CN104377330A - Gel polymer modified lithium ion battery diagraph and preparing method and application thereof - Google Patents
Gel polymer modified lithium ion battery diagraph and preparing method and application thereof Download PDFInfo
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- CN104377330A CN104377330A CN201410623479.4A CN201410623479A CN104377330A CN 104377330 A CN104377330 A CN 104377330A CN 201410623479 A CN201410623479 A CN 201410623479A CN 104377330 A CN104377330 A CN 104377330A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/463—Separators, membranes or diaphragms characterised by their shape
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Abstract
The invention relates to a gel polymer modified lithium ion battery diagraph and a preparing method and application thereof. The diagraph comprises a microporous polymer layer and at least one layer of gel polymer coating coated with which the microporous polymer layer is coated. The peel strength between the gel polymer coating and the microporous polymer layer in a 180-degree-condition is over 1.0N/cm. The surface and the interior of the gel polymer coating are in reticular porous connecting structures. The porosity of the gel polymer coating is over 40%. A gel polymer is a copolymer of vinylidene fluoride and hexafluoropropylene. According to the invention, the problems that the adhesion between the gel polymer coating and the microporous polymer layer is poor and the gel polymer coating is easy to strip from the polymer microporous layer are solved, and the problem that the gel polymer coating swells in electrolyte as to enable the coating porosity to be reduced, and further the battery internal resistance is increased is solved.
Description
Technical field
The present invention relates to technical field of lithium ion, particularly a kind of gelatin polymer modification lithium-ion battery barrier film and preparation method thereof.
Background technology
Along with the development of microelectric technique, miniaturized equipment is increasing, proposes very high requirement to power supply.The useful performances such as lithium ion battery has that operating voltage is high, energy density is large, have extended cycle life, self-discharge rate is little, low stain, memory-less effect, be widely used in a lot of aspect by people, such as, on mobile phone, palmtop PC, notebook computer, electric tool, electric motor car, street lamp stand-by power supply, navigation lights, video camera, camera, family expenses small electric apparatus.Gel polymer lithium ion battery wherein has demonstrated powerful growth momentum, and its use has been not limited to the field such as portable type electronic product, electric motor car, is also generalized to the field such as artificial satellite, space flight and aviation.
Gel polymer lithium ion battery conventional is at present the lithium ion battery that barrier film has gelation coating, and due to the special construction of gel, gel polymer lithium ion battery has high-energy-density and long circulation life; There is excellent machinability, add thermoplasticity and the forming technique of gelatin polymer, gel polymer lithium ion battery shell is made to make various shape, not only improve the problems such as leakage that liquid lithium ionic cell may occur, burning and blast, and the configuration design assembling of battery is also flexible.
Chinese patent 201180049838.4 and 201180049820.4 discloses and adopts wet coating method to prepare gelatin polymer modification lithium-ion battery barrier film, that is: first, is dissolved in by gelatin polymer in solvent, prepares coating fluid; By coating solution on many microporous substrates, afterwards, immerse coagulating bath, by bringing out to be separated, gel polymer coating being solidified, obtaining the lithium ion battery separator of the gel polymer coating with multi-cellular structure.Compared with dry coating method, the environment that wet coating method can avoid use low boiling point solvent to cause and suitability for industrialized production safety problem, realize the accurate control to gel polymer coating aperture, porosity, but coating after gel polymer coating and substrate adherence poor, coating is easy to peel off from base material, and gelatin polymer is in the electrolytic solution due to swelling, causes coating porosity to reduce, and cause the internal resistance of cell to increase thereupon.
Summary of the invention
The object of the invention is to the above-mentioned defect overcoming prior art, a kind of gelatin polymer modification lithium-ion battery barrier film is provided, solve gel polymer coating and substrate adherence is poor, be easy to the problem peeled off from base material, and gel polymer coating is in the electrolytic solution due to swelling, cause coating porosity to reduce, cause the problem that the internal resistance of cell increases.
For achieving the above object, the technical scheme that the present invention takes is:
A kind of gelatin polymer modification lithium-ion battery barrier film, comprise polymer microporous layer and at least one deck be coated in the gel polymer coating on polymer microporous layer, the peel strength between described gel polymer coating and described polymer microporous layer under 180 ° of DEG C of conditions is more than 1.0N/cm; Described gel polymer coating surface and inside are in mesh structural porous syndeton; The porosity of described gel polymer coating is 40% ~ 80%;
Described gelatin polymer is the copolymer of vinylidene and hexafluoropropylene, and wherein, the mass percent that hexafluoropropylene accounts for gelatin polymer is 5% ~ 20%;
Described gel polymer coating is in the mixed solvent be made up of ethylene carbonate, dimethyl carbonate, diethyl carbonate (electrolyte solvent), swelling ratio when 40 DEG C is lower than 40%, swelling ratio when 80 DEG C lower than 400%, ethylene carbonate in described mixed solvent: dimethyl carbonate: the volume ratio of diethyl carbonate is 2:2:1.
Above-mentioned gelatin polymer modification lithium-ion battery barrier film, described polymer microporous layer is the microporous membrane that one or more the composition resins in polyethylene, polypropylene, polybutene or polyvinyl chloride are formed.
Above-mentioned gelatin polymer modification lithium-ion battery barrier film, described polymer microporous layer is the microporous membrane of one or more resins formation in polycyclic alkene, polyether sulfone, PETG, polyamide, polyimides, polyimide amide or polytetrafluoroethylene or the microporous membrane of described resin fibre braiding, or the nonwoven fabrics microporous membrane that described resin fibre is formed.
Above-mentioned gelatin polymer modification lithium-ion battery barrier film, described polymer microporous layer is single layer structure, double-decker, three-decker or sandwich construction.
Above-mentioned gelatin polymer modification lithium-ion battery barrier film, thickness≤20 μm of described polymer microporous layer.
Above-mentioned gelatin polymer modification lithium-ion battery barrier film, the number-average molecular weight of described gelatin polymer is 100000 ~ 1500000.
A preparation method for gelatin polymer modification lithium-ion battery barrier film, preparation process is as follows:
(1) be dissolved in solvent I by gelatin polymer, be uniformly mixed, obtain coating fluid, wherein, the mass percent that described gelatin polymer accounts for coating fluid is 1% ~ 20%, and the flash-point of solvent I is more than 50 DEG C;
(2) by the surface of described coating solution at polymer microporous layer, obtain the film A containing gel polymer coating, wherein, coating weight is 10g/m
2~ 100g/m
2;
(3) described film A is immersed in solvent II, stop 5s ~ 35s, obtain the film B of the gel polymer coating containing microcellular structure;
(4) described film B is immersed in the water, stops 5s ~ 35s, after removing the organic solvent in film surface and micropore, dry at 20 DEG C ~ 80 DEG C, obtain described gelatin polymer modification lithium-ion battery barrier film.
Described solvent I is selected from one or more in DMF, DMA, 1-METHYLPYRROLIDONE;
Solvent II is water and the mixed solvent being selected from one or more compositions in DMF, DMA, 1-METHYLPYRROLIDONE, ethylene glycol, dimethyl sulfoxide (DMSO), absolute ethyl alcohol.
A kind of lithium ion battery, comprises above-mentioned gelatin polymer modification lithium-ion battery barrier film, positive pole, negative pole and electrolyte.
A kind of lithium ion battery, comprises the gelatin polymer modification lithium-ion battery barrier film obtained according to said method.
The present invention compared with prior art, has following beneficial effect:
(1), the present invention adopts the gelatin polymer be made up of the copolymer of vinylidene and hexafluoropropylene, and the mass percent that hexafluoropropylene accounts for gelatin polymer is 5% ~ 20%; Gelatin polymer swelling ratio is in the electrolytic solution made to control in suitable scope, thus make gelatin polymer modification lithium-ion battery barrier film have good ionic conductivity, have the property such as mechanical property, heat-resisting quantity, chemical resistance and dielectricity, piezoelectricity, pyroelectricity concurrently simultaneously.
(2), inventive gel polymer swelling ratio in the electrolytic solution controls in suitable scope, solves gelatin polymer in the electrolytic solution due to swelling, causes coating porosity to reduce, cause the problem that the internal resistance of cell increases.
(3) the present invention is by controlling coating fluid formula and preparation technology, peel strength under 180 ° of conditions between described gel polymer coating and described microporous polyolefin film is more than 1.0N/cm, solves gelatin polymer and substrate adherence is poor, be easy to the problem peeled off from base material.
Accompanying drawing explanation
Fig. 1 is the SEM photo of gelatin polymer modification lithium-ion battery barrier film in the embodiment of the present invention 1.
Embodiment
Below in conjunction with specific embodiment, further detailed description is done to the present invention, but embodiments of the present invention are not limited to these embodiments.
Gelatin polymer modification lithium-ion battery barrier film of the present invention forms by microporous polyolefin film basis material with at the gel polymer coating that its single or double applies.
Polymeric poromeric layer
In gelatin polymer modification lithium-ion battery barrier film disclosed by the invention, the polymeric poromeric layer as base material can for not having electronic conductivity arbitrarily but having ionic conductivity and have the fine multiple aperture plasma membrane in solvent resistance, chemical stability, aperture.Optional from polyolefin microporous membrane, wherein, polyolefin is one or more in polyethylene, polypropylene, polybutene and polyvinyl chloride.The also formation microporous membrane of the resin such as optional autohemagglutination cycloolefin, polyether sulfone, PETG, polyamide, polyimides, polyimide amide, polytetrafluoroethylene or the nonwoven fabrics microporous membrane etc. that is made up of microporous membrane or its fiber of its fibrage.
Polymer microporous membrane can be the single layer structure of the above-mentioned any microporous membrane composition enumerated, double-decker, three-decker or sandwich construction.From be easy to lithium ion battery separator paste compound disclosed by the invention coating and membrane thicknesses can be reduced and improve inside lithium ion cell active material ratio and there is closed pore characteristic and improve lithium ion battery separator safety perspective consider, preferred polyolefm microporous membrane, the polyolefin microporous membrane of further preferred single layer structure, particularly preferred single layer polyethylene or polypropylene microporous membrane.
Wherein, described polymer microporous membrane is single layer structure, double-decker, three-decker or sandwich construction, is preferably single layer structure, its thickness≤20 μm, is preferably≤16 μm, be more preferably≤12 μm.
Gel polymer coating
Gelatin polymer coating solution, on polymer microporous layer, through solidifying, washing, after drying, obtains gel polymer coating.Gel polymer coating surface and inside are in mesh structural porous syndeton.The porosity of gel polymer coating is 40% ~ 80%, preferably 50% ~ 70%.When gel polymer coating porosity lower than 40% time, cause the porosity of gelatin polymer modified diaphragm to reduce, its ionic conductivity reduced; When gel polymer coating porosity higher than 80% time, be difficult to the network structure that impact is crosslinked, easily cause the phenomenon such as holes, ceasma.
Gelatin polymer in gelatin polymer coating fluid is the copolymer of vinylidene and hexafluoropropylene, i.e. P (VDF-HFP), and the mass percent of hexafluoropropylene is 5% ~ 20%.Compared with other gelatin polymer, Kynoar has the property such as good mechanical property, heat-resisting quantity, chemical resistance and dielectricity, piezoelectricity, pyroelectricity.But because the degree of crystallinity of pure Kynoar is higher, swelling ratio is in the electrolytic solution lower, causes ionic conductivity to reduce.The present invention selects the copolymer p (VDF-HFP) of vinylidene and hexafluoropropylene, and regulate the ratio of vinylidene and hexafluoropropylene, make gelatin polymer swelling ratio in the electrolytic solution control in suitable scope, make gelatin polymer barrier film have good ionic conductivity.Gelatin polymer is in mixed solvent, and swelling ratio when 40 DEG C is lower than 40%, and swelling ratio when 80 DEG C is lower than 400%.Wherein, mixed solvent is EC(ethylene carbonate), DMC(dimethyl carbonate), DEC(diethyl carbonate) mixture, the ratio of mixed solvent is EC:DMC:DEC is 2:2:1.If the swelling ratio of gelatin polymer 40 DEG C time is higher than 40%, after causing gelatin polymer modification lithium-ion battery barrier film in the electrolytic solution swelling, the microcellular structure of coating is disappeared, the internal resistance of cell is increased.
The number-average molecular weight of gelatin polymer is 100000 ~ 1500000, is preferably 200000 ~ 1000000.When number-average molecular weight lower than 100000 time, swelling ratio is excessive in the electrolytic solution will to cause gelatin polymer, reduces the porosity of gel polymer coating, causes the internal resistance of gel polymer lithium ion battery excessive; When number-average molecular weight higher than 1500000 time, in coating fluid preparation process, make gelatin polymer be difficult to dissolve, coating fluid viscosity is excessive, affects follow-up coating and solidifies pore-creating operation.
Be explained, the gelatin polymer commercially available arbitrarily meeting above-mentioned condition all can with coating material of the present invention.
The preparation method of gelatin polymer modification lithium-ion battery barrier film
The present invention adopts wet coating method to prepare gelatin polymer modification lithium-ion battery barrier film, and wet coating method prepares the conventional method of microporous membrane or many micro porous coatings, do not do specified otherwise at this.
The concrete preparation process of inventive gel polymer modification lithium ion battery separator is:
(1) be dissolved in solvent I by gelatin polymer, be uniformly mixed, obtain coating fluid, wherein, the mass percent that gelatin polymer accounts for coating fluid is 1% ~ 20%, and the flash-point of solvent I is more than 50 DEG C.
(2) by the surface of coating solution in microporous polyolefin film, obtain the film A containing gel polymer coating, wherein, coating weight is 10g/m
2~ 100g/m
2.
By the method for coating solution on microporous polyolefin film surface, as long as required coating layer thickness can be realized, coating homogeneity is then not particularly limited.Optional method has: gravure coating process, micro-gravure coating process, reverse rod rubbing method, transfer roll rubbing method, dip coating, stick coating method, extrusion coated method, silk screen printing, spraying process etc.
Coating fluid can be applied to the single or double of microporous polyolefin film, is preferably coated to the two-sided of microporous polyolefin film.
(3) immerse in solvent II by film A, stop 5s ~ 35s, obtain the film B of the gel polymer coating containing microcellular structure, wherein, solvent II is water and the mixed solvent being selected from one or more compositions in DMF, DMAc, NMP, EG, DMAc, EtOH.
(4) film B is immersed in the water, stops 5s ~ 35s, after removing the organic solvent in film surface and micropore, dry, obtain gelatin polymer modification lithium-ion battery barrier film.
Wherein, the microporous polyolefin film in step (2) is selected from one or more in PE, PP, and polymer microporous membrane is single layer structure, double-decker, three-decker or sandwich construction.
Wherein, in step (1), solvent I is selected from one or more in DMF, DMAc, NMP.
Baking temperature in step (4) is 20 DEG C ~ 80 DEG C.
The present invention is by designing gelatin polymer coating fluid formula and preparation method, the accurate control to coating aperture and porosity can be realized, and realizing the present invention by controlling coating fluid formula and preparation technology, the peel strength under 180 ° of conditions between described gel polymer coating and described microporous polyolefin film is more than 1.0N/cm.
Method of testing
The definition of the porosity of gel polymer coating is the ratio that the volume in the space of gel polymer coating accounts for whole gel polymer coating volume, with P(%) represent, 1. can be calculated by use formula.
①
Wherein, ρ (g/cm
3): the density of gelatin polymer; M(g/cm
2): the quality of the per unit area of gel polymer coating; D(cm): be the thickness of gel polymer coating.
The method of testing of the gel polymer coating described in the present invention and the peel strength between described microporous polyolefin film under 180 ° of conditions is based on JIS Z0237 standard.First, gelatin polymer modification lithium-ion battery barrier film is cut into the test film of horizontal 20mm × vertical 150mm size, attaches adhesive tape in gel polymer coating side, by adhesive tape doubling 180 °, then peel off 25mm from this sample; Then, the barrier film one end after stripping is fixed on the lower jaw of cupping machine, upper jaw is fixed in the adhesive tape one end after peeling off, stretches with the speed of 10mm/min; After mensuration, ignore the measured value of initial 25mm length, the peel strength measured value being peeled off 50mm length by test film is averaged, using its mean value as peel strength.
Lithium ion battery
Lithium ion battery of the present invention refers to the lithium ion battery using and have gelation coated separator, and it comprises the modification lithium-ion battery of gelatin polymer disclosed in the present invention barrier film, positive pole, negative pole and electrolyte.Wherein, positive pole, negative pole and electrolyte are material general arbitrarily, specifically do not limit.
In conjunction with foregoing, the invention provides following preferred embodiment, main technical parameter is listed in table 1, is described in detail as follows:
Embodiment 1
(1) by 200g molecular weight be 100000 P (VDF-HFP) be dissolved in 800g DMF, be uniformly mixed, obtain coating fluid.
(2) adopt micro-gravure coating process by coating solution thickness be 16 μm PP/PE duplicature surface, control coating weight is 10g/m
2, obtain film A,
(3) film A being immersed water: EG:DMAc is in the mixed solvent of 80:18:2, stops 5s, obtains the film B containing microcellular structure coating.
(4) film B is immersed in the water, stops 5s, after removing the organic solvent in film surface and micropore, dry at 50 DEG C, obtain gelatin polymer modification lithium-ion battery barrier film.
Wherein, in gelatin polymer P (VDF-HFP), the ratio of HFP is 5%.As shown in Figure 1, as can be seen from the figure, gel polymer coating has uniform aperture result to the microscopic appearance of the gelatin polymer modification lithium-ion battery barrier film obtained.The thickness of gel polymer coating is 2.5 μm, and coating porosity is 45%, 180 ° of peel strengths is 1.2N, and swelling ratio when swelling ratio when 40 DEG C is 15%, 80 DEG C is 300%.
Embodiment 2
(1) by 10g molecular weight be 1500000 P (VDF-HFP) be dissolved in 990g NMP, be uniformly mixed, obtain coating fluid.
(2) coating solution is the PP/PE/PP trilamellar membrane surface of 20 μm at thickness by employing dip coating, and control coating weight is 100g/m
2, obtain film A,
(3) film A being immersed water: DMF:EtOH is in the mixed solvent of 50:10:40, stops 15s, obtains the film B containing microcellular structure coating.
(4) film B is immersed in the water, stops 15s, after removing the organic solvent in film surface and micropore, dry at 80 DEG C, obtain gelatin polymer modification lithium-ion battery barrier film.
Wherein, in gelatin polymer P (VDF-HFP), the ratio of HFP is 7%.The microscopic appearance of the gelatin polymer modification lithium-ion battery barrier film obtained is close with embodiment, no longer provides herein.The thickness of gel polymer coating is 1.2 μm, and coating porosity is 47%, 180 ° of peel strengths is 1.4N, and swelling ratio when swelling ratio when 40 DEG C is 26%, 80 DEG C is 350%.
Embodiment 3
(1) by 30g molecular weight be 400000 P (VDF-HFP) be dissolved in 970g DMAc, be uniformly mixed, obtain coating fluid.
(2) coating solution is the PE monofilm surface of 12 μm at thickness by employing stick coating method, and control coating weight is 70g/m
2, obtain film A,
(3) film A being immersed water: EG:EtOH is in the mixed solvent of 60:20:20, stops 25s, obtains the film B containing microcellular structure coating.
(4) film B is immersed in the water, stops 25s, after removing the organic solvent in film surface and micropore, dry at 50 DEG C, obtain gelatin polymer modification lithium-ion battery barrier film.
Wherein, in gelatin polymer P (VDF-HFP), the ratio of HFP is 7%.The microscopic appearance of the gelatin polymer modification lithium-ion battery barrier film obtained is close with embodiment, no longer provides herein.The thickness of gel polymer coating is 2.0 μm, and coating porosity is 59%, 180 ° of peel strengths is 2.1N, and swelling ratio when swelling ratio when 40 DEG C is 27%, 80 DEG C is 360%.
Embodiment 4
(1) by 40g molecular weight be 600000 P (VDF-HFP) be dissolved in 960g DMAc, be uniformly mixed, obtain coating fluid.
(2) employing reverses the PE monofilm surface that coating solution at thickness is 16 μm by rod rubbing method, and control coating weight is 35g/m
2, obtain film A,
(3) film A being immersed water: EG is in the mixed solvent of 40:60, stops 20s, obtains the film B containing microcellular structure coating.
(4) film B is immersed in the water, stops 20s, after removing the organic solvent in film surface and micropore, dry at 50 DEG C, obtain gelatin polymer modification lithium-ion battery barrier film.
Wherein, in gelatin polymer P (VDF-HFP), the ratio of HFP is 10%.The microscopic appearance of the gelatin polymer modification lithium-ion battery barrier film obtained is close with embodiment, no longer provides herein.The thickness of gel polymer coating is 1.0 μm, and coating porosity is 80%, 180 ° of peel strengths is 2.0N, and swelling ratio when swelling ratio when 40 DEG C is 29%, 80 DEG C is 370%.
Embodiment 5
(1) by 50g molecular weight be 1000000 P (VDF-HFP) be dissolved in 950g NMP, be uniformly mixed, obtain coating fluid.
(2) coating solution is the PE monofilm surface of 12 μm at thickness by employing transfer roll rubbing method, and control coating weight is 30g/m
2, obtain film A,
(3) film A being immersed water: EtOH is in the mixed solvent of 60:40, stops 30s, obtains the film B containing microcellular structure coating.
(4) film B is immersed in the water, stops 30s, after removing the organic solvent in film surface and micropore, dry at 50 DEG C, obtain gelatin polymer modification lithium-ion battery barrier film.
Wherein, in gelatin polymer P (VDF-HFP), the ratio of HFP is 15%.The microscopic appearance of the gelatin polymer modification lithium-ion battery barrier film obtained is close with embodiment, no longer provides herein.The thickness of gel polymer coating is 2.1 μm, and coating porosity is 40%, 180 ° of peel strengths is 1.8N, and swelling ratio when swelling ratio when 40 DEG C is 32%, 80 DEG C is 380%.
Embodiment 6
(1) by 100g molecular weight be 500000 P (VDF-HFP) be dissolved in 900g NMP, be uniformly mixed, obtain coating fluid.
(2) coating solution is the PE monofilm surface of 20 μm at thickness by employing extrusion coated method, and control coating weight is 25g/m
2, obtain film A,
(3) film A being immersed water: NMP:EtOH is in the mixed solvent of 60:2:38, stops 35s, obtains the film B containing microcellular structure coating.
(4) film B is immersed in the water, stops 35s, after removing the organic solvent in film surface and micropore, dry at 60 DEG C, obtain gelatin polymer modification lithium-ion battery barrier film.
Wherein, in gelatin polymer P (VDF-HFP), the ratio of HFP is 20%.The microscopic appearance of the gelatin polymer modification lithium-ion battery barrier film obtained is close with embodiment, no longer provides herein.The thickness of gel polymer coating is 3.0 μm, and coating porosity is 47%, 180 ° of peel strengths is 1.5N, and swelling ratio when swelling ratio when 40 DEG C is 39%, 80 DEG C is 400%.
Comparative example 1
(1) by 30g molecular weight be 1500000 P (VDF-HFP) be dissolved in 970g acetone, be uniformly mixed, obtain coating fluid.
(2) coating solution is the PE monofilm surface of 12 μm at thickness by employing dip coating, and control coating weight is 50g/m
2, obtain film A,
(3) film A is dry at 30 DEG C, obtain gelatin polymer modification lithium-ion battery barrier film.
Wherein, in gelatin polymer P (VDF-HFP), the ratio of HFP is 7%.The thickness of gel polymer coating is 2.0 μm, and coating porosity is 42%, 180 ° of peel strengths is 0.3N, and swelling ratio when swelling ratio when 40 DEG C is 27%, 80 DEG C is 360%.
The gel polymer lithium ion battery barrier film of this comparative example adopts dry coating method to be prepared, compared with embodiment 3, the gelatin polymer adopted is identical, when adopting identical basement membrane, coating layer thickness identical, coating porosity will be starkly lower than the gel polymerisation lithium ion battery separator adopting wet coating method obtained.180 ° of peel strengths of coating are also obvious low compared with the gel polymerisation lithium ion battery separator prepared by embodiment 3.
Comparative example 2
(1) by 30g molecular weight be 400000 PVDF be dissolved in 970g DMAc, be uniformly mixed, obtain coating fluid.
(2) coating solution is the PE monofilm surface of 12 μm at thickness by employing stick coating method, and control coating weight is 70g/m
2, obtain film A,
(3) film A being immersed water: EG:EtOH is in the mixed solvent of 60:20:20, stops 25s, obtains the film B containing microcellular structure coating.
(4) film B is immersed in the water, stops 25s, after removing the organic solvent in film surface and micropore, dry at 50 DEG C, obtain gelatin polymer modification lithium-ion battery barrier film.
Wherein, gelatin polymer PVDF is the homopolymers of vinylidene, not containing HFP.The thickness of gel polymer coating is 2.0 μm, and coating porosity is 59%, 180 ° of peel strengths is 0.2N, and swelling ratio when swelling ratio when 40 DEG C is 5%, 80 DEG C is 120%.
Compared with embodiment 3, the gelatin polymer that the present embodiment adopts is the homopolymers of vinylidene, when adopting identical basement membrane, coating layer thickness identical, 180 ° of peel strengths of coating are also obvious low compared with the gel polymerisation lithium ion battery separator prepared by embodiment 3, degree of crystallinity mainly due to pure Kynoar is higher, cause the adhesiveness between itself and base material poor, and its swelling ratio in the electrolytic solution can be made lower, ionic conductivity is reduced, affects the performance of final gel polymer lithium ion battery.
The above; be only the embodiment of the best of the present invention, but protection scope of the present invention is not limited thereto, is anyly familiar with within the scope of core technology that those skilled in the art disclose in the present invention; the equivalent variations done or replacement, all should be encompassed within protection scope of the present invention.
Claims (9)
1. a gelatin polymer modification lithium-ion battery barrier film, comprise polymer microporous layer and at least one deck be coated in the gel polymer coating on polymer microporous layer, it is characterized in that, the peel strength between described gel polymer coating and described polymer microporous layer under 180 ° of DEG C of conditions is more than 1.0N/cm; Described gel polymer coating surface and inside are in mesh structural porous syndeton; The porosity of described gel polymer coating is 40% ~ 80%;
Described gelatin polymer is the copolymer of vinylidene and hexafluoropropylene, and wherein, the mass percent that hexafluoropropylene accounts for gelatin polymer is 5% ~ 20%;
Described gelatin polymer is in the mixed solvent be made up of ethylene carbonate, dimethyl carbonate, diethyl carbonate, swelling ratio when 40 DEG C is lower than 40%, swelling ratio when 80 DEG C lower than 400%, ethylene carbonate in described mixed solvent: dimethyl carbonate: the volume ratio of diethyl carbonate is 2:2:1.
2. gelatin polymer modification lithium-ion battery barrier film according to claim 1, is characterized in that: described polymer microporous layer is the microporous membrane that one or more the composition resins in polyethylene, polypropylene, polybutene or polyvinyl chloride are formed.
3. gelatin polymer modification lithium-ion battery barrier film according to claim 2, it is characterized in that: described polymer microporous layer is the microporous membrane of one or more resins formation in polycyclic alkene, polyether sulfone, PETG, polyamide, polyimides, polyimide amide or polytetrafluoroethylene or the microporous membrane of described resin fibre braiding, or the nonwoven fabrics microporous membrane that described resin fibre is formed.
4. the gelatin polymer modification lithium-ion battery barrier film according to Claims 2 or 3, is characterized in that: described polymer microporous layer is single layer structure, double-decker, three-decker or sandwich construction.
5. gelatin polymer modification lithium-ion battery barrier film according to claim 4, is characterized in that, thickness≤20 μm of described polymer microporous layer.
6. gelatin polymer modification lithium-ion battery barrier film according to claim 5, is characterized in that, the number-average molecular weight of described gelatin polymer is 100000 ~ 1500000.
7. prepare a method for gelatin polymer modification lithium-ion battery barrier film as described in claim 1-6, it is characterized in that, preparation is carried out as follows:
(1) be dissolved in solvent I by gelatin polymer, be uniformly mixed, obtain coating fluid, wherein, the mass percent that described gelatin polymer accounts for coating fluid is 1% ~ 20%, and the flash-point of solvent I is more than 50 DEG C;
(2) by the surface of described coating solution at polymer microporous layer, obtain the film A containing gel polymer coating, wherein, coating weight is 10g/m
2~ 100g/m
2;
(3) described film A is immersed in solvent II, stop 5s ~ 35s, obtain the film B of the gel polymer coating containing microcellular structure;
(4) described film B is immersed in the water, stops 5s ~ 35s, after removing the organic solvent in film surface and micropore, dry at 20 DEG C ~ 80 DEG C, obtain described gelatin polymer modification lithium-ion battery barrier film;
Described solvent I is selected from one or more in DMF, DMA, 1-METHYLPYRROLIDONE
Solvent II is water and the mixed solvent being selected from one or more compositions in DMF, DMA, 1-METHYLPYRROLIDONE, ethylene glycol, dimethyl sulfoxide (DMSO), absolute ethyl alcohol.
8. a lithium ion battery, is characterized in that, comprises gelatin polymer modification lithium-ion battery barrier film, positive pole, negative pole and electrolyte as described in claim 1 ~ 6.
9. a lithium ion battery, is characterized in that, comprises the gelatin polymer modification lithium-ion battery barrier film prepared according to method described in claim 7.
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| CN107785521A (en) * | 2016-08-29 | 2018-03-09 | 比亚迪股份有限公司 | A kind of battery diaphragm and lithium ion battery and preparation method thereof |
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| CN110336081A (en) * | 2019-06-27 | 2019-10-15 | 武汉工程大学 | Gel electrolyte of zinc ion battery and preparation method and application thereof |
| CN110336081B (en) * | 2019-06-27 | 2021-08-24 | 武汉工程大学 | Gel electrolyte of zinc ion battery and preparation method and application thereof |
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