CN109841785A - A kind of battery diaphragm and preparation method thereof and the lithium ion battery comprising the diaphragm - Google Patents
A kind of battery diaphragm and preparation method thereof and the lithium ion battery comprising the diaphragm Download PDFInfo
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- CN109841785A CN109841785A CN201910258155.8A CN201910258155A CN109841785A CN 109841785 A CN109841785 A CN 109841785A CN 201910258155 A CN201910258155 A CN 201910258155A CN 109841785 A CN109841785 A CN 109841785A
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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
Abstract
The invention belongs to technical field of lithium ion, more particularly to a kind of battery diaphragm, including diaphragm base and it is set to the hot melt polymeric nitride layer on a diaphragm base at least surface, the diaphragm base includes at least one of glass fibre and ceramic fibre and first bonding agents, and the hot melt polymeric nitride layer includes hot-melt polymer and second bonding agents.Compared with the prior art, which has better thermal stability and higher mechanical strength, protects liquid and imbibition ability is stronger.In addition, the present invention also provides a kind of preparation method of battery diaphragm and containing the lithium ion battery of the diaphragm.
Description
Technical field
The invention belongs to technical field of lithium ion more particularly to a kind of battery diaphragm and preparation method thereof and include this
The lithium ion battery of diaphragm.
Background technique
Lithium ion battery is the new electrochmical power source system developed rapidly in recent years, with traditional ni-Cd or nickel-metal hydride battery
It compares, it has many advantages, such as high-energy-density, long circulation life, memory-less effect and quick charge and discharge, is widely used in portable electric
Sub- product, electric car and hybrid electric vehicle etc..
Lithium ion battery is usually mainly by anode, cathode, diaphragm, electrolyte, battery case composition.Lithium ion battery structure
In, diaphragm is crucial one of interior layer assembly.The main function of diaphragm is to separate the positive and negative electrode of battery, is prevented positive and negative
Extremely directly contact and it is short-circuit, while electrolyte ion also to be enable to pass through in battery charge and discharge process, formation electric current,
When battery operating temperature is abnormal raising, the migrating channels of electrolyte ion are closed, cutting electric current guarantees cell safety.By
This directly affects capacity, circulation and the safety of battery as it can be seen that the performance of diaphragm determines the interfacial structure of battery, internal resistance etc.
The characteristics such as performance, the diaphragm haveing excellent performance play an important role the comprehensive performance for improving battery.
Currently, we are generally monolayer polyethylene diaphragm, single-layer polypropylene in commercially use lithium ion battery separator
Diaphragm or polyethylene/polypropylene composite diaphragm, although polyalkene diaphragm has a preferable anti acid alkali performance, higher tensile strength,
The performances such as higher porosity, but polyalkene diaphragm still has following deficiency: 1) fusing point of polyethylene be about 140 DEG C, is gathered
The fusing point of propylene is about 160 DEG C, when battery local temperature is increased to its fusing point or more, it is possible to because the fusing of diaphragm leads to electricity
Pond positive and negative anodes contact and short circuit occur, and the high-temperature thermal stability performance of diaphragm is still to be improved；2) polyalkene diaphragm mechanical strength
It is low, it is easily pierced, causes positive and negative anodes short-circuit, generate safety accident；3) polyalkene diaphragm imbibition and liquid-keeping property are poor.
Summary of the invention
It is an object of the present invention to: in view of the deficiencies of the prior art, and a kind of battery diaphragm is provided, improves diaphragm
Thermal stability and mechanical strength, enhancing diaphragm protect liquid and imbibition ability.
To achieve the goals above, the invention adopts the following technical scheme:
A kind of battery diaphragm including diaphragm base and is set to the hot melt polymeric on a diaphragm base at least surface
Nitride layer, the diaphragm base include at least one of glass fibre and ceramic fibre and first bonding agents, the hot melt
Polymeric layer includes hot-melt polymer and second bonding agents.
As a kind of improvement of battery diaphragm of the present invention, the coating quality of the hot melt polymeric nitride layer accounts for described
The 0.5~1% of diaphragm base layer quality.The very few hot-melt polymer that will cause of the coating quality accounting of hot melt polymeric nitride layer is in electricity
Pond temperature crosses all micropores for being not enough to block after relative superiority or inferiority melts in diaphragm base, can not achieve good closed pore performance.Hot melt
Property polymeric layer coating quality accounting it is also unsuitable excessive, be to belong to inert matter in the battery, when its content is excessive,
The energy quality ratio of battery entirety can be reduced.
As a kind of improvement of battery diaphragm of the present invention, the diaphragm base with a thickness of 9~12 μm, it is described every
The porosity of film base is 40~50%.When the thickness of diaphragm base is too small, mechanical strength is not ideal enough, cannot play very well
Isolation protective effect, and when the thickness of diaphragm base is excessive, and the volume energy density of battery entirety can be reduced.In addition,
The porosity of diaphragm base, which crosses conference, reduces the mechanical strength of diaphragm base, and the porosity of diaphragm base is too small to will affect lithium ion
Conduction and reduce imbibition and the liquid-keeping property of diaphragm.
As a kind of improvement of battery diaphragm of the present invention, the quality of the first bonding agents accounts for the glass fibre
The 5~15% of ceramic fibre quality total amount and/or.The excessive hole that will increase diaphragm base of the quality accounting of first bonding agents
Rate reduces the mechanical strength of diaphragm.
As a kind of improvement of battery diaphragm of the present invention, the diameter of the glass fibre and the ceramic fibre
Diameter is respectively 0.2~0.5 μm.The glass fibre and/or ceramic fibre that diameter is 0.2~0.5 μm have bigger specific surface
Product.
As a kind of improvement of battery diaphragm of the present invention, the hot melt polymeric nitride layer with a thickness of 3~10 μm.
The thickness of hot melt polymeric nitride layer is too small, and heat-insulated closed pore ability cannot be effectively improved, and the thickness of hot melt polymeric nitride layer
It spends greatly, the volume energy density of battery entirety can be reduced.
As a kind of improvement of battery diaphragm of the present invention, the fusing point of the hot-melt polymer is 120~200
℃.Preferably, the hot-melt polymer can be selected from polyethylene wax, polystyrene, polyvinyl chloride, polyacrylate copolymer
With polyethylene-polyvinyl acetate copolymer at least one.Compared to general blowout disk, fusing point is 120~200 DEG C
Hot-melt polymer can carry out hot closing earlier, preferably promote the security performance of battery when battery temperature is excessively high.
As a kind of improvement of battery diaphragm of the present invention, the first bonding agents and the second bonding agents include
Polyacrylic acid, polymethylacrylic acid, polymethyl acrylate, polyethyl acrylate, pure-acrylic emulsion, polyacrylic acid-are styrene copolymerized
Object, butadiene-styrene rubber, epoxy resin, neopentylglycol diacrylate, Sodium Polyacrylate series, gathers inclined fluorine at polyvinylpyrrolidone
At least one of ethylene.
Compared with the prior art, battery diaphragm of the invention at least has the advantages that
1) glass fibre and ceramic fibre are the inorganic non-metallic materials haveing excellent performance, and advantage is good insulating, heat-resisting
Property it is strong, corrosion resistance is good, high mechanical strength, therefore, glass fibre and ceramic fibre are applied to diaphragm and are conducive to improve diaphragm
Mechanical performance and heat resistance.
2) when battery temperature is more than the melting temperature of hot-melt polymer, hot-melt polymer can melt in a short time
Melt, it is blocking microporous rapidly, achieve the purpose that diaphragm closed pore, to realize the high temperature protection function of battery diaphragm.
3) glass fibre and ceramic fibre are formed by diaphragm base with porous structure, have good imbibition ability and
Liquid-keeping property, to be effectively improved imbibition and the liquid-keeping property of diaphragm.
The second object of the present invention is: providing a kind of preparation method of battery diaphragm, comprising the following steps:
S1 mixes at least one of glass fibre and ceramic fibre with first bonding agents according to mass ratio, is added
Deionized water stirs evenly, and forms slurry, and the viscosity of the slurry is 2000~10000mPas, the solid content of the slurry
It is 40~70%；
Diaphragm base is made in S2, the slurry coated and molded that S1 is obtained after dehydration and drying；
Hot-melt polymer is added in solvent by S3, is added the second binder, is stirred evenly, using spraying or
The method of intaglio plate coating is coated in diaphragm base, forms hot melt polymeric nitride layer.
Compared with the prior art, the preparation method of battery diaphragm is easy to operate in the present invention, is suitable for producing in enormous quantities.
The third object of the present invention is: providing a kind of lithium ion battery, including successively by positive plate, diaphragm, negative electrode tab
The naked battery core and its electrolyte of formation are wound after stacking in the same direction, the diaphragm is previously described battery diaphragm.
Compared with the prior art, lithium ion battery of the invention has better mechanical performance and high temperature resistance energy, energy
The on fire or explosion phenomenon occurred by battery short circuit effectively is avoided, to improve the safety of battery.
Specific embodiment
The present invention is described in further detail With reference to embodiment, but embodiments of the present invention are not
It is limited to this.
Embodiment 1
The preparation of positive plate:
By cobalt acid lithium, conductive agent superconduction carbon (Super-P), binder Kynoar (PVDF) 97:1.5 in mass ratio:
1.5 be uniformly mixed the lithium ion battery anode glue size with certain viscosity is made, slurry is coated in current collector aluminum foil, 85
It is cold-pressed after being dried at DEG C；Then carry out trimming, cut-parts, slitting, after slitting under vacuum conditions 110 DEG C dry 4 hours, weldering
Tab is connect, based lithium-ion battery positive plate is made.
The preparation of negative electrode tab:
By graphite and conductive agent superconduction carbon (Super-P), thickener sodium carboxymethylcellulose (CMC), binder butylbenzene rubber
Slurry is made in glue (SBR) 96:2.0:1.0:1.0 in mass ratio, is coated on copper foil of affluxion body and dries at 85 DEG C, is cut
Side, cut-parts, slitting, after slitting under vacuum conditions 110 DEG C dry 4 hours, anode plate for lithium ionic cell is made in soldering polar ear.
The preparation of diaphragm:
1) by diameter be 0.2 μm glass fibre and account for 5% polyacrylic acid of glass fiber quality and mix, addition goes
Ionized water stirs evenly, and forms slurry, and the viscosity of slurry is 2000mPas, and the solid content of slurry is 40%；
2) the slurry coated and molded that will 1) obtain, after dehydration and drying be made diaphragm base, diaphragm base with a thickness of 9
μm, the porosity of diaphragm base is 40%；
3) polyethylene wax is added in nmp solvent, adds polymethylacrylic acid, stirred evenly, using spraying or
The method of intaglio plate coating is coated in diaphragm base, forms hot melt polymeric nitride layer, and the coating quality of hot melt polymeric nitride layer is
The 0.5% of diaphragm base layer quality, hot melt polymeric nitride layer with a thickness of 3 μm.
The preparation of electrolyte: by lithium hexafluoro phosphate (LiPF6) it is dissolved in ethylene carbonate (EC), dimethyl carbonate (DMC)
And (mass ratio of three is 1 to the in the mixed solvent of methyl ethyl carbonate (EMC) composition；2:1), the electricity that concentration is 1mol/L is obtained
Solve liquid.
The preparation of lithium ion battery: being wound into battery core for above-mentioned positive plate, diaphragm and negative electrode tab, diaphragm be located at positive plate and
Between negative electrode tab, and make fluoropolymer coating face face positive plate, makes acrylic polymer coating layer face face negative electrode tab, anode
With aluminium pole ears spot welding extraction, cathode is with nickel tab spot welding extraction；Then battery core is placed in aluminium plastic packaging bag, injects above-mentioned electrolysis
Liquid, the processes such as encapsulated, chemical conversion, capacity, is made lithium ion battery.
Embodiment 2
The preparation of diaphragm unlike the first embodiment:
1) by diameter be 0.3 μm glass fibre and account for glass fiber quality 6% polymethylacrylic acid mix, add
Enter deionized water to stir evenly, form slurry, the viscosity of slurry is 2500mPas, and the solid content of slurry is 45%；
2) the slurry coated and molded that will 1) obtain, after dehydration and drying be made diaphragm base, diaphragm base with a thickness of
10 μm, the porosity of diaphragm base is 42%；
3) polystyrene is added in nmp solvent, adds polymethyl acrylate, stirred evenly, using spraying or
The method of intaglio plate coating is coated in diaphragm base, forms hot melt polymeric nitride layer, and the coating quality of hot melt polymeric nitride layer is
The 0.6% of diaphragm base layer quality, hot melt polymeric nitride layer with a thickness of 4 μm.
Remaining is with embodiment 1, and which is not described herein again.
Embodiment 3
The preparation of diaphragm unlike the first embodiment:
1) by diameter be 0.4 μm glass fibre and account for glass fiber quality 7% polymethyl acrylate mix, add
Enter deionized water to stir evenly, form slurry, the viscosity of slurry is 3000mPas, and the solid content of slurry is 50%；
2) the slurry coated and molded that will 1) obtain, after dehydration and drying be made diaphragm base, diaphragm base with a thickness of
11 μm, the porosity of diaphragm base is 45%；
3) polyvinyl chloride is added in nmp solvent, adds polyethyl acrylate, stirred evenly, using spraying or
The method of intaglio plate coating is coated in diaphragm base, forms hot melt polymeric nitride layer, and the coating quality of hot melt polymeric nitride layer is
The 0.7% of diaphragm base layer quality, hot melt polymeric nitride layer with a thickness of 5 μm.
Remaining is with embodiment 1, and which is not described herein again.
Embodiment 4
The preparation of diaphragm unlike the first embodiment:
1) by diameter be 0.5 μm glass fibre and account for glass fiber quality 8% polyethyl acrylate mix, add
Enter deionized water to stir evenly, form slurry, the viscosity of slurry is 3500mPas, and the solid content of slurry is 50%；
2) the slurry coated and molded that will 1) obtain, after dehydration and drying be made diaphragm base, diaphragm base with a thickness of
12 μm, the porosity of diaphragm base is 50%；
3) polyacrylate copolymer is added in nmp solvent, adds pure-acrylic emulsion, stirred evenly, using spraying
Or the method for intaglio plate coating is coated in diaphragm base, forms hot melt polymeric nitride layer, the painting cloth of hot melt polymeric nitride layer
Amount be diaphragm base layer quality 0.8%, hot melt polymeric nitride layer with a thickness of 6 μm.
Remaining is with embodiment 1, and which is not described herein again.
Embodiment 5
The preparation of diaphragm unlike the first embodiment:
1) by diameter be 0.2 μm ceramic fibre and account for 9% pure-acrylic emulsion of ceramic fibre quality and mix, addition goes
Ionized water stirs evenly, and forms slurry, and the viscosity of slurry is 4000mPas, and the solid content of slurry is 55%；
2) the slurry coated and molded that will 1) obtain, after dehydration and drying be made diaphragm base, diaphragm base with a thickness of 9
μm, the porosity of diaphragm base is 40%；
3) polyethylene-polyvinyl acetate copolymer is added in nmp solvent, it is total adds polyacrylic acid-styrene
Polymers stirs evenly, and is coated in diaphragm base using the method for spraying or intaglio plate coating, forms hot melt polymeric nitride layer,
The coating quality of hot melt polymeric nitride layer be diaphragm base layer quality 0.9%, hot melt polymeric nitride layer with a thickness of 7 μm.
Remaining is with embodiment 1, and which is not described herein again.
Embodiment 6
The preparation of diaphragm unlike the first embodiment:
1) by diameter be 0.3 μm ceramic fibre and account for ceramic fibre quality 10% polyacrylic acid-styrene it is total
Polymers mixing is added deionized water and stirs evenly, and forms slurry, the viscosity of slurry is 4500mPas, and the solid content of slurry is
60%；
2) the slurry coated and molded that will 1) obtain, after dehydration and drying be made diaphragm base, diaphragm base with a thickness of
10 μm, the porosity of diaphragm base is 45%；
3) polyethylene wax is added in nmp solvent, adds polyvinylpyrrolidone, stirred evenly, using spraying or
The method of person's intaglio plate coating is coated in diaphragm base, forms hot melt polymeric nitride layer, the coating quality of hot melt polymeric nitride layer
Be the 1% of diaphragm base layer quality, hot melt polymeric nitride layer with a thickness of 8 μm.
Remaining is with embodiment 1, and which is not described herein again.
Embodiment 7
The preparation of diaphragm unlike the first embodiment:
1) by diameter be 0.4 μm ceramic fibre and account for 12% polyvinylpyrrolidone of ceramic fibre quality and mix
It closes, deionized water is added and stirs evenly, form slurry, the viscosity of slurry is 5000mPas, and the solid content of slurry is 65%；
2) the slurry coated and molded that will 1) obtain, after dehydration and drying be made diaphragm base, diaphragm base with a thickness of
11 μm, the porosity of diaphragm base is 48%；
3) polystyrene is added in nmp solvent, adds butadiene-styrene rubber, stirred evenly, using spraying or intaglio plate
The method of coating is coated in diaphragm base, forms hot melt polymeric nitride layer, and the coating quality of hot melt polymeric nitride layer is diaphragm
The 0.5% of base layer quality, hot melt polymeric nitride layer with a thickness of 9 μm.
Remaining is with embodiment 1, and which is not described herein again.
Embodiment 8
The preparation of diaphragm unlike the first embodiment:
1) by diameter be 0.5 μm ceramic fibre and account for ceramic fibre quality 10% butadiene-styrene rubber mix, be added
Deionized water stirs evenly, and forms slurry, and the viscosity of slurry is 6000mPas, and the solid content of slurry is 70%；
2) the slurry coated and molded that will 1) obtain, after dehydration and drying be made diaphragm base, diaphragm base with a thickness of
12 μm, the porosity of diaphragm base is 50%；
3) polyvinyl chloride is added in nmp solvent, adds epoxy resin and Kynoar, stirred evenly, used
The method of spraying or intaglio plate coating is coated in diaphragm base, forms hot melt polymeric nitride layer, the painting of hot melt polymeric nitride layer
Cloth quality be diaphragm base layer quality 0.75%, hot melt polymeric nitride layer with a thickness of 10 μm.
Remaining is with embodiment 1, and which is not described herein again.
Embodiment 9
The preparation of diaphragm unlike the first embodiment:
1) by diameter be 0.2 μm glass fibre, the ceramic fibre that diameter is 0.5 μm and to account for glass fibre and ceramics fine
The 5% epoxy resin mixing for tieing up gross mass, is added deionized water and stirs evenly, form slurry, the viscosity of slurry is
7000mPas, the solid content of slurry are 55%；
2) the slurry coated and molded that will 1) obtain, after dehydration and drying be made diaphragm base, diaphragm base with a thickness of
10 μm, the porosity of diaphragm base is 40%；
3) polyacrylate copolymer is added in nmp solvent, adds neopentylglycol diacrylate, stirring is equal
It is even, it is coated in diaphragm base using the method for spraying or intaglio plate coating, forms hot melt polymeric nitride layer, hot-melt polymer
Layer coating quality be diaphragm base layer quality 0.68%, hot melt polymeric nitride layer with a thickness of 8 μm.
Remaining is with embodiment 1, and which is not described herein again.
Embodiment 10
The preparation of diaphragm unlike the first embodiment:
1) by diameter be 0.3 μm glass fibre, the ceramic fibre that diameter is 0.4 μm and to account for glass fibre and ceramics fine
The 15% neopentylglycol diacrylate mixing for tieing up gross mass, is added deionized water and stirs evenly, and forms slurry, and slurry glues
Degree is 8000mPas, and the solid content of slurry is 60%；
2) the slurry coated and molded that will 1) obtain, after dehydration and drying be made diaphragm base, diaphragm base with a thickness of
12 μm, the porosity of diaphragm base is 50%；
3) polyethylene-polyvinyl acetate copolymer is added in nmp solvent, adds Kynoar, stirring is equal
It is even, it is coated in diaphragm base using the method for spraying or intaglio plate coating, forms hot melt polymeric nitride layer, hot-melt polymer
Layer coating quality be diaphragm base layer quality 1%, hot melt polymeric nitride layer with a thickness of 6 μm.
Remaining is with embodiment 1, and which is not described herein again.
Embodiment 11
The preparation of diaphragm unlike the first embodiment:
1) by diameter be 0.3 μm glass fibre, the ceramic fibre that diameter is 0.4 μm and to account for glass fibre and ceramics fine
The 20% neopentylglycol diacrylate mixing for tieing up gross mass, is added deionized water and stirs evenly, and forms slurry, and slurry glues
Degree is 8000mPas, and the solid content of slurry is 60%；
2) the slurry coated and molded that will 1) obtain, after dehydration and drying be made diaphragm base, diaphragm base with a thickness of
14 μm, the porosity of diaphragm base is 55%；
3) polyethylene-polyvinyl acetate copolymer is added in nmp solvent, adds Kynoar, stirring is equal
It is even, it is coated in diaphragm base using the method for spraying or intaglio plate coating, forms hot melt polymeric nitride layer, hot-melt polymer
Layer coating quality be diaphragm base layer quality 1%, hot melt polymeric nitride layer with a thickness of 6 μm.
Remaining is with embodiment 1, and which is not described herein again.
Embodiment 12
The preparation of diaphragm unlike the first embodiment:
1) by diameter be 0.3 μm glass fibre, the ceramic fibre that diameter is 0.4 μm and to account for glass fibre and ceramics fine
The 3% neopentylglycol diacrylate mixing for tieing up gross mass, is added deionized water and stirs evenly, and forms slurry, and slurry glues
Degree is 8000mPas, and the solid content of slurry is 60%；
2) the slurry coated and molded that will 1) obtain, after dehydration and drying be made diaphragm base, diaphragm base with a thickness of 8
μm, the porosity of diaphragm base is 30%；
3) polyethylene-polyvinyl acetate copolymer is added in nmp solvent, adds Kynoar, stirring is equal
It is even, it is coated in diaphragm base using the method for spraying or intaglio plate coating, forms hot melt polymeric nitride layer, hot-melt polymer
Layer coating quality be diaphragm base layer quality 1%, hot melt polymeric nitride layer with a thickness of 6 μm.
Remaining is with embodiment 1, and which is not described herein again.
Embodiment 13
The preparation of diaphragm unlike the first embodiment:
1) by diameter be 0.3 μm glass fibre, the ceramic fibre that diameter is 0.4 μm and to account for glass fibre and ceramics fine
The 15% neopentylglycol diacrylate mixing for tieing up gross mass, is added deionized water and stirs evenly, and forms slurry, and slurry glues
Degree is 8000mPas, and the solid content of slurry is 60%；
2) the slurry coated and molded that will 1) obtain, after dehydration and drying be made diaphragm base, diaphragm base with a thickness of
12 μm, the porosity of diaphragm base is 50%；
3) polyethylene-polyvinyl acetate copolymer is added in nmp solvent, adds Kynoar, stirring is equal
It is even, it is coated in diaphragm base using the method for spraying or intaglio plate coating, forms hot melt polymeric nitride layer, hot-melt polymer
Layer coating quality be diaphragm base layer quality 0.2%, hot melt polymeric nitride layer with a thickness of 2 μm.
Remaining is with embodiment 1, and which is not described herein again.
Embodiment 14
The preparation of diaphragm unlike the first embodiment:
1) by diameter be 0.3 μm glass fibre, the ceramic fibre that diameter is 0.4 μm and to account for glass fibre and ceramics fine
The 15% neopentylglycol diacrylate mixing for tieing up gross mass, is added deionized water and stirs evenly, and forms slurry, and slurry glues
Degree is 8000mPas, and the solid content of slurry is 60%；
2) the slurry coated and molded that will 1) obtain, after dehydration and drying be made diaphragm base, diaphragm base with a thickness of
12 μm, the porosity of diaphragm base is 50%；
3) polyethylene-polyvinyl acetate copolymer is added in nmp solvent, adds Kynoar, stirring is equal
It is even, it is coated in diaphragm base using the method for spraying or intaglio plate coating, forms hot melt polymeric nitride layer, hot-melt polymer
Layer coating quality be diaphragm base layer quality 1.2%, hot melt polymeric nitride layer with a thickness of 12 μm.
Remaining is with embodiment 1, and which is not described herein again.
Comparative example 1
The preparation of positive plate:
By cobalt acid lithium, conductive agent superconduction carbon (Super-P), binder Kynoar (PVDF) 97:1.5 in mass ratio:
1.5 be uniformly mixed the lithium ion battery anode glue size with certain viscosity is made, slurry is coated in current collector aluminum foil, 85
It is cold-pressed after being dried at DEG C；Then carry out trimming, cut-parts, slitting, after slitting under vacuum conditions 110 DEG C dry 4 hours, weldering
Tab is connect, based lithium-ion battery positive plate is made.
The preparation of negative electrode tab:
By graphite and conductive agent superconduction carbon (Super-P), thickener sodium carboxymethylcellulose (CMC), binder butylbenzene rubber
Slurry is made in glue (SBR) 96:2.0:1.0:1.0 in mass ratio, is coated on copper foil of affluxion body and dries at 85 DEG C；It is cut
Side, cut-parts, slitting, after slitting under vacuum conditions 110 DEG C dry 4 hours, anode plate for lithium ionic cell is made in soldering polar ear.
The preparation of diaphragm: take 16 μm of polyethene microporous membranes as diaphragm.
The preparation of electrolyte: by lithium hexafluoro phosphate (LiPF6) it is dissolved in ethylene carbonate (EC), dimethyl carbonate (DMC)
And (mass ratio of three is 1 to the in the mixed solvent of methyl ethyl carbonate (EMC) composition；2:1), the electricity that concentration is 1mol/L is obtained
Solve liquid.
The preparation of lithium ion battery: being wound into battery core for above-mentioned positive plate, diaphragm and negative electrode tab, diaphragm be located at it is adjacent just
Between pole piece and negative electrode tab, anode is with aluminium pole ears spot welding extraction, and cathode is with nickel tab spot welding extraction；Then battery core is placed in plastic-aluminum
In packaging bag, above-mentioned electrolyte is injected, lithium ion battery is made in the processes such as encapsulated, chemical conversion, capacity.
Comparative example 2
This comparative example is improved on the basis of comparative example 1, wherein the preparation of positive plate, the preparation of negative electrode tab, electricity
The preparation of the preparation and battery that solve liquid is identical as comparative example 1, repeats no more, and diaphragm is different from comparative example 1, below to diaphragm and its
Preparation is described in detail.
1) by diameter be 0.3 μm glass fibre, the ceramic fibre that diameter is 0.4 μm and to account for glass fibre and ceramics fine
The 15% neopentylglycol diacrylate mixing for tieing up gross mass, is added deionized water and stirs evenly, and forms slurry, and slurry glues
Degree is 8000mPas, and the solid content of slurry is 60%；
2) the slurry coated and molded that will 1) obtain, is made diaphragm after dehydration and drying, diaphragm with a thickness of 12 μm, diaphragm
Porosity be 50%.
Comparative example 3
This comparative example is improved on the basis of comparative example 1, wherein the preparation of positive plate, the preparation of negative electrode tab, electricity
The preparation of the preparation and battery that solve liquid is identical as comparative example 1, repeats no more, and diaphragm is different from comparative example 1, below to diaphragm and its
Preparation is described in detail.
1) take the polyethene microporous membrane with a thickness of 16 μm as basement membrane；
2) polyethylene-polyvinyl acetate copolymer is added in nmp solvent, adds Kynoar, stirring is equal
It is even, it is coated in diaphragm base using the method for spraying or intaglio plate coating, forms hot melt polymeric nitride layer, hot-melt polymer
Layer coating quality be diaphragm base layer quality 1%, hot melt polymeric nitride layer with a thickness of 6 μm.
Performance test
The diaphragm and lithium ion battery of embodiment 1~14 and comparative example 1~3 are tested for the property, wherein
Safety of acupuncture performance test: battery is fully charged to after 4.2V in a manner of constant current and constant pressure, with Φ 3mm~Φ
The high temperature resistant steel needle of 8mm is run through, steel needle is rested on the speed of 10mm/s~40mm/s from the direction perpendicular to battery pole plates
1h in battery.
The test of external short circuit security performance: battery is fully charged to after 4.2V in a manner of constant current and constant pressure, using internal resistance < 5m
The outside line of Ω is shorted 10min.
Hot tank safety test: being started to warm up with the speed of 2 DEG C/min from 80 DEG C, until 120 DEG C of holding 2h, until 150 DEG C of holdings
2h, until 200 DEG C of holding 30min.
Define the result of security performance test: " do not smolder, is not on fire, not exploding " is " passing through "；It " smolders, have Mars, not
Explosion " is " undetermined "；" explosion on fire " is " failure ".
Specific data are shown in Table 1.
1 the performance test results of table
Membrane properties of the invention are substantially better than individual polyalkene diaphragm, individual fiber it can be seen from 1 data of table
Diaphragm and polyalkene diaphragm coated with hot melt polymeric nitride layer, and the property of the lithium ion battery containing diaphragm of the invention
The lithium ion battery containing other three kinds of diaphragms can be also significantly better than.This is because first, glass is contained in septation base of the present invention
Glass fiber and/or ceramic fibre, so that barrier film base material has good mechanical strength and thermal stability, therefore, diaphragm
Percent thermal shrinkage is lower, and phenomena such as on fire, explosion will not occur under needle thorn and the environment such as hot tank for battery.Second, this hair
It is bright to be provided with one layer of hot melt polymeric nitride layer in diaphragm base, wherein the hot-melt polymer for being 120~200 DEG C containing fusing point,
It when battery temperature is excessively high, can melt in a short time, and block the micropore in diaphragm base, play closed pore function.
In addition, by the comparison of embodiment 10~12 it is found that the content of first bonding agents should not be excessive or very few in diaphragm base,
When the content of first bonding agents excessive (embodiment 11), the porosity of diaphragm base will increase, reduce the machinery of diaphragm base
The percent thermal shrinkage of intensity and thermal stability, diaphragm will increase, and in needle thorn etc. under environment, it may occur that smolders, catch fire or even quick-fried
Fried phenomenon, reduces the security performance of battery；And when the content of first bonding agents is very few, the porosity of diaphragm base can be reduced,
To influence the permeability of battery.
In addition to this, it is compared by embodiment 10,13 and 14 it is found that the coating quality of hot melt polymeric nitride layer accounts for diaphragm base
Quality should not be too large or too small, when the coating quality accounting of hot melt polymeric nitride layer too small (embodiment 13), hot melt is poly-
The thickness for closing nitride layer also can be reduced accordingly, not have ideal effect, cannot be fully when battery is in the condition of high temperature
The micropore of diaphragm base is blocked；And when the coating quality accounting of hot melt polymeric nitride layer excessive (embodiment 14), hot melt
The thickness of polymeric layer is also corresponding thicker, to increase the volume of entire battery, reduces the volume energy ratio of battery.
According to the disclosure and teachings of the above specification, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula is changed and is modified.Therefore, the invention is not limited to above-mentioned specific embodiment, all those skilled in the art exist
Made any conspicuous improvement, replacement or modification all belong to the scope of protection of the present invention on the basis of the present invention.This
Outside, although using some specific terms in this specification, these terms are merely for convenience of description, not to the present invention
Constitute any restrictions.
Claims (10)
1. a kind of battery diaphragm, it is characterised in that: including diaphragm base and be set to a diaphragm base at least surface
Hot melt polymeric nitride layer, the diaphragm base include at least one of glass fibre and ceramic fibre and first bonding agents,
The hot melt polymeric nitride layer includes hot-melt polymer and second bonding agents.
2. battery diaphragm according to claim 1, it is characterised in that: the coating quality of the hot melt polymeric nitride layer accounts for institute
State the 0.5~1% of diaphragm base layer quality.
3. battery diaphragm according to claim 1, it is characterised in that: the diaphragm base with a thickness of 9~12 μm, it is described
The porosity of diaphragm base is 40~50%.
4. battery diaphragm according to claim 1, it is characterised in that: the quality of the first bonding agents accounts for the glass fibers
The 5~15% of dimension and/or ceramic fibre quality total amount.
5. battery diaphragm according to claim 1, it is characterised in that: the diameter of the glass fibre and the ceramic fibre
Diameter be respectively 0.2~0.5 μm.
6. battery diaphragm according to claim 1, it is characterised in that: the hot melt polymeric nitride layer with a thickness of 3~10 μ
m。
7. battery diaphragm according to claim 1, it is characterised in that: the fusing point of the hot-melt polymer is 120~200
℃。
8. battery diaphragm according to claim 1, it is characterised in that: the first bonding agents and the second bonding agents packet
It is total to include polyacrylic acid, polymethylacrylic acid, polymethyl acrylate, polyethyl acrylate, pure-acrylic emulsion, polyacrylic acid-styrene
Polymers, butadiene-styrene rubber, epoxy resin, neopentylglycol diacrylate, Sodium Polyacrylate series, gathers partially polyvinylpyrrolidone
At least one of vinyl fluoride.
9. a kind of preparation method of battery diaphragm according to any one of claims 1 to 8, which comprises the following steps:
S1 mixes at least one of glass fibre and ceramic fibre with first bonding agents according to mass ratio, addition go from
Sub- water stirs evenly, and forms slurry, and the viscosity of the slurry is 2000~10000mPas, and the solid content of the slurry is 40
~70%；
Diaphragm base is made in S2, the slurry coated and molded that S1 is obtained after dehydration and drying；
Hot-melt polymer is added in solvent by S3, is added the second binder, is stirred evenly, using spraying or intaglio plate
The method of coating is coated in diaphragm base, forms hot melt polymeric nitride layer.
10. a kind of lithium ion battery, including winding is formed in the same direction after being stacked gradually by positive plate, diaphragm, negative electrode tab
Naked battery core and its electrolyte, it is characterised in that: the diaphragm is battery diaphragm according to any one of claims 1 to 8.
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| CN201910258155.8A CN109841785A (en) | 2019-04-01 | 2019-04-01 | A kind of battery diaphragm and preparation method thereof and the lithium ion battery comprising the diaphragm |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910258155.8A CN109841785A (en) | 2019-04-01 | 2019-04-01 | A kind of battery diaphragm and preparation method thereof and the lithium ion battery comprising the diaphragm |
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| CN201910258155.8A Pending CN109841785A (en) | 2019-04-01 | 2019-04-01 | A kind of battery diaphragm and preparation method thereof and the lithium ion battery comprising the diaphragm |
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| CN110600659A (en) * | 2019-08-08 | 2019-12-20 | 江苏塔菲尔新能源科技股份有限公司 | Lithium ion battery diaphragm, preparation method thereof and lithium ion battery |
| CN112266795A (en) * | 2020-10-12 | 2021-01-26 | 江苏塔菲尔新能源科技股份有限公司 | Fireproof heat-insulating material, battery module and battery pack |
| CN112886107A (en) * | 2020-12-31 | 2021-06-01 | 天津国安盟固利新材料科技股份有限公司 | Optimized button cell assembling method |
| CN112909426A (en) * | 2021-01-21 | 2021-06-04 | 河北金力新能源科技股份有限公司 | Lithium battery modified coating diaphragm and preparation method thereof |
| CN113045694A (en) * | 2019-12-10 | 2021-06-29 | 旭化成株式会社 | Polyethylene resin composition |
| CN113328205A (en) * | 2021-05-28 | 2021-08-31 | 安徽壹石通新能源材料有限公司 | Composition, electrode containing composition and application of composition |
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| CN112909426B (en) * | 2021-01-21 | 2022-11-01 | 河北金力新能源科技股份有限公司 | Lithium battery modified coating diaphragm and preparation method thereof |
| CN113328205A (en) * | 2021-05-28 | 2021-08-31 | 安徽壹石通新能源材料有限公司 | Composition, electrode containing composition and application of composition |
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