CN105140450A - Lithium ion battery composite separator, preparation method thereof, and lithium ion battery - Google Patents
Lithium ion battery composite separator, preparation method thereof, and lithium ion battery Download PDFInfo
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- CN105140450A CN105140450A CN201510593139.6A CN201510593139A CN105140450A CN 105140450 A CN105140450 A CN 105140450A CN 201510593139 A CN201510593139 A CN 201510593139A CN 105140450 A CN105140450 A CN 105140450A
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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
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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
- H01M10/058—Construction or manufacture
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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
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention relates to a lithium ion battery composite separator, a preparation method thereof, and a lithium ion battery, and belongs to the technical field of lithium ion batteries. The lithium ion battery composite separator comprises a base film; one side of the base film is coated with a hot-melting polymer coating; the other side of the base film is coated with a heat-proof coating; the melting temperature of the hot-melting polymer coating is lower than the hot-melting temperature of the base film; the melting temperature of the heat-proof coating is higher than the hot-melting temperature of the base film; the hot-melting polymer coating comprises the following ingredients by weight: 50 to 98 parts of one or more hot-melt polymer materials, and 2 to 50 parts of one or more agglomerants; the heat-proof coating comprises the following ingredients by weight: 50 to 92 parts of one or more heat-proof polymer materials, and 3 to 20 parts of one or more agglomerants. The lithium ion battery composite separator is favorable in liquid sucking and retention properties, low in heat blocking hole temperature, and high in separator breaking temperature, thereby being capable of obviously improving the safety and the electrochemical property of the battery.
Description
Technical field
The present invention relates to a kind of lithium ion battery composite separation membrane and preparation method thereof, lithium ion battery, belong to technical field of lithium ion.
Background technology
Along with the continuous expansion of lithium ion battery applications scope, the safety issue that lithium ion self exists more and more is subject to people and payes attention to.And the development of ev industry, more harsh requirement be also been proposed to the security performance of lithium ion battery.Causing a lot of because have of the safety issue of lithium ion battery, all may bring out lithium ion battery as overcharge, inside and outside short circuit, extruding, collision etc. and producing safety issue.And these factors are inherently closely related with the thermal runaway of lithium ion battery, namely when lithium ion battery in use causes internal temperature rise larger because of a variety of causes, the side reaction of inside battery is just easily induced, as rise when internal temperature of battery more than 120 DEG C time, carbon anode surface passivating film will decompose, the embedding Li-C Electrode of exposed high activity in the electrolytic solution reacts with organic solvent generation very exothermic thereupon, temperature is caused to rise further, and progressively cause electrolytic salt and the decomposition of cathode material and the very exothermic reaction etc. between embedding Li-C Electrode and adhesive, thus cause battery thermal runaway, there is burnup or blast.Because now widely used electrolyte solvent system is low-flash organic carbonate class, the aggravation of burning also can be caused.
In order to improve the fail safe of lithium ion battery, just needing to stop the temperature of inside battery sharply to rise, avoiding the appearance of thermal runaway.At the surface-coated inorganic material coating of traditional lithium-ion polyolefin membrane, polyalkene diaphragm shrinkage degree at high temperature can be reduced, thus when avoiding internal temperature of battery to raise, the both positive and negative polarity short circuit that polyolefin shrink causes, thus the fail safe improving battery.But the closed pore temperature of this composite diaphragm is higher, when the temperature that battery causes due to external short circuit raises, the micropore of barrier film is closed not in time, and ion transfer channels is still unimpeded, and short circuit current still can pass through, and then causes heat to assemble rapidly.
Publication number is the Chinese invention patent (publication date is on November 19th, 2014) of CN104157811A, disclose a kind of lithium ion battery composite separation membrane, take microporous polyolefin film as basement membrane, at the side of microporous polyolefin film coating hot melt polymeric coating layer, this hot melt polymeric coating layer is organic high polymer microsphere coating, at another side coating inorganic ceramic coating.This invention does not change the hot melting temperature of microporous polyolefin film self, but after the compound of organic high polymer microsphere coating, reduces the hot closed pore temperature of composite diaphragm.When battery temperature reaches the initial temperature that side reaction may occur, organic high polymer microsphere base coating generation melting, the macromolecule of melting enters the micropore of microporous polyolefin film, blocking duct, cut off ion transfer channels, prevent the continuation of battery side reaction from occurring, serve the effect reducing composite diaphragm closed pore temperature.
Also there is some problems in above-mentioned composite diaphragm, is mainly manifested in the poor aspect of wettability of ceramic coating and lithium-ion battery electrolytes, reduces the imbibition of composite diaphragm, liquid-keeping property, be unfavorable for the large multiplying power discharging of lithium ion battery.And the density of ceramic material is comparatively large, improves the weight of battery to a certain extent, reduces the mass energy density of lithium ion battery.Multiplying power discharging property and mass energy density are two very important indexs for power battery of electric motor car, and the reduction of this two indices will have a strong impact on the application of lithium ion battery in power battery of electric motor car field.
In addition, this ceramic material, when closing slurry, is difficult to be uniformly dispersed in the slurry, has had a strong impact on the uniformity consistency of the coating on composite diaphragm.And above-mentioned ceramic material, when applying on barrier film, easily causes the damage to equipment, adds production cost.
Summary of the invention
The object of the present invention is to provide a kind of lithium-ion electric composite diaphragm, to solve lithium ion battery composite separation membrane of the prior art and the poor problem of electrolyte wettability.
In order to realize above object, the technical scheme of lithium ion battery composite separation membrane of the present invention is as follows:
A kind of lithium ion battery composite separation membrane, comprise basement membrane, described basement membrane side is coated with hot melt polymeric coating layer, opposite side is coated with refractory coating, the fusion temperature of described hot melt polymeric coating layer is lower than the hot melting temperature of described basement membrane, and the fusion temperature of described refractory coating is higher than the hot melting temperature of described basement membrane; Described hot melt polymeric coating layer comprises the component of following parts by weight: hot melt macromolecular material 50-98 part, binding agent 2-50 part; Described refractory coating comprises the component of following parts by weight: heat-proof macromolecule material 50-92 part, binding agent 3-20 part.
Lithium ion battery composite separation membrane of the present invention is at basement membrane side coating hot melt polymeric coating layer, when battery temperature increases above the hot melting temperature of hot melt macromolecular material, hot melt macromolecular material is melting or swelling at short notice, the micropore of rapid blocking basement membrane, realize the Thermal shutdown of barrier film, cut off lithium ion transport passage, prevent internal short-circuit of battery, achieve the heat of hot melt polymeric coating layer to battery and clamp down on effect.The refractory coating being coated in basement membrane opposite side forms primarily of heat-resisting high-molecular organic material, there is excellent resistance to elevated temperatures, effectively can stop the contraction of microporous polyolefin film, avoid anode pole piece and contact the short circuit caused with cathode pole piece, achieve the high temperature protection function of refractory coating to battery, in addition, compared with inorganic refractory materials, its advantage mainly contains: (1) heat-resisting high-molecular organic material and lithium-ion battery electrolytes have good wettability, improve the water retainability of composite diaphragm, be conducive to the cycle performance improving lithium ion battery; (2) heat-resisting high-molecular organic material is compared with inorganic refractory materials, and inorganic refractory materials can be avoided the degree of injury of plant equipment, reduces production cost, can also ensure the uniformity that coating applies and consistency; (3) heat-resisting high-molecular organic material is compared with inorganic refractory materials, can alleviate the weight of composite diaphragm, is conducive to the mass energy density improving lithium ion battery; (4) pliability and the elasticity of composite diaphragm is substantially increased.
In order to keep composite diaphragm, there is higher intensity, described refractory coating can also comprise the inorganic filler of certain content, the too high performance that can affect heat-resisting organic polymer performance of the inorganic filler content of this part, general, inorganic filler parts by weight in refractory coating are 5-47 part, more preferably 3-10 part.
The impact of binding agent on hot melt polymeric coating layer and refractory coating conductivity is reduced in order to improve, the amount of binding agent controls usually in more among a small circle, general described hot melt polymeric coating layer comprises the component of following parts by weight: hot melt macromolecular material 90-93 part, binding agent 7-10 part; Described refractory coating comprises the component of following parts by weight: heat-proof macromolecule material 85-95 part, binding agent 5-7 part.
The selection of hot melt macromolecular material mainly considers to have appropriate thermal melting temperatur and have the material of better compatibility with electrolyte, one or more in general selection polystyrene, polyvinyl chloride, polyacrylate and copolymer, vinylacetate and copolymer thereof, polyethylene, polypropylene and copolymer thereof, are specially one or more in polystyrene, polyvinyl chloride, polyacrylate, vinylacetate, polyethylene, polypropylene, acrylate copolymer, vinyl acetate co-polymer, polypropylene copolymer.
The hot melting temperature of hot melt macromolecular material will lower than the hot melting temperature of conventional lithium ion battery microporous polyolefin film, to ensure its blockage of the micro orifice before microporous polyolefin film melting, the hot melting temperature of hot melt macromolecular material again can not be too low, to avoid its fusing when battery is dry, general, the fusion temperature of hot melt macromolecular material is 90 ~ 140 DEG C, more preferably 100 ~ 120 DEG C.
The too thick resistance that can increase composite diaphragm of thickness of hot melt polymeric coating layer, reduce the conductance of composite diaphragm, its thickness is too little, can cause being used for melting plug-hole macromolecular material very little, plug-hole effect is poor, general, the thickness of described hot melt polymeric coating layer is 2-6 μm, more preferably 3-4 μm.
The particle diameter of hot melt macromolecular material is crossed conference and is caused its particle slower at elevated temperature melts, blocking microporous efficiency can be reduced, cause micropore can not quick and complete blocking and internal short-circuit still occurs, cause cell safety problem, general, the particle diameter of hot melt macromolecular material is 0.01-2.0 μm, more preferably 0.7-1.5 μm.
Heat-proof macromolecule material usually select heat resisting temperature high, with the good material of compatibility of electrolyte, as being one or more in polyimides and derivative, aromatic nylon and modifier thereof, phenolic resins, polytetrafluoroethylene.
The fusion temperature of the heat-proof macromolecule material in refractory coating is high as much as possible, and during to ensure that internal temperature of battery is elevated to suddenly higher temperature, barrier film also can not shrink, and general, the fusion temperature of heat-proof macromolecule material is greater than 300 DEG C.
Inorganic filler is the heat resisting ceramic materials that this area is commonly used, and is generally Al
2o
3, TiO
2, SiO
2, MgO, ZnO, ZrO
2, SnO
2in one or more.
The too thick resistance of composite diaphragm that also can cause of the thickness of refractory coating increases, and its thickness is too little, can not prevent diaphragm retracts fully, general, and refractory coating thickness is 2-6 μm, more preferably 3-4 μm.
The particle diameter of heat-proof macromolecule material and inorganic filler is crossed conference and is caused the coating uniformity coefficient of heat-proof macromolecule coating to reduce, particle diameter is too small easily reunites again, causes dispersion difficulty to increase, general, the particle diameter of heat-proof macromolecule material is 0.01-2.0 μm, more preferably 0.8-1.2 μm.The particle diameter of described inorganic filler is 0.01-2.0 μm, more preferably 0.9-1.2 μm.
The thickness of described lithium ion battery composite separation membrane is 12-72 μm; Wherein, the thickness of microporous polyolefin film microporous barrier is 8-60 μm, and the thickness of refractory coating is 2-6 μm, and the thickness of hot melt polymeric coating layer is 2-6 μm.Wherein microporous polyolefin film can be microporous polypropylene membrane or polyethene microporous membrane, also can be the multilayer complex films of the two.
Described binding agent is the conventional binding agent in this area, as described in binding agent be one or more in Kynoar and copolymer, acrylate and copolymer thereof, acrylic acid and copolymer thereof, polyvinyl alcohol, carboxymethyl cellulose, polyurethane.In order to ensure that hot melt polymeric coating layer is in suitable temperature melting, the binding agent in hot melt polymeric coating layer preferably has the fusing point close with hot melt macromolecular material or the binding agent of softening point, as being the one in LA132, PVA.In order to ensure that refractory coating is in suitable temperature melting, the binding agent in refractory coating preferably has the binding agent of higher melt, as PVDF.
The technical scheme of the preparation method of lithium ion battery composite separation membrane of the present invention is as follows:
A preparation method for above-mentioned lithium ion battery composite separation membrane, comprises the steps:
1) slurry preparation
By heat-proof macromolecule material, binding agent and the first solvent Homogeneous phase mixing, obtain heat-proof macromolecule slurry;
By hot melt macromolecular material, binding agent and the second solvent Homogeneous phase mixing, obtain hot melt high molecule size;
2) apply
By step 1) in obtained heat-proof macromolecule slurry and hot melt high molecule size be coated in respectively on two sides of basement membrane, be drying to obtain.
Described step 2) in coating method be one in the modes such as rotogravure application, electrostatic spraying, high-voltage electrostatic spinning coating, anti-phase pore-creating film forming.
For ensureing that heat-proof macromolecule material and hot melt macromolecular material disperse better, described step 1) in the first solvent and the second solvent independently be selected from NMAC, deionized water any one.
In order to ensure the drying effect of refractory coating, described step 2) in after coating heat-proof macromolecule slurry, carry out solvent vapo(u)r process with steam.Containing 2-3% activating agent in described steam.
The technical scheme of lithium ion battery of the present invention is as follows:
A kind of lithium ion battery, uses above-mentioned lithium ion battery composite separation membrane.
Lithium ion battery composite separation membrane in the present invention has good imbibition and protects fluidity, and low hot closed pore temperature, high broken film temperature, can significantly improve fail safe and the chemical property of battery.In composite diaphragm, the fusing point of hot melt polymeric coating layer or softening point are 90 ~ 140 DEG C, when battery temperature raises, can block rapidly the aperture of microporous polyolefin film, complete the Thermal shutdown effect of barrier film; In high temperature resistant base coating, high-temperature resistant material has excellent resistance to elevated temperatures simultaneously, realizes the high temperature protection function of high temperature resistant base functional layer to battery.
The present invention all has space in the coating on composite diaphragm two sides, can significantly improve the porosity of composite diaphragm, makes up microporous polyolefin film and the low defect of pole piece porosity, improves the liquid-keeping property of composite diaphragm, thus increase the cycle performance of lithium ion battery.
Embodiment
Below in conjunction with specific embodiment, technical scheme of the present invention is further detailed.
Embodiment 1
The lithium ion battery composite separation membrane of the present embodiment comprises basement membrane, this basement membrane is polyethene microporous membrane, a side of this polyethene microporous membrane is coated with hot melt polymeric coating layer, another side is coated with refractory coating, the fusion temperature of described hot melt polymeric coating layer is lower than the hot melting temperature of described basement membrane, and the fusion temperature of described refractory coating is higher than the hot melting temperature of described basement membrane; Hot melt polymeric coating layer comprises hot melt macromolecular material styrene divinyl copolymer (PS base co-polymer) 90 parts, binding agent PVA10 part, and the particle diameter of styrene divinyl copolymer is 0.7 μm; Refractory coating comprises heat-proof macromolecule material polyimides 95 parts, binding agent PVDF5 part, and the particle diameter of polyimides is 1.1 μm; The thickness of above-mentioned composite diaphragm is 28 μm, and wherein the thickness of polyethene microporous membrane is 20 μm, and the porosity of polyethene microporous membrane is 40%, and the thickness of hot melt polymeric coating layer is 4 μm, and the thickness of refractory coating is 4 μm.
The preparation method of the lithium ion battery composite separation membrane of the present embodiment comprises the steps:
1) slurry preparation
Added by the polyimides of 95 parts in solvent NMAC (N methylacetamide), mix to obtain solution, then add the binding agent PVDF of 5 parts, high speed dispersor stirs 1h, obtains heat-proof macromolecule slurry; The solid content of this heat-proof macromolecule slurry is 20%;
Add in deionized water by the styrene divinyl copolymer of 90 parts (PS base co-polymer) microballoon, high speed dispersor stirs 1h, then adds the binding agent PVA of 10 parts, and continue to stir 1h, obtained solid content is the hot melt high molecule size of 25%;
2) apply
By step 1) in obtained heat-proof macromolecule slurry use continuous gravure coating process to be coated in the side of polyethene microporous membrane, then solvent vapo(u)r process is carried out with steam, dry at 75 DEG C again, afterwards by step 1) obtained hot melt high molecule size uses continuous gravure coating process to be coated in the opposite side of polyethene microporous membrane, dry at 60 DEG C, to obtain final product.
The barrier film of the lithium ion battery of the present embodiment uses above-mentioned lithium ion battery composite separation membrane.
The preparation method of the lithium ion battery of the present embodiment comprises the steps:
1) positive pole preparation:
The positive active material LiNi of 94 weight portions is added in solvent NMP
1/3co
1/3mn
1/3o
2, the conductive agent carbon black of 3 weight portions and the binding agent PVDF of 3 weight portions, mix obtained anode sizing agent, anode sizing agent being evenly coated in thickness is on the plus plate current-collecting body aluminium foil of 20 μm, and dry, roll-in, obtains positive pole;
2) negative pole preparation:
The negative electrode active material graphite powder of 95 weight portions is added in solvent deionized water, the binding agent SBR of the conductive agent carbon black of 1 weight portion, the thickener CMC of 1.5 weight portions and 2.5 weight portions, mix and obtain cathode size, cathode size being evenly coated in thickness is on the negative current collector Copper Foil of 10 μm, dry, roll-in, obtains negative pole;
3) battery core preparation:
Above-mentioned positive pole, negative pole and composite diaphragm lamination are made battery core;
4) lithium ion battery preparation:
To obtain battery core loads in flexible-packed battery housing, and inject electrolyte, described electrolyte is with lithium hexafluoro phosphate LiPF
6for electrolytic salt, with the mixed solvent of dimethyl carbonate DMC, ethylene carbonate EC, methyl ethyl carbonate EMC for solvent, wherein the volume ratio of DMC, EC, EMC is 1:1:1, and in electrolyte, the concentration of lithium hexafluoro phosphate is 1mol/L, sealing, the soft bag lithium ionic cell of obtained 50Ah.
Embodiment 2
The lithium ion battery composite separation membrane of the present embodiment comprises basement membrane, this basement membrane is microporous polypropylene membrane, a side of this microporous polypropylene membrane is coated with hot melt polymeric coating layer, another side is coated with refractory coating, the fusion temperature of described hot melt polymeric coating layer is lower than the hot melting temperature of described basement membrane, and the fusion temperature of described refractory coating is higher than the hot melting temperature of described basement membrane; Hot melt polymeric coating layer comprises hot melt macromolecular material AN-AE 93 parts, binding agent LA132 (polyacrylic acid analog copolymer) 7 parts, and the particle diameter of AN-AE is 1.2 μm; Refractory coating comprises heat-proof macromolecule material polyimides 85 parts, binding agent PVDF5 part, inorganic filler Al
2o
310 parts, the particle diameter of polyimides is 2.0 μm, inorganic filler Al
2o
3particle diameter be 0.9 μm; The thickness of above-mentioned composite diaphragm is 28 μm, and wherein the thickness of microporous polypropylene membrane is 20 μm, and the porosity of microporous polypropylene membrane is 40%, and the thickness of hot melt polymeric coating layer is 4 μm, and the thickness of refractory coating is 4 μm.
The preparation method of the lithium ion battery composite separation membrane of the present embodiment comprises the steps:
1) slurry preparation
The polyimides of 85 parts is added in solvent NMAC, mixes to obtain solution, then add the Al of binding agent PVDF and 10 part of 5 parts
2o
3, high speed dispersor stirs 1h, obtains the heat-proof macromolecule slurry that solid content is 20%;
Add in deionized water by the AN-AE microballoon of 93 parts, high speed dispersor stirs 1h, then adds the binding agent LA132 of 7 parts, and continue to stir 1h, obtained solid content is the hot melt high molecule size of 15%;
2) apply
By step 1) in obtained heat-proof macromolecule slurry use continuous gravure coating process to be coated in the side of microporous polypropylene membrane, then solvent vapo(u)r process is carried out with steam, dry at 85 DEG C again, afterwards by step 1) obtained hot melt high molecule size uses continuous gravure coating process to be coated in the opposite side of polyethene microporous membrane, dry at 60 DEG C, to obtain final product.
The barrier film of the lithium ion battery of the present embodiment uses above-mentioned lithium ion battery composite separation membrane.
The preparation method of the lithium ion battery of the present embodiment is with embodiment 1.
Embodiment 3
The lithium ion battery composite separation membrane of the present embodiment comprises basement membrane, this basement membrane is microporous polypropylene membrane, a side of this microporous polypropylene membrane is coated with hot melt polymeric coating layer, another side is coated with refractory coating, the fusion temperature of described hot melt polymeric coating layer is lower than the hot melting temperature of described basement membrane, and the fusion temperature of described refractory coating is higher than the hot melting temperature of described basement membrane; Hot melt polymeric coating layer comprises hot melt macromolecular material ethylene-vinyl acetate copolymer (EVA, wherein VA content is 9%) 90 parts, binding agent LA132 (polyacrylic acid analog copolymer) 10 parts, the particle diameter of ethylene-vinyl acetate copolymer is 0.7 μm; Refractory coating comprises heat-proof macromolecule material polytetrafluoroethylene 90 parts, binding agent PVDF7 part, inorganic filler SiO
23 parts, the particle diameter of polytetrafluoroethylene is 1 μm, inorganic filler SiO
2particle diameter be 1.2 μm; The thickness of above-mentioned composite diaphragm is 38 μm, and wherein the thickness of microporous polypropylene membrane is 32 μm, and the porosity of microporous polypropylene membrane is 40%, and the thickness of hot melt polymeric coating layer is 3 μm, and the thickness of refractory coating is 3 μm.
The preparation method of the lithium ion battery composite separation membrane of the present embodiment comprises the steps:
1) slurry preparation
By the SiO of the polytetrafluoroethylene of 90 parts and 3 parts
2particle adds in solvent deionized water, and high speed dispersor stirs 1h, then adds the binding agent PVDF of 7 parts, and high speed dispersor stirs 1h, obtains the heat-proof macromolecule slurry that solid content is 30%;
Add in deionized water by the ethylene-vinyl acetate copolymer microballoon of 90 parts, high speed dispersor stirs 1h, then adds the binding agent LA132 of 10 parts, and continue to stir 1h, obtained solid content is the hot melt high molecule size of 15%;
2) apply
By step 1) in obtained heat-proof macromolecule slurry use continuous gravure coating process to be coated in the side of microporous polypropylene membrane, dry at 85 DEG C, afterwards by step 1) obtained hot melt high molecule size uses continuous gravure coating process to be coated in the opposite side of polyethene microporous membrane, dry at 60 DEG C, to obtain final product.
The barrier film of the lithium ion battery of the present embodiment uses above-mentioned lithium ion battery composite separation membrane.
The preparation method of the lithium ion battery of the present embodiment is with embodiment 1.
Embodiment 4
The lithium ion battery composite separation membrane of the present embodiment comprises basement membrane, this basement membrane is polypropylene-polyethylene-polypropylene three layers of microporous barrier, a side of these three layers of microporous barriers is coated with hot melt polymeric coating layer, another side is coated with refractory coating, the fusion temperature of described hot melt polymeric coating layer is lower than the hot melting temperature of described basement membrane, and the fusion temperature of described refractory coating is higher than the hot melting temperature of described basement membrane; Hot melt polymeric coating layer comprises hot melt macromolecular material polystyrene 60 parts, binding agent LA13240 part, and the particle diameter of polystyrene is 1.5 μm; Refractory coating comprises 60 parts, heat-proof macromolecule material phenolic resins, binding agent PVDF5 part, inorganic filler TiO
235 parts, the particle diameter of phenolic resins is 1.5 μm, inorganic filler TiO
2particle diameter be 1.5 μm; The thickness of above-mentioned composite diaphragm is 42 μm, and wherein the thickness of double-deck microporous barrier is 32 μm, and the porosity of double-deck microporous barrier is 40%, and the thickness of hot melt polymeric coating layer is 5 μm, and the thickness of refractory coating is 5 μm.
The preparation method of the lithium ion battery composite separation membrane of the present embodiment comprises the steps:
1) slurry preparation
By the TiO of the phenolic resins of 60 parts and 35 parts
2particle adds in solvent deionized water, and high speed dispersor stirs 1h, then adds the binding agent PVDF of 5 parts, and high speed dispersor stirs 1h, obtains the heat-proof macromolecule slurry that solid content is 30%;
Add in deionized water by the polystyrene microsphere of 60 parts, high speed dispersor stirs 1h, then adds the binding agent LA132 of 40 parts, and continue to stir 1h, obtained solid content is the hot melt high molecule size of 25%;
2) apply
By step 1) in obtained heat-proof macromolecule slurry use continuous gravure coating process to be coated in the side of microporous polypropylene membrane, dry at 80 DEG C, afterwards by step 1) obtained hot melt high molecule size uses continuous gravure coating process to be coated in the opposite side of polyolefin three-layer microporous barrier, dry at 70 DEG C, to obtain final product.
The barrier film of the lithium ion battery of the present embodiment uses above-mentioned lithium ion battery composite separation membrane.
The preparation method of the lithium ion battery of the present embodiment is with embodiment 1.
Embodiment 5
The lithium ion battery composite separation membrane of the present embodiment comprises basement membrane, this basement membrane is microporous polypropylene membrane, a side of this microporous polypropylene membrane is coated with hot melt polymeric coating layer, another side is coated with refractory coating, the fusion temperature of described hot melt polymeric coating layer is lower than the hot melting temperature of described basement membrane, and the fusion temperature of described refractory coating is higher than the hot melting temperature of described basement membrane; Hot melt polymeric coating layer comprises hot melt macromolecular material polypropylene 80 parts, binding agent LA13220 part, and polyacrylic particle diameter is 0.1 μm; Refractory coating comprises heat-proof macromolecule material aramid fiber MXD6 nylon 70 parts, binding agent PVDF15 part, inorganic filler ZrO
2(zirconia) 15 parts, the particle diameter of MXD6 nylon is 1.5 μm, inorganic filler ZrO
2particle diameter be 0.1 μm; The thickness of above-mentioned composite diaphragm is 42 μm, and wherein the thickness of microporous polypropylene membrane is 36 μm, and the porosity of microporous polypropylene membrane is 40%, and the thickness of hot melt polymeric coating layer is 3 μm, and the thickness of refractory coating is 3 μm.
The preparation method of the lithium ion battery composite separation membrane of the present embodiment comprises the steps:
1) slurry preparation
By the MXD6 nylon of 70 parts and the ZrO of 15 parts
2particle adds in solvent deionized water, and high speed dispersor stirs 1h, then adds the binding agent PVDF of 15 parts, and high speed dispersor stirs 1h, obtains the heat-proof macromolecule slurry that solid content is 25%;
Add in deionized water by the polypropylene microballoon of 80 parts, high speed dispersor stirs 1h, then adds the binding agent LA132 of 20 parts, and continue to stir 1h, obtained solid content is the hot melt high molecule size of 20%;
2) apply
By step 1) in obtained heat-proof macromolecule slurry use continuous gravure coating process to be coated in the side of microporous polypropylene membrane, dry at 80 DEG C, afterwards by step 1) obtained hot melt high molecule size uses continuous gravure coating process to be coated in the opposite side of polyethene microporous membrane, dry at 75 DEG C, to obtain final product.
The barrier film of the lithium ion battery of the present embodiment uses above-mentioned lithium ion battery composite separation membrane.
The preparation method of the lithium ion battery of the present embodiment is with embodiment 1.
Test example
(1) permeability of composite diaphragm under different temperatures
The permeability of composite diaphragm under table 1 different temperatures
Lithium ion battery composite separation membrane prepared by Example 1 ~ 5, is placed in the vacuum drying oven 30min that temperature is 80 DEG C, 120 DEG C, 125 DEG C, 140 DEG C, and the ventilative value of composite diaphragm under mensuration different temperatures, the results detailed in Table 1.
As can be seen from Table 1, lithium ion battery composite separation membrane plug-hole completely at 125 DEG C of preparing of embodiment 1 ~ 5.Illustrate that heat-fusible materials infiltrates basement membrane micropore at 120 ~ 125 DEG C of temperature range fast melt, cause barrier film duct to block, reach closed pore effect.And common microporous polyolefin film still has gas permeability after 140 DEG C of process, show that just barrier film base material softens, pore size influences is little.It can thus be appreciated that hot melt functional layer reduces the closed pore temperature of barrier film, be conducive to the raising of battery security.
(2) heat-shrinkable of composite diaphragm under different temperatures
Lithium ion battery composite separation membrane prepared by Example 1 ~ 5, is placed in the baking oven 2h that temperature is 80 DEG C, 100 DEG C, 120 DEG C, 140 DEG C, 160 DEG C, and the percent thermal shrinkage of composite diaphragm under mensuration different temperatures, the results detailed in following table 2.
As can be seen from Table 2, the lithium ion battery composite separation membrane heat-shrinkable at each temperature that prepared by embodiment 1 ~ 5 is all obviously better than common microporous polyolefin film.When the temperature increases, because the thermal endurance of refractory coating is comparatively strong, composite diaphragm shrinkage phenomenon is less; When temperature reaches 160 DEG C, the percent thermal shrinkage of composite diaphragm is still less than 2.0%, and common microporous polyolefin film melts completely.
The heat-shrinkable of composite diaphragm under table 2 different temperatures
(3) cycle performance of the lithium ion battery of different barrier film is applied
Lithium ion battery prepared by Example 1 ~ 5 and the lithium ion battery adopting common polyolefin film to prepare, the capability retention of the different cycle period of test lithium ion battery, the results detailed in Table 3.
As can be seen from Table 3, the life-span that embodiment 1 ~ 5 prepares lithium ion battery, in circulation after 500 weeks, capability retention reached more than 90%, and the capability retention of common PP film, PE film lithium ion battery only 80.1%, 82.9%.Illustrate that the wettability of lithium ion battery composite separation membrane prepared by embodiment 1 ~ 5 and electrolyte is better, thus make battery have superior cycle performance.
The cycle performance of the lithium ion battery of different barrier film applied by table 3
(4) security performance of the lithium ion battery of different barrier film is applied
Lithium ion battery prepared by Example 1 ~ 5 and adopt the lithium ion battery of common polyolefin micropore film preparation, measures its security performance, respectively the results detailed in Table 4.
The security performance of the lithium ion battery of different barrier film applied by table 4
As can be seen from Table 4, the lithium ion battery that prepared by embodiment 1 ~ 5 has superior security performance.
Claims (10)
1. a lithium ion battery composite separation membrane, it is characterized in that, comprise basement membrane, described basement membrane side is coated with hot melt polymeric coating layer, opposite side is coated with refractory coating, the fusion temperature of described hot melt polymeric coating layer is lower than the hot melting temperature of described basement membrane, and the fusion temperature of described refractory coating is higher than the hot melting temperature of described basement membrane; Described hot melt polymeric coating layer comprises the component of following parts by weight: hot melt macromolecular material 50-98 part, binding agent 2-50 part; Described refractory coating comprises the component of following parts by weight: heat-proof macromolecule material 50-92 part, binding agent 3-20 part.
2. lithium ion battery composite separation membrane as claimed in claim 1, it is characterized in that, described refractory coating also comprises inorganic filler 5-47 part.
3. lithium ion battery composite separation membrane as claimed in claim 1, it is characterized in that, described hot melt macromolecular material is one or more in polystyrene, polyvinyl chloride, polyacrylate, vinylacetate, polyethylene, polypropylene, acrylate copolymer, vinyl acetate co-polymer, polypropylene copolymer.
4. lithium ion battery composite separation membrane as claimed in claim 1, is characterized in that, described heat-proof macromolecule material is one or more in polyimides and derivative, aromatic nylon and modifier thereof, phenolic resins, polytetrafluoroethylene.
5. lithium ion battery composite separation membrane as claimed in claim 3, it is characterized in that, the fusion temperature of described hot melt macromolecular material is 90 ~ 140 DEG C.
6. lithium ion battery composite separation membrane as claimed in claim 4, it is characterized in that, the fusion temperature of described heat-proof macromolecule material is greater than 300 DEG C.
7. lithium ion battery composite separation membrane as claimed in claim 2, it is characterized in that, described inorganic filler is Al
2o
3, TiO
2, SiO
2, MgO, ZnO, ZrO
2, SnO
2in one or more.
8. lithium ion battery composite separation membrane as claimed in claim 1, it is characterized in that, the thickness of described hot melt polymeric coating layer is 2-6 μm, and the thickness of described refractory coating is 2-6 μm.
9. a preparation method for lithium ion battery composite separation membrane as claimed in claim 1, is characterized in that, comprises the steps:
1) slurry preparation
By heat-proof macromolecule material, binding agent and the first solvent Homogeneous phase mixing, obtain heat-proof macromolecule slurry;
By hot melt macromolecular material, binding agent and the second solvent Homogeneous phase mixing, obtain hot melt high molecule size;
2) apply
By step 1) in obtained heat-proof macromolecule slurry and hot melt high molecule size be coated in respectively on two sides of basement membrane, be drying to obtain.
10. a lithium ion battery, is characterized in that, uses composite diaphragm as claimed in claim 1.
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