CN106025156B - A kind of lithium ion battery nanometer plasticizing porous polyethylene dry-stretched membrane and preparation method thereof - Google Patents
A kind of lithium ion battery nanometer plasticizing porous polyethylene dry-stretched membrane and preparation method thereof Download PDFInfo
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- CN106025156B CN106025156B CN201610339092.5A CN201610339092A CN106025156B CN 106025156 B CN106025156 B CN 106025156B CN 201610339092 A CN201610339092 A CN 201610339092A CN 106025156 B CN106025156 B CN 106025156B
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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
- 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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- 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 discloses a kind of lithium ion battery nanometers to be plasticized porous polyethylene dry-stretched membrane and preparation method thereof, the polyethylene dry-stretched membrane is mainly made of the raw material of following mass percent: nucleating agent 3%~10%, crosslinking agent 0.4%~2%, plasticiser 0.9%~3%, surplus are polyvinyl resin；Nucleating agent is organic nucleating agent or nano-powder nucleating agent；Organic nucleating agent is 1,3:2,4- dibenzyl sorbitol；Nano-powder nucleating agent is the nano-powder by coupling agent surface modification.Crosslinking points of the nucleating agent as polyethylene, obtain the structure for having solid netted after crosslinking agent causes, and make polyethylene inner generate uniform crazing at stretching initial stage, continue crazing after stretching and tear into uniform micropore；The porous polyethylene dry-stretched membrane average pore size is moderate, with a thickness of 8~25 μm, has good permeability, and film surface vertical and horizontal air permeability is very poor small, to improve the cycle life of battery.
Description
Technical field
The invention belongs to diaphragm for lithium ion battery technical fields, and in particular to a kind of lithium ion battery is more with nanometer plasticizing
Hole polyethylene dry-stretched membrane also relates to a kind of system of lithium ion battery nanometer plasticizing porous polyethylene dry-stretched membrane
Preparation Method.
Background technique
Lithium ion battery separator, lithium ion battery positive/negative material, electrolyte and battery case packaging material are lithium ions
The big component part of the four of battery, battery diaphragm primarily serve separation positive and negative anodes, avoid battery in the charge and discharge process of lithium ion
Short circuit, it is ensured that Li+Passability, guarantee inside battery circuit clear effect.The lithium ion battery separator of most of commercial is adopted
It is polyethylene either polypropylene material, this is because polyolefin has good mechanical performance and thermal stability (PP
Microporous barrier is at 160 DEG C or so, and PE microporous barrier is at 130 DEG C or so), therefore MIcroporous polyolefin film can be lithium ion battery separator
Processing and assembling provide enough mechanical strengths, prevent battery from overcharging and cause security risk.
The processing method of lithium ion battery separator mainly has dry method (fusion drawn method) and wet process (thermally induced phase separation) two
Kind.
Dry method melting simple tension method exactly squeezes out polymer melting, and longitudinal stretching, thermal finalization prepares the side of microporous barrier
Method.By polymer melting extrusion under stress field, lamellar structure arranged in parallel is obtained on perpendicular to extrusion direction, then first
Quick cold stretch at a lower temperature, then separate lamellar structure at relatively high temperatures with lesser rate hot-stretch, it generates micro-
Pore structure.Dry method is more convenient also more environmentally friendly because not needing solvent, and most producer uses the side of simple tension at present
Formula.But the hole of crack formula that simple tension obtains has anisotropy, lateral tensile strength is relatively low, general former
Material uses polypropylene (PP).
Wet process is that polymer and the high boiling diluent mixing of small-molecular-weight are formed homogeneous phase solution at high temperature, will be equal
Solid-liquid phase separation or liquid-liquid phase separation occur after squeezing out at a certain temperature for phase solution, are dispersed in diluent poly-
It closes in object phase, finally extracts diluent using extracting reagent with low boiling point, finally obtain polymer microporous film.Such method is available
The film in aperture and even pore distribution, but due to using a large amount of organic solvent, environmental pollution, and production line to invest
Greatly, be not suitable for large-scale industrial production.
Summary of the invention
The object of the present invention is to provide a kind of lithium ion battery nanometers to be plasticized porous polyethylene dry-stretched membrane.
A second object of the present invention is to provide a kind of lithium ion battery nanometers to be plasticized porous polyethylene dry-stretched membrane
Preparation method.
In order to achieve the goal above, the technical scheme adopted by the invention is that:
A kind of lithium ion battery nanometer plasticizing porous polyethylene dry-stretched membrane, mainly by the original of following mass percent
Material is made of dry method biaxial tension: nucleating agent 3%~10%, crosslinking agent 0.4%~2%, plasticiser 0.9%~3%, surplus
For polyvinyl resin；
Wherein, the nucleating agent is organic nucleating agent or nano-powder nucleating agent；The organic nucleating agent is 1,3:2,4-
Dibenzyl sorbitol (DBS)；The nano-powder nucleating agent is the nano-powder by coupling agent surface modification, the nanometer
Powder is P-hydroxybenzoic acid (HBA), potassium stearate, zinc stearate, calcium stearate, talcum powder, sodium bicarbonate (NaHCO3), oxygen
Change zinc (ZnO), aluminum oxide (Al2O3), silica (SiO2), any one or two kinds in TM-3 type nucleating agent.
Lithium ion battery of the invention is plasticized porous polyethylene dry-stretched membrane with nanometer, is mainly with nucleating agent, crosslinking
Agent, plasticiser and polyvinyl resin are raw material, using made of the stretching of dry method two-phase；The evenly dispersed nanometer in polyvinyl resin
The nano particle of particulate nucleants, this nucleating agent can be used as the crosslinking points of polyethylene, be had after crosslinking agent causes
Solid netted structure.These reticular structures make polyethylene inner generate uniform crazing, after continuing stretching at stretching initial stage
Crazing is torn into uniform micropore.
Average grain diameter≤100nm of the nano-powder.In use, nano-powder nucleating agent is directly mixed with polyvinyl resin
It closes；Organic nucleating agent can be directly dissolved in organic solvent and solution is made, and be mixed by the way of directly spraying with polyvinyl resin.
The dosage of the coupling agent is the 0.1%~5% of nano-powder quality.
The coupling agent is silane coupling agent, titanate coupling agent, aluminate coupling agent, any in bimetallic coupling agent
It is one or two kinds of.
The silane coupling agent is vinyltriethoxysilane, appointing in vinyl three ('beta '-methoxy ethyoxyl) silane
Meaning is one or two kinds of；The titanate coupling agent is isopropyl three (dioctyl phosphoric acid acyloxy) titanate esters, monoalkoxy insatiable hunger
With any one or two kinds in fatty acid titanate esters, Di(dioctylpyrophosphato) ethylene titanate；The Aluminate
Coupling agent is distearyl acyl-oxygen isopropyl Aluminate；The bimetallic coupling agent is zirconium Al bimetal coupling agent.
The crosslinking agent is bis- (tert-butyl peroxy base) hexanes of 2,5- dimethyl -2,5-, bis- (the tertiary fourths of 2,5- dimethyl -2,5-
Peroxy) hexin -3, α, bis- (tert-butyl peroxy base) diisopropylbenzene (DIPB)s of α -, cumyl peroxide (DCP), bis- (the peroxidating uncles of 2,2-
Butyl) butane, any one or two kinds in 4- dihydroxy benaophenonel laurate (BPL).Wherein, 2,5- dimethyl -2,5-
Bis- (tert-butyl peroxy base) hexanes, 2,5- dimethyl -2,5- bis- (tert-butyl peroxy base) hexins -3, α, bis- (the tert-butyl peroxy bases) two of α-are different
Propyl benzene, cumyl peroxide are powder；Bis- (tert-butyl peroxide) butane of 2,2- are liquid.
4- dihydroxy benaophenonel laurate (BPL) is photocatalyzed crossing agent；It is urged in use, needing to carry out ultraviolet light
Change makes it generate crosslinked action.
Phthalic acid lipid or maleic acid esters plasticiser can be used in the plasticiser.
Preferably, the plasticiser is diisooctyl phthalate (DIOP), dibutyl maleate (DMB), maleic acid
Any one in diisobutyl ester (DIBM).
The polyvinyl resin be high density polyethylene (HDPE) (HDPE), ultra-high molecular weight polyethylene (UHMW-PE) it is any one
The mixing of kind or both.
Above-mentioned lithium ion battery is plasticized porous polyethylene dry-stretched membrane with nanometer, is made of using dry method biaxial tension
's；It also needs to use a small amount of organic solvent in preparation process；The dosage of the organic solvent is can dissolve crosslinking agent, plasticiser
(and organic nucleating agent)；The preferred acetone of organic solvent.
A kind of above-mentioned lithium ion battery is plasticized the preparation method of porous polyethylene dry-stretched membrane with nanometer, including following
Step:
1) polyvinyl resin of formula ratio is mixed with crosslinking agent, plasticiser, nucleating agent, is melted under the conditions of 160~210 DEG C
Melt extrusion, is cooled to 50~100 DEG C and sheet is made；
2) by sheet obtained by step 1) under the conditions of 60~110 DEG C using film forming is stretched by the way of lateral behind elder generation longitudinal direction, i.e.,
?.
In step 1), polyvinyl resin used is pellet or powder.
In step 1), the mixing refers to that crosslinking agent, plasticiser, which are dissolved in organic solvent, is made solution, and acquired solution is sprayed
It spills into the pellet of polyvinyl resin or powder, adds nano-powder nucleating agent and be uniformly mixed；Alternatively, it is described mixing refer to by
Crosslinking agent, plasticiser, organic nucleating agent are dissolved in organic solvent and solution are made, and acquired solution is sprayed to the pellet of polyvinyl resin
Or it is uniformly mixed in powder.The organic solvent is acetone；The dosage of acetone, which is subject to, can dissolve above-mentioned substance.
Double screw extruder can be used in the melting extrusion.
In the preparation method, when crosslinking agent used is photocatalyzed crossing agent, sheet obtained by step 1) is carried out ultraviolet
After light irradiation, then carry out the operation of step 2)；The time of the ultraviolet light is 5~20min.
In step 2), longitudinal stretching multiplying power is 3~10 times, and cross directional stretch multiplying power is 2~5 times.
Lithium ion battery of the invention is plasticized the preparation method of porous polyethylene dry-stretched membrane with nanometer, is by ethylene tree
Rouge and crosslinking agent, plasticiser, nucleating agent mixed melting squeeze out, cooling to be made sheet, then draw using by the way of lateral behind elder generation longitudinal direction
It is stretched into film；The average pore size of polyethylene dry-stretched membrane obtained by the preparation method is 80~300nm, is of moderate size, both will not hole
Diameter is too small, lithium ion by difficulty, will not aperture it is excessive, generate Li dendrite and cause internal short-circuit and reduce the safety of battery；
Gained polyethylene dry-stretched membrane with a thickness of 8~25 μm, porosity is 45%~65%, and air permeability is 100~300s/
100mL has good permeability, and film surface vertical and horizontal air permeability is very poor in ± 30s, even aperture distribution, film
The pass in hole is ellipse, and more conducively non-aqueous eletrolyte passes through, and improves the cycle life of battery.
Lithium ion battery of the invention is plasticized the preparation method of porous polyethylene dry-stretched membrane with nanometer, is received by being crosslinked
Rice grain generates crazing defect inside film, after stretching, the even aperture distribution of film, and air permeability height；It is compared compared with wet process, it is raw
Production process does not use organic solvent, and no pollution to the environment, simple process, investment is small, at low cost；It is compared compared with dry method, the system
Preparation Method can produce 10 μm of diaphragms below of thickness, and film-forming temperature is low, and energy consumption is small.
Detailed description of the invention
Fig. 1 is the SEM figure that 5 gained lithium ion battery nanometer of embodiment is plasticized porous polyethylene dry-stretched membrane.
Specific embodiment
The present invention is further illustrated With reference to embodiment.
Embodiment 1
The lithium ion battery of the present embodiment is plasticized porous polyethylene dry-stretched membrane with nanometer, mainly by following quality percentage
The raw material of ratio is made of dry method biaxial tension: 1,3:2,4- dibenzyl sorbitol (DBS) 3.1%, 2,5- dimethyl -2,5-
Bis- (tert-butyl peroxy base) hexanes 0.52%, diisooctyl phthalate (DIOP) 1.0%, surplus is high density polyethylene (HDPE)
(HDPE)。
The lithium ion battery of the present embodiment is plasticized the preparation method of porous polyethylene dry-stretched membrane with nanometer, including following
Step:
1) 1,3:2,4- dibenzyl sorbitol (DBS) 65g is taken, is dissolved in acetone and solution is made；
Take high density polyethylene (HDPE) 2.0kg, above-mentioned solution, 2,5- dimethyl -2,5- bis- (tert-butyl peroxy base) hexane 11g, neighbour
Phthalic acid di-isooctyl (DIOP) 21g, is added in double screw extruder and mixes, melting extrusion under the conditions of 160 DEG C, then
It is cooled to 50 DEG C on chill roll and casts sheet；
2) sheet obtained by step 1) is carried out to the gradually stretching of first longitudinal 3 multiplying powers, rear oblong rate under the conditions of 60 DEG C,
Be made film forming to get.
Embodiment 2
The lithium ion battery of the present embodiment is plasticized porous polyethylene dry-stretched membrane with nanometer, mainly by following quality percentage
The raw material of ratio is made of dry method biaxial tension: nanoparticle nucleated dose 3.9%, the bis- (tert-butyl peroxies of 2,5- dimethyl -2,5-
Base) hexin -30.94%, dibutyl maleate (DMB) 0.94%, surplus is high density polyethylene (HDPE) (HDPE).
Wherein, described nanoparticle nucleated dose is the nano-powder by vinyltriethoxysilane surface modification；Institute
Stating nano-powder is potassium stearate, average grain diameter 80nm；The quality of vinyltriethoxysilane used is potassium stearate matter
The 4% of amount.
The lithium ion battery of the present embodiment is plasticized the preparation method of porous polyethylene dry-stretched membrane with nanometer, including following
Step:
1) 80g nano-powder (potassium stearate) is taken, is first surface modified with 3.2g vinyltriethoxysilane, must be received
Rice grain nucleating agent；
Take high density polyethylene (HDPE) 2.0kg, nanoparticle nucleated dose above-mentioned, 2,5- dimethyl -2,5- bis- (tert-butyl peroxy bases)
Hexane -320g, dibutyl maleate (DMB) 20g, are added in double screw extruder and mix, and melt and squeeze under the conditions of 170 DEG C
Out, then on chill roll 60 DEG C are cooled to and casts sheet；
2) sheet obtained by step 1) is carried out to the gradually stretching of first longitudinal 4 multiplying powers, rear oblong rate under the conditions of 70 DEG C,
Be made film forming to get.
Embodiment 3
The lithium ion battery of the present embodiment is plasticized porous polyethylene dry-stretched membrane with nanometer, mainly by following quality percentage
The raw material of ratio is made of dry method biaxial tension: nanoparticle nucleated dose 4.9%, α, bis- (tert-butyl peroxy base) diisopropylbenzene (DIPB)s of α-
0.93%, diisobutyl maleate (DIMB) 1.4%, surplus are high density polyethylene (HDPE) (HDPE).
Wherein, described nanoparticle nucleated dose is by isopropyl three (dioctyl phosphoric acid acyloxy) titanate esters surface modification
Nano-powder；The nano-powder is calcium stearate, average grain diameter 75nm；Three (dioctyl phosphoric acid acyl-oxygen of isopropyl used
Base) titanate esters quality be calcium stearate quality 5%.
The lithium ion battery of the present embodiment is plasticized the preparation method of porous polyethylene dry-stretched membrane with nanometer, including following
Step:
1) 100g nano-powder (calcium stearate) is taken, is first carried out with 5g isopropyl three (dioctyl phosphoric acid acyloxy) titanate esters
Surface modification obtains nanoparticle nucleated dose；
Take high density polyethylene (HDPE) 2.0kg, nanoparticle nucleated dose above-mentioned, α, bis- (tert-butyl peroxy base) the diisopropylbenzene (DIPB) 20g of α-,
Diisobutyl maleate (DIMB) 30g, is added in double screw extruder and mixes, melting extrusion under the conditions of 180 DEG C, then cold
But it is cooled to 80 DEG C on roller and casts sheet；
2) sheet obtained by step 1) is carried out to the gradually stretching of first longitudinal 5 multiplying powers, rear laterally 3 multiplying powers under the conditions of 90 DEG C,
Be made film forming to get.
Embodiment 4
The lithium ion battery of the present embodiment is plasticized porous polyethylene dry-stretched membrane with nanometer, mainly by following quality percentage
The raw material of ratio is made of dry method biaxial tension: nanoparticle nucleated dose 5.5%, cumyl peroxide (DCP) 1.4%, horse
Carry out dibutyl phthalate (DMB) 1.8%, surplus is high density polyethylene (HDPE) (HDPE).
Wherein, described nanoparticle nucleated dose is the nanometer by monoalkoxy unsaturated fatty acid titanate esters surface modification
Powder；The nano-powder is zinc stearate, average grain diameter 90nm；The matter of monoalkoxy unsaturated fatty acid titanate esters used
Amount is the 0.1% of zinc stearate quality.
The lithium ion battery of the present embodiment is plasticized the preparation method of porous polyethylene dry-stretched membrane with nanometer, including following
Step:
1) 120g nano-powder (zinc stearate) is taken, first carries out table with 0.12g monoalkoxy unsaturated fatty acid titanate esters
Face modification, obtains nanoparticle nucleated dose；
Take high density polyethylene (HDPE) 2.0kg, nanoparticle nucleated dose above-mentioned, cumyl peroxide (DCP) 30g, maleic acid
Dibutyl ester (DMB) 40g, is added in double screw extruder and mixes, melting extrusion under the conditions of 190 DEG C, then on chill roll it is cold
But sheet is cast to 90 DEG C；
2) sheet obtained by step 1) is carried out to the gradually stretching of first longitudinal 7 multiplying powers, rear laterally 4 multiplying powers under the conditions of 100 DEG C,
Be made film forming to get.
Embodiment 5
The lithium ion battery of the present embodiment is plasticized porous polyethylene dry-stretched membrane with nanometer, mainly by following quality percentage
The raw material of ratio is made of dry method biaxial tension: nanoparticle nucleated dose 6.5%, bis- (tert-butyl peroxide) butane of 2,2-
0.91%, diisooctyl phthalate (DIOP) 1.8%, surplus are high density polyethylene (HDPE) (HDPE).
Wherein, described nanoparticle nucleated dose is by Di(dioctylpyrophosphato) ethylene titanate surface modification
Nano-powder；The nano-powder is sodium bicarbonate (NaHCO3), average grain diameter 85nm；Bis- (two octyloxy coke phosphorus used
Perester radical) ethylene titanate esters quality be NaHCO3The 2% of quality.
The lithium ion battery of the present embodiment is plasticized the preparation method of porous polyethylene dry-stretched membrane with nanometer, including following
Step:
1) 140g nano-powder (NaHCO is taken3), first carried out with 2.8g Di(dioctylpyrophosphato) ethylene titanate
Surface modification obtains nanoparticle nucleated dose；
Take high density polyethylene (HDPE) 2.0kg, nanoparticle nucleated dose above-mentioned, bis- (tert-butyl peroxide) the butane 20g of 2,2-, neighbour
Phthalic acid di-isooctyl (DIOP) 40g, is added in double screw extruder and mixes, melting extrusion under the conditions of 200 DEG C, then
It is cooled to 100 DEG C on chill roll and casts sheet；
2) sheet obtained by step 1) is carried out to the gradually stretching of first longitudinal 8 multiplying powers, rear laterally 4 multiplying powers under the conditions of 105 DEG C,
Be made film forming to get.
Porous polyethylene dry-stretched membrane is plasticized with nanometer to lithium ion battery obtained by the present embodiment and is scanned Electronic Speculum sight
It examines, SEM figure is as shown in Figure 1.It will be seen from figure 1 that nanometer plasticizing porous polyethylene dry method tension membrane aperture is moderate, aperture point
Cloth is uniform, and the pass of fenestra is ellipse, and more conducively non-aqueous eletrolyte passes through.
Embodiment 6
The lithium ion battery of the present embodiment is plasticized porous polyethylene dry-stretched membrane with nanometer, mainly by following quality percentage
The raw material of ratio is made of dry method biaxial tension: nanoparticle nucleated dose 7.2%, 4- dihydroxy benaophenonel laurate (BPL)
0.44%, bis- (tert-butyl peroxide) butane 1.3% of 2,2-, diisobutyl maleate (DIMB) 2.2%, surplus are poly- for high density
Ethylene (HDPE) and ultra-high molecular weight polyethylene (UHMW-PE)；The mass ratio of HDPE and UHMW-PE is 3:1.
Wherein, described nanoparticle nucleated dose is the nano powder by distearyl acyl-oxygen isopropyl Aluminate surface modification
Body；The nano-powder is Al2O3, average grain diameter 80nm；The quality of distearyl acyl-oxygen isopropyl Aluminate used is Al2O3
The 1% of quality.
The lithium ion battery of the present embodiment is plasticized the preparation method of porous polyethylene dry-stretched membrane with nanometer, including following
Step:
1) 160g nano-powder (Al is taken2O3), it is first surface modified, is obtained with 1.6g distearyl acyl-oxygen isopropyl Aluminate
Nanoparticle nucleated dose；
Take high density polyethylene (HDPE) 1.5kg, ultra-high molecular weight polyethylene 0.5kg, nanoparticle nucleated dose above-mentioned, 4- hydroxyl two
Benzophenone laurate (BPL) 10g, bis- (tert-butyl peroxide) the butane 30g of 2,2-, diisobutyl maleate (DIMB) 50g, add
Enter and is mixed into double screw extruder, melting extrusion under the conditions of 180 DEG C, then be cooled to 80 DEG C on chill roll and cast sheet；
By gained sheet ultraviolet light 10min, illumination sheet is obtained；
2) illumination sheet obtained by step 1) is carried out to the gradually drawing of first longitudinal 6 multiplying powers, rear laterally 3 multiplying powers under the conditions of 90 DEG C
Stretch, be made film forming to get.
Embodiment 7
The lithium ion battery of the present embodiment is plasticized porous polyethylene dry-stretched membrane with nanometer, mainly by following quality percentage
The raw material of ratio is made of dry method biaxial tension: nanoparticle nucleated dose 8.2%, the bis- (tert-butyl peroxies of 2,5- dimethyl -2,5-
Base) hexin -30.45%, dibutyl maleate (DMB) 2.2%, surplus is ultra-high molecular weight polyethylene (UHMW-PE).
Wherein, described nanoparticle nucleated dose is the nano-powder by coupling agent surface modification；The nano-powder is
SiO2The mixed powder that mass ratio with TM-3 type nucleating agent is 100:80, average grain diameter 80nm；Coupling agent used is ethylene
The mass ratio of ethyl triethoxy silicane alkane and vinyl three ('beta '-methoxy ethyoxyl) silane is the mixture of 2.8:0.8, idol used
The quality for joining agent is the 2% of nano-powder quality.
The lithium ion battery of the present embodiment is plasticized the preparation method of porous polyethylene dry-stretched membrane with nanometer, including following
Step:
1) nano-powder (SiO is taken2100g, TM-3 type nucleating agent 80g), first with 2.8g vinyltriethoxysilane and
0.8g vinyl three ('beta '-methoxy ethyoxyl) silane is surface modified, and obtains nanoparticle nucleated dose；
Take ultra-high molecular weight polyethylene 2.0kg, the nanoparticle nucleated dose above-mentioned, bis- (tert-butyl peroxies of 2,5- dimethyl -2,5-
Base) -3 10g of hexin, dibutyl maleate (DMB) 50g, it is added in double screw extruder and mixes, melted under the conditions of 200 DEG C
It squeezes out, then is cooled to 100 DEG C on chill roll and casts sheet；
2) sheet obtained by step 1) is carried out to the gradually stretching of first longitudinal 4 multiplying powers, rear oblong rate under the conditions of 100 DEG C,
Be made film forming to get.
Embodiment 8
The lithium ion battery of the present embodiment is plasticized porous polyethylene dry-stretched membrane with nanometer, mainly by following quality percentage
The raw material of ratio is made of dry method biaxial tension: nanoparticle nucleated dose 9.2%, α, bis- (tert-butyl peroxy base) diisopropylbenzene (DIPB)s of α-
0.44%, bis- (tert-butyl peroxy base) hexanes 0.44% of 2,5- dimethyl -2,5-, dibutyl maleate (DMB) 2.6%, surplus are
High density polyethylene (HDPE) (HDPE).
Wherein, described nanoparticle nucleated dose is the nano-powder by coupling agent surface modification；The nano-powder is
The mass ratio of P-hydroxybenzoic acid (HBA) and talcum powder is the mixed powder of 150:60, average grain diameter 100nm；Coupling used
Agent is the mixture that the mass ratio of ('beta '-methoxy ethyoxyl) silane of vinyl three and vinyltriethoxysilane is 1:1, institute
With 0.95% that the quality of coupling agent is nano-powder quality.
The lithium ion battery of the present embodiment is plasticized the preparation method of porous polyethylene dry-stretched membrane with nanometer, including following
Step:
1) take nano-powder (HBA 150g, talcum powder 60g), first with ('beta '-methoxy ethyoxyl) silane of 1g vinyl three and
1g vinyltriethoxysilane is surface modified, and obtains nanoparticle nucleated dose；
Take high density polyethylene (HDPE) 2.0kg, nanoparticle nucleated dose above-mentioned, α, bis- (tert-butyl peroxy base) the diisopropylbenzene (DIPB) 10g of α-,
Bis- (tert-butyl peroxy base) the hexane 10g of 2,5- dimethyl -2,5-, dibutyl maleate (DMB) 60g, are added to double screw extruder
Middle mixing, melting extrusion under the conditions of 210 DEG C, then be cooled to 100 DEG C on chill roll and cast sheet；
2) sheet obtained by step 1) is carried out to the gradually drawing of first longitudinal 10 multiplying powers, rear laterally 5 multiplying powers under the conditions of 110 DEG C
Stretch, be made film forming to get.
Experimental example 1
This experimental example is plasticized porous polyethylene dry-stretched membrane with nanometer to lithium ion battery obtained by embodiment 1-8 and examines
It surveys, the results are shown in Table 1.
Lithium ion battery obtained by 1 embodiment 1-8 of table is plasticized the testing result of porous polyethylene dry-stretched membrane with nanometer
As it can be seen from table 1 lithium ion battery obtained by embodiment 1-8 is plasticized porous polyethylene dry-stretched membrane with nanometer
Average pore size is 80-280nm, porosity 45%-65%, air permeability 100-300s/100mL, and air permeability is very poor to be not more than
± 30s, with a thickness of 8-25 μm.Testing result shows gained lithium ion battery nanometer plasticizing porous polyethylene dry method of the invention
Stretched film has relatively mild aperture, biggish porosity and air permeability, lesser air permeability very poor and thickness, be used as lithium from
Sub- battery diaphragm can significantly improve the chemical property and service life of lithium ion battery.
Claims (10)
1. a kind of lithium ion battery is plasticized porous polyethylene dry-stretched membrane with nanometer, it is characterised in that: mainly by following quality
The raw material of percentage is made of dry method biaxial tension: nucleating agent 3%~10%, crosslinking agent 0.4%~2%, plasticiser 0.9%~3%,
Surplus is polyvinyl resin；
Wherein, the nucleating agent is organic nucleating agent or nano-powder nucleating agent；The organic nucleating agent is 1,3:2,4- bis- sub-
Benzyl sorbitol；The nano-powder nucleating agent is the nano-powder by coupling agent surface modification, and the nano-powder is pair
Hydroxybenzoic acid, potassium stearate, zinc stearate, calcium stearate, talcum powder, sodium bicarbonate, zinc oxide, aluminum oxide, dioxy
Any one in SiClx, TM-3 type nucleating agent or two kinds；
The nanometer plasticizing porous polyethylene dry-stretched membrane is made by the method included the following steps:
1) polyvinyl resin of formula ratio is mixed with crosslinking agent, plasticiser, nucleating agent, melts and squeezes under the conditions of 160~210 DEG C
Out, 50~100 DEG C are cooled to, sheet is made；
2) by sheet obtained by step 1) under the conditions of 60~110 DEG C using stretch by the way of lateral behind first longitudinal direction form a film to get.
2. lithium ion battery according to claim 1 is plasticized porous polyethylene dry-stretched membrane with nanometer, it is characterised in that:
The dosage of the coupling agent is the 0.1%~5% of nano-powder quality.
3. lithium ion battery according to claim 1 or 2 is plasticized porous polyethylene dry-stretched membrane with nanometer, feature exists
In: the coupling agent be silane coupling agent, titanate coupling agent, aluminate coupling agent, any one in bimetallic coupling agent
Or two kinds.
4. lithium ion battery according to claim 3 is plasticized porous polyethylene dry-stretched membrane with nanometer, it is characterised in that:
The silane coupling agent be vinyltriethoxysilane, in vinyl three ('beta '-methoxy ethyoxyl) silane any one or
Two kinds；The titanate coupling agent is isopropyl three (dioctyl phosphoric acid acyloxy) titanate esters, monoalkoxy unsaturated fatty acid
Any one in titanate esters, Di(dioctylpyrophosphato) ethylene titanate or two kinds；The aluminate coupling agent is
Distearyl acyl-oxygen isopropyl Aluminate；The bimetallic coupling agent is zirconium Al bimetal coupling agent.
5. lithium ion battery according to claim 1 is plasticized porous polyethylene dry-stretched membrane with nanometer, it is characterised in that:
The crosslinking agent be bis- (tert-butyl peroxy base) hexanes of 2,5- dimethyl -2,5-, 2,5- dimethyl -2,5- bis- (tert-butyl peroxy bases) oneself
Alkynes -3, α, bis- (tert-butyl peroxy base) diisopropylbenzene (DIPB)s of α -, cumyl peroxide, bis- (tert-butyl peroxide) butane of 2,2-, 4- hydroxyl
Any one in base benzophenone laurate or two kinds.
6. lithium ion battery according to claim 1 is plasticized porous polyethylene dry-stretched membrane with nanometer, it is characterised in that:
The plasticiser is diisooctyl phthalate, dibutyl maleate, any one in diisobutyl maleate.
7. the preparation side that a kind of lithium ion battery as described in claim 1 is plasticized porous polyethylene dry-stretched membrane with nanometer
Method, it is characterised in that: include the following steps:
1) polyvinyl resin of formula ratio is mixed with crosslinking agent, plasticiser, nucleating agent, melts and squeezes under the conditions of 160~210 DEG C
Out, 50~100 DEG C are cooled to, sheet is made；
2) by sheet obtained by step 1) under the conditions of 60~110 DEG C using stretch by the way of lateral behind first longitudinal direction form a film to get.
8. lithium ion battery according to claim 7 is plasticized the preparation method of porous polyethylene dry-stretched membrane with nanometer,
It is characterized by: the mixing refers to that crosslinking agent, plasticiser, which are dissolved in organic solvent, is made solution, and gained is molten in step 1)
Liquid is sprayed in the pellet or powder of polyvinyl resin, is added nano-powder nucleating agent and is uniformly mixed；Alternatively, the mixing is
Crosslinking agent, plasticiser, organic nucleating agent are dissolved in organic solvent and solution are made by finger, and acquired solution is sprayed to polyvinyl resin
It is uniformly mixed in pellet or powder.
9. lithium ion battery according to claim 7 is plasticized the preparation method of porous polyethylene dry-stretched membrane with nanometer,
It is characterized by: when crosslinking agent used is photocatalyzed crossing agent, after sheet obtained by step 1) is carried out ultraviolet light, then
Carry out the operation of step 2；The time of the ultraviolet light is 5~20min.
10. the preparation side that the lithium ion battery according to claim 7 or 9 is plasticized porous polyethylene dry-stretched membrane with nanometer
Method, it is characterised in that: in step 2, longitudinal stretching multiplying power is 3~10 times, and cross directional stretch multiplying power is 2~5 times.
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| JP2018144480A (en) * | 2017-03-03 | 2018-09-20 | 住友化学株式会社 | Film production device and film production method |
| CN107221627A (en) * | 2017-06-16 | 2017-09-29 | 河南福森新能源科技有限公司 | A kind of polyolefin diaphragm of lithium ion battery and preparation method thereof |
| CN109054073B (en) * | 2018-07-19 | 2021-07-23 | 合肥星源新能源材料有限公司 | Polyolefin microporous membrane and preparation method thereof |
| CN110165129A (en) * | 2019-05-28 | 2019-08-23 | 大连中比动力电池有限公司 | Anti-oxidant high puncture strength dry method diaphragm of one kind and its preparation method and application |
| CN110197884A (en) * | 2019-06-10 | 2019-09-03 | 张雪花 | A kind of lithium battery diaphragm polyethene microporous membrane and preparation method |
| CN114561043B (en) * | 2022-04-07 | 2023-01-31 | 涿州市隽诚化工有限公司 | Polypropylene nucleating agent composition, and preparation method and application thereof |
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