502-2003, with the test of GURLEY Permeability gauge.
3, hot strength: use standard and the method for testing of GB/T1040.3-2006 to test.
4, shrinkage: use standard and the method test of GB12027-2004; 120 ℃ of test conditions, 2h calculates the reduce in scale of shrinking rear specimen size.
Two, the battery in embodiment 1-11 and Comparative Examples 1-3 is carried out following test, the results are shown in Table 2.
1,130 ℃ of furnace temperature tests: use standard and the method for UL2054/UL1624 to test.The battery of 5 random chooses is charged to 4.2V in the 1C mode, be placed in the box type furnace of air circulation, be warming up to 130 ℃ with the speed of 5 ± 2 ℃ per minute from normal temperature and transfer constant temperature to, keep 10min, return room temperature after testing and observe.Require in the whole process of battery without blast, phenomenon on fire.
2,150 ℃ of furnace temperature tests: the battery of 5 random chooses is charged to 4.2V in the 1C mode, be placed in the box type furnace of air circulation, be warming up to 150 ℃ with the speed of 5 ± 2 ℃ per minute from normal temperature and transfer constant temperature to, keep 10min, return room temperature after testing and observe.Require in the whole process of battery without blast, phenomenon on fire.
3,1A-5V overcharges test: under 23 ± 3 ℃ of normal temperature, randomly draw 5 batteries and carry out charging measurement with 1A-5V under full electric attitude, require battery in the whole process that overcharges test until temperature drops to 40 ℃ without blast, on fire, the phenomenon of smoldering.
4, self discharge test: under 23 ± 3 ℃ of normal temperature, randomly draw 5 batteries with the 1C constant current charge, then charge cutoff voltage 3.8V carries out constant voltage charge with 3.8V, cut-off current 0.1C.Test initial open circuit voltage after shelving 3h.Then battery is stored 30 days under 23 ± 3 ℃ of normal temperature, the test open circuit voltage.Calculate the drop-out value of battery voltage after 30 days, respectively get the mean value of 5 batteries.
Table 1
Table 2: battery performance test result
As can be seen from Table 1, barrier film of the present invention is guaranteeing to possess excellent comprehensive performance under certain porosity and air permeability, and shrinkage at high temperature is little.
As can be seen from Table 2, overcharge test far away higher than the battery with the barrier film of Comparative Examples with 150 ℃ of furnace temperature test percent of pass of the battery of barrier film of the present invention and 1A-5V; And low with the self discharge of the battery of barrier film of the present invention, and it is very high to contain the self discharge of battery of the barrier film that Comparative Examples obtains.
The above is only preferred embodiment of the present invention, not in order to limiting the present invention, all any modifications of doing within the spirit and principles in the present invention, is equal to and replaces and improvement etc., within all should being included in protection scope of the present invention.
Claims (18)
1. a lithium ion battery separator, is characterized in that, this barrier film comprises that barrier film base material and physical vapour deposition (PVD) are in the organic polymer layers at least one surface of base material.
2. barrier film according to claim 1, is characterized in that, also contains solid electrolyte in described organic polymer layers.
3. barrier film according to claim 1, is characterized in that, described barrier film also comprises the solid-state electrolyte layer that is positioned at the organic polymer layers surface.
4. barrier film according to claim 1, is characterized in that, described barrier film also comprises the solid-state electrolyte layer between organic polymer layers and base material.
5. barrier film according to claim 1, is characterized in that, described barrier film also comprises solid-state electrolyte layer, and described organic polymer layers is positioned at a surface of base material, and described solid electrolyte layer is positioned at another surface of base material.
6. according to claim 1-5 described barrier films of any one, it is characterized in that, described organic polymer is at least a in Kynoar-hexafluoropropylene, polyimides, polyamide, polytetrafluoroethylene, polyacrylate, polyvinyl chloride, Kynoar, polyethylene glycol oxide.
7. according to claim 2-5 described barrier films of any one, is characterized in that, the lithium ion conductivity of described solid electrolyte is higher than 10
-8S
/Cm, electronic conductivity is lower than 10
-9S/cm.
8. according to claim 2-5 described barrier films of any one, is characterized in that, described solid electrolyte is Li
x1PO
y1N
z1, LiNbO
3, Li
10GeP
2S
12, LiTaO
3, Li
x2La
(1/3-x2)TaO
3, Li
3PO
4, Li
x3Ti
y3(PO
4)
3, Li
x4Al
y4Ti
z4(PO
4)
3, Li
2SiO
3, Li
2O, Li
2S, Li
2S-P
2S
5, Li
2S-SiS
2-P
2S
5, Li
x5Si
y5S
z5, Li
x6P
y6S
z6, LiBO
2, Li
3.6Si
0.6P
0.4O
4And Li
3At least a in N; 2＜x1＜4,3＜y1＜5,0.1＜z1＜0.9 wherein; 0＜x2＜3; 0＜x3＜2,0＜y3＜3; 0＜x4＜2,0＜y4＜1,0＜z4＜3; 0＜x5＜3,0＜y5＜2,0＜z5＜4; 0＜x6＜3,0＜y6＜3,0＜z6＜7.
9. according to claim 1-5 described barrier films of any one, is characterized in that, described base material is at least a in polyethylene, polypropylene or polyimides.
10. according to claim 1-5 described barrier films of any one, is characterized in that, the porosity of described base material is 20%-70%, and the thickness of described base material is the 8-35 micron.
11. the preparation method of a lithium ion battery separator is characterized in that, the method is in substrate surface physical vapour deposition (PVD) one deck organic polymer layers.
12. preparation method according to claim 11 is characterized in that, also contains solid electrolyte in described organic polymer layer.
13. preparation method according to claim 11 is characterized in that, also is included in the step of organic polymer layers surface physics gaseous phase deposition solid state dielectric substrate after substrate surface physical vapour deposition (PVD) organic polymer layers.
14. preparation method according to claim 11 is characterized in that, also is included in the step of substrate surface physical vapour deposition (PVD) solid-state electrolyte layer before substrate surface physical vapour deposition (PVD) organic polymer layers.
15. preparation method according to claim 11 is characterized in that, at a basic surface physics vapour deposition organic polymer layers, another surface physics gaseous phase deposition solid state dielectric substrate.
16. according to claim 11-15 described preparation methods of any one is characterized in that, described physical vapour deposition (PVD) is a kind of in magnetron sputtering, ion beam sputtering, pulsed laser deposition, ald and electron beam evaporation plating.
17. a winding continuous coating equipment is characterized in that, described equipment comprises:
Vacuum control unit; Be in unwinding device, pretreating device, the first filming drum, the first physical vapor deposition device, the second plated film drum, the second physical vapor deposition device, wrap-up in the cavity of vacuum control unit;
Unwinding device and wrap-up lay respectively at the both sides of the first filming drum and the second plated film drum; Described the first physical vapor deposition device is positioned at the below of the first filming drum; Described the second physical vapor deposition device is positioned at the top of the second plated film drum;
Between described unwinding device and the first filming drum, pretreating device is set;
Between described unwinding device and pretreating device, between pretreating device and the first filming drum, between the first filming drum and the second plated film drum, be provided with deflector roll between the second plated film drum and wrap-up.
18. a lithium ion battery, this battery comprise housing and are positioned at pole piece and the electrolyte of housing; Described pole piece comprises positive pole, negative pole and is in barrier film between positive and negative electrode, and it is characterized in that, described barrier film is the described barrier film of claim 1-5 any one.
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| CN103137930A true CN103137930A (en) | 2013-06-05 |
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| CN103996877A (en) * | 2013-11-26 | 2014-08-20 | 深圳市星源材质科技股份有限公司 | Method for processing lithium ion battery cell by diaphragm coating |
| CN104681858A (en) * | 2015-01-30 | 2015-06-03 | 中南大学 | Ultrathin flexible lithium ion battery and preparation method thereof |
| WO2016046452A1 (en) | 2014-09-24 | 2016-03-31 | Picodeon Ltd Oy | Method for coating separator films of lithium batteries and a coated separator film |
| CN105977541A (en) * | 2016-06-28 | 2016-09-28 | 盈天科技（深圳）有限公司 | Production apparatus of lithium ion battery |
| CN106067528A (en) * | 2015-04-23 | 2016-11-02 | Sk新技术株式会社 | Composite separating film and preparation method thereof |
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| CN111293259A (en) * | 2020-02-26 | 2020-06-16 | 中航锂电技术研究院有限公司 | Battery diaphragm and lithium ion battery |
| CN115020801A (en) * | 2022-08-08 | 2022-09-06 | 国联汽车动力电池研究院有限责任公司 | Solid electrolyte composite membrane and preparation method and application thereof |
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| WO2016046452A1 (en) | 2014-09-24 | 2016-03-31 | Picodeon Ltd Oy | Method for coating separator films of lithium batteries and a coated separator film |
| CN104681858A (en) * | 2015-01-30 | 2015-06-03 | 中南大学 | Ultrathin flexible lithium ion battery and preparation method thereof |
| CN106067528A (en) * | 2015-04-23 | 2016-11-02 | Sk新技术株式会社 | Composite separating film and preparation method thereof |
| CN106960933A (en) * | 2015-12-02 | 2017-07-18 | Sk新技术株式会社 | Heat resistance and the excellent secondary cell barrier film of closing property |
| US11139542B2 (en) | 2015-12-02 | 2021-10-05 | Sk Innovation Co., Ltd. | Separator for secondary cell having excellent heat resistance and shutdown properties |
| CN105977541A (en) * | 2016-06-28 | 2016-09-28 | 盈天科技（深圳）有限公司 | Production apparatus of lithium ion battery |
| CN106099260A (en) * | 2016-08-12 | 2016-11-09 | 洁能电投（北京）新能源科技有限公司 | Solid electrolyte composite diaphragm and preparation method and flow battery electrolyte system |
| CN106282953A (en) * | 2016-09-20 | 2017-01-04 | 江苏阳帆机电设备制造有限公司 | The manufacture method of a kind of wear-resisting line cutting steel wire and prepare wear-resisting line cutting steel wire vacuum covering filming equipment |
| US11959166B2 (en) | 2018-08-14 | 2024-04-16 | Massachusetts Institute Of Technology | Methods of fabricating thin films comprising lithium-containing materials |
| CN111293259A (en) * | 2020-02-26 | 2020-06-16 | 中航锂电技术研究院有限公司 | Battery diaphragm and lithium ion battery |
| CN115020801A (en) * | 2022-08-08 | 2022-09-06 | 国联汽车动力电池研究院有限责任公司 | Solid electrolyte composite membrane and preparation method and application thereof |
| WO2024065151A1 (en) * | 2022-09-27 | 2024-04-04 | 宁德时代新能源科技股份有限公司 | Separator and preparation method therefor, secondary battery, battery module, battery pack, and electrical apparatus |
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