CN107742688A - A kind of polyolefin lithium electric separator and preparation method thereof - Google Patents
A kind of polyolefin lithium electric separator and preparation method thereof Download PDFInfo
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- CN107742688A CN107742688A CN201710812779.0A CN201710812779A CN107742688A CN 107742688 A CN107742688 A CN 107742688A CN 201710812779 A CN201710812779 A CN 201710812779A CN 107742688 A CN107742688 A CN 107742688A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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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 polyolefin lithium electric separator, using porous polyolefin barrier film as matrix, the unilateral or bilateral electrospinning of the polyalkene diaphragm has modified polyethylene terephthalate (PET) fiber coat, the fiber that the pet fiber of described modification is inorganic oxide nanoparticles and polyethylene terephthalate is combined.The problem of present invention is directed to existing polypropylene or relatively low polyethylene porous separator high temperature integrity, and the problems such as pore structure existing for existing electrostatic spinning barrier film or uneven composite construction, a kind of polyolefin lithium electric separator is provided, can bearing temperature can reach 250~260 DEG C, effectively avoid the problem of the material melts closed pore under the maximum conditions of battery abuse, with good high temperature integrity, it can significantly improve the thermal safety of battery.
Description
Technical field
The invention belongs to new energy materialses field, and in particular to a kind of polyolefin lithium electric separator and preparation method thereof.
Background technology
Barrier film is the most critical material for determining lithium battery security, typically passes through dry method list by polypropylene or polyethylene
Draw, the double drawings of dry method or wet processing are prepared.Overcharge/cross put or other incorrect maximum conditions used under, lithium electricity
The temperature of pond inside battery very fast can rise to more than polyolefin fusing point, make barrier film generation fusing, both positive and negative polarity straight in regional area
Contact and short circuit, battery catches fire or blast.
At present, the method for improving lithium battery diaphragm is mainly (to be mainly in membrane surface coated inert high polymer binder
Kynoar PVDF, the ethylene copolymer PVD-HFP of vinylidene-hexafluoro third) bond nano inorganic oxide grain coating.
In the temperature range that polypropylene or base polyethylene film melt, such as 120~160 DEG C, inorganic oxide has preferable size steady
Qualitative, specific method is：It is in the presence of aqueous dispersion that binding agent and inorganic oxide is fully dispersed into slurry, re-coating
Ceramic coating is formed after being dried on barrier film, such as patent CN201110048688 discloses one kind and uses Kynoar high score
The inorganic particles such as sub- binding agent and aluminum oxide disperse in aqueous, so as to make under the aqueous dispersions such as polyethylene glycol auxiliary
The method of standby inorganic coating；Patent CN201310017708 discloses one kind under the thickeners such as carboxymethyl cellulose auxiliary, adopts
The method for being mixed with barrier film ceramic coating with the binding agents such as the ethylene copolymer of vinylidene~hexafluoro third and zeolite；Patent
CN201510706160.2 discloses lithium battery diaphragm of a kind of porous inorganic oxide containing lithium ion conduction and preparation method thereof,
Formed using lithium ion conduction polymer under Action of Surfactant with inorganic oxide precursor body it is first compound, then in hydro-thermal
Under the conditions of crystallization, formed can conducting lithium ions porous inorganic oxide, then with binding agent, stabilizer, the ultraviolet friendship of alkyl chain
Connection agent be mixed with slurry, be finally coated on lithium ion battery separator surface, ultraviolet irradiation and drying, obtain it is band coating every
Film.But the thermal stable temperature of high polymer binder also has a great impact to the heat endurance of coating in coating, binding agent is soft
Cohesive force is lost after change to come off；In addition, this coating can not be individually present after septum body softening, the barrier film sheet of larger area
Body melts the efflorescence that can cause coating, so as to be difficult to play a part of to obstruct both positive and negative polarity in extreme circumstances.
Electrostatic spinning (electrospinning) technology can obtain the barrier film of high porosity using the preferable polymer of melt temperature as raw material
Or coating.As patent CN201510849210.2 discloses the preparation method of electrostatic spinning composite diaphragm, using electrostatic spinning
Technology, the Kynoar precursor solution A compound with another polymer, Kynoar are mixed with inorganic nano material
Precursor solution B, be prepared into holey composite fibre barrier film；Patent CN201610747668.1 uses a kind of coaxial electrostatic
Spining technology prepares the composite cellulosic membrane of core/shell structure, and two layers of the nucleocapsid of composite cellulosic membrane is in concentric shaft-like, and stratum nucleare is by high-melting-point
Poly (aryl ether sulfone ketone) nanofiber form, shell is made up of the polyvinylidene fluoride nanometer fiber of low melting point, and porosity reaches 75%
More than, it is resistant to 180 DEG C of high temperature.But static spinning membrane has two directly as battery diaphragm, one is barrier film hole
Rate is very high, and representative value reaches 60~80%, causes that barrier film electronics isolation capacity is relatively low, and self-discharge of battery is serious, the second is quiet
Electrospun barrier film does not pass through orientation stretching, and common intensity is only 5~20MPa, far below stretched conventional membrane
More than 100MPa, it is difficult to meet battery manufacturing process and the needs of mechanical safety.
CN201510069176.7 discloses a kind of compound lithium ion battery separator, includes non-woven fabrics base material layer, electrostatic
Spinning layer and polyalcohol stephanoporate coating, specifically do base material with non-woven fabrics, ensure that the high porosity and heat resistance of barrier film；In nothing
Spin cloth base material upper and lower surface and electrostatic spinning layer is set, reduce non-woven fabrics pore size so that uniform pore diameter；Patent
CN201510069135.8 uses similar technique, and electrostatic spinning layer is prepared with the water soluble polymer of environment-friendly type, but Static Spinning
Cortina self discharge the problem of intensity with not still being solved.Patent CN201210128618.7 discloses a kind of three layers of Nanowire
Tie up composite lithium ion cell film and its technology of preparing, the battery membranes include positioned at intermediate layer non-woven fabrics or nano-fiber film and
The first outer layer and the second outer layer positioned at intermediate layer both sides, the first outer layer and the second outer layer are prepared using electrostatic spinning technique, so
Afterwards with the compound acquisition composite construction of intermediate layer hot pressing, but hot pressing is compound to polyalcohol stephanoporate base material and the hole knot of porous coating
Structure has considerable influence, needs monofilm to have larger thickness moreover, hot pressing is compound, does not meet that current diaphragm is thin layer to become
Gesture.
Patent CN201710142596.2 discloses a kind of polymer composite lithium battery membrane and preparation method thereof, and it polymerize
Thing composite lithium battery membrane includes basement membrane and the inorganic particulate coating coated in basement membrane one or both sides, also, inorganic particulate applies
The surface of layer be coated with least one layer of high-temperature resin layer, coating use dip coated, intaglio printing, spraying coating, extrusion coated,
A kind of method in electrostatic spinning and transfer coated is transferred on basement membrane, and still, inorganic oxide is physics side in this structure
Formula is added, and is existed and is difficult to scattered difficulty.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of polyolefin for above-mentioned the shortcomings of the prior art
Lithium electric separator, there is good high temperature integrity, can bearing temperature reach 240~260 DEG C, can significantly improve the heat of battery
Security.
The present invention is to solve the problems, such as that used technical scheme set forth above is：
A kind of polyolefin lithium electric separator, using porous polyolefin barrier film as matrix, the unilateral or bilateral of the polyalkene diaphragm
Coated with modified polyethylene terephthalate (PET) fiber coat, the polyethylene terephthalate of described modification
The fiber that ester (PET) fiber is inorganic oxide nanoparticles and polyethylene terephthalate is combined.
By such scheme, described porous polyolefin barrier film, thickness is 6~50 μm, and porosity is 35~50vol%；Change
Property polyethylene terephthalate (PET) fiber coat thickness be 2~10 μm.
By such scheme, described porous polyolefin barrier film base material is mainly selected from dry method list and draws double draw of polypropylene, dry method to gather
Any one in propylene or wet method polyethylene lithium electric separator etc..
By such scheme, the coating mainly uses electrostatic spinning (electrospinning).
By such scheme, the inorganic oxide is mainly selected from silica, alundum (Al2O3), titanium dioxide etc..
The present invention also provides the preparation method of said polyolefins lithium electric separator, and main process is：
The first step, in the mixed solution of terephthalic acid (TPA) and ethylene glycol, inorganic oxide precursor body uses electrostatic from group
The method synthesis inorganic oxide nanoparticles of dress, obtain the dispersion liquid of inorganic oxide nanoparticles, i.e., the dispersion liquid is with right
Phthalic acid and ethylene glycol are solvent, using inorganic oxide nanoparticles as solute；
Second step, the dispersion liquid of inorganic oxide nanoparticles obtained by the first step is heated, makes ethylene glycol therein
Esterification and polycondensation reaction occurs with terephthalic acid (TPA), obtains the compound polyethylene terephthalate of inorganic oxide nanoparticles
Ester (PET) dispersion liquid；
3rd step, after the compound PET dispersion liquids dilution of inorganic oxide nanoparticles obtained by second step, as spinning pulp
Material；Then spinning slurry is subjected to one side or two-sided electrostatic spinning in porous polyolefin barrier film, obtains modified poly- terephthaldehyde
The polyolefin lithium electric separator of sour glycol ester (PET) fiber composite.
By such scheme, in the first step, the weight ratio of terephthalic acid (TPA), inorganic oxide precursor body and ethylene glycol is 1：
0.01~0.1：2~5.
By such scheme, in the first step, described inorganic oxide precursor body is selected from tetraethyl orthosilicate, tetraethoxy-silicane
Any one in alkane, tetraethyl titanate, aluminium isopropoxide etc..
By such scheme, in the first step, the reaction condition of electrostatic self-assembled is：Inorganic acid is as hydrolyst, pH
0.1~2, the reaction time is 1~4h for 0.1~2, reaction system pH control.
By such scheme, in the first step, described inorganic acid preferred concentration is 10~30wt% aqueous solution, such as：Nitric acid
Any one in the aqueous solution, aqueous hydrochloric acid solution etc..
By such scheme, in the first step, the step of Disacidifying and dewatering is also included after the step of synthesizing inorganic oxide nanoparticles
Suddenly, it is specially：Heat under agitation and remove free inorganic acid and low boiling aqueous solvent to distill.Wherein, heating-up temperature is
180~193 DEG C.
By such scheme, in second step, the condition of esterification and polycondensation reaction to be heated to 220~240 DEG C, insulation 30~
40min.Wherein, preferably 2~5 DEG C/min of heating rate during heating.
By such scheme, in the 3rd step, viscosity is diluted between 1000~3000mPa.S, preferably isopropanol is as dilute
Release agent.
By such scheme, in the 3rd step, the environment temperature control of electrostatic spinning is 10~30 DEG C, humid control be 50~
70RH%；30~50kV of spinning positive voltage, negative voltage are -30~-10kV, and spinning layer thickness control is 2~10 μm.
Further, the present invention also provides a kind of preparation method of more specifically polyolefin lithium electric separator, detailed process
For：
1) terephthalic acid (TPA), inorganic oxide precursor body are dispersed in ethylene glycol, before terephthalic acid (TPA), inorganic oxide
The weight ratio for driving body and ethylene glycol is 1：0.01~0.1：2~5,0.5~2h is stirred after mixing；Then, delay under stirring
For the slow inorganic acid aqueous solution for adding concentration as 10~30wt% as hydrolyst, controlling the addition speed of acid makes solution system
PH value is maintained between 0.1~2, is continued 1~4h of stirring and is fully hydrolyzed completely；After the completion of hydrolysis, heat under agitation molten
Liquid system to solution temperature rises to 180~193 DEG C, removes free inorganic acid and low boiling aqueous solvent with distillation, then cools down
To room temperature, the dispersion liquid of inorganic oxide nanoparticles is obtained；
2) dispersion liquid of inorganic oxide nanoparticles obtained by the first step is warming up to 220~240 DEG C with 2~5 DEG C/min,
30~40min of insulation makes ethylene glycol and terephthalic acid (TPA) that esterification and polycondensation reaction occur, and obtains inorganic oxide nanoparticles and answers
The PET dispersion liquids of conjunction；
3) by the compound PET dispersion liquids of inorganic oxide nanoparticles obtained by second step be diluted to viscosity 1000~
After between 3000mPa.S, as spinning slurry；Then spinning slurry is carried out in porous polyolefin diaphragm matrix one side or
Two-sided electrostatic spinning, spinning environment temperature control is 10~30 DEG C, humid control is 50~70RH%；Spinning positive voltage 30~
50kV, negative voltage are -30~-10kV, and spinning layer thickness control is 2~10 μm；After the completion of spinning after drying, polyolefin is obtained
Lithium electric separator.
Compared with prior art, the beneficial effects of the invention are as follows：
First, the problem of being directed to existing polypropylene or relatively low polyethylene porous separator high temperature integrity of the invention, and
The problems such as pore structure existing for existing electrostatic spinning barrier film or uneven composite construction, there is provided a kind of polyolefin lithium electricity every
Film, because the modified PET fiber itself of inorganic oxide nanoparticles forms stable single layer structure, therefore can bearing temperature
240~260 DEG C can be reached, effectively avoid the problem of the material melts closed pore under the maximum conditions of battery abuse, had good
High temperature integrity, can significantly improve the thermal safety of battery.
Second, the method that the present invention uses In-situ reaction, the composite inorganic oxide nano particles in PET are inorganic
The functional group of oxide surface and the polarity of electrolyte are closer to can improve the toughness of PET coating and to electrolyte
Affinity, beneficial to the performance for improving composite diaphragm.
Brief description of the drawings
Fig. 1 is the cross-sectional scans electron microscopic picture of composite diaphragm in embodiment 1；
Fig. 2 is the ion milling high-resolution-ration transmission electric-lens photo of composite diaphragm fiber coat in embodiment 1.
Embodiment
For a better understanding of the present invention, with reference to the embodiment content that the present invention is furture elucidated, but the present invention
Content is not limited solely to the following examples.
Embodiment 1
A kind of polyolefin lithium electric separator, polypropylene lithium electric separator (20 μm, porosity 42vol%) is drawn as base with dry method list
Body, the bilateral electrospinning of the polyalkene diaphragm have modified polyethylene terephthalate (PET) fiber coat, and modified is poly-
The thickness of ethylene glycol terephthalate (PET) fiber coat is 2 μm；The polyethylene terephthalate of described modification
(PET) fiber is the fiber that nano SiO 2 particle and polyethylene terephthalate are combined.
The preparation method of said polyolefins lithium electric separator, is comprised the following steps that：
1) terephthalic acid (TPA), tetraethyl orthosilicate are dispersed in ethylene glycol and stir 0.5h, terephthalic acid (TPA), tetraethyl orthosilicate
Weight ratio with ethylene glycol is 1：0.05：2；Then, continue to be slowly added into the nitric acid aqueous solution that concentration is 10wt% under stirring
For solution as hydrolyst, control, which adds speed, makes solution system pH be maintained between 0.1~0.3, and it is abundant to continue stirring 1h
Hydrolysis；After the completion of hydrolysis, heated solution system to solution temperature rises to 180 DEG C under agitation, and distillation removes free nothing
Machine acid and low boiling aqueous solvent, are subsequently cooled to room temperature, obtain the dispersion liquid of nano SiO 2 particle；
2) dispersion liquid of nano SiO 2 particle obtained by step 1) is added in reactor, 220 is warming up to 2 DEG C/min
DEG C, insulation 30min makes ethylene glycol and terephthalic acid (TPA) that esterification and polycondensation reaction occur, and it is compound to obtain nano SiO 2 particle
PET dispersion liquids；
3) isopropanol will be added in the compound PET dispersion liquids of nano SiO 2 particle obtained by step 2) and is diluted regulation
It is 2800~3000mPa.S to viscosity, as spinning slurry, the wherein addition of isopropanol is phthalic acid weight in step 1)
5 times；Then by spinning slurry by nanofiber spinning-drawing machine dry method list draw polypropylene lithium electric separator (20 μm, porosity
Two-sided electrostatic spinning 42vol%) is carried out on matrix, spinning environment temperature control is 10 DEG C, humid control 50RH%, and spinning is just
Voltage 30kV, negative voltage are -10kV, and spinning layer thickness control is 2 μm；After the completion of spinning, gained film is positioned over 90 DEG C of baking ovens
Middle drying 10 hours, obtain the compound polyolefin lithium electric separator of modified PET fiber.
The cross-sectional scans electromicroscopic photograph of polyolefin lithium electric separator obtained by the present embodiment is as shown in Figure 1, it can be seen that electrostatic
The fiber coat and polypropylene matrix of spinning are tightly combined, uniform cross, also, the modification of inorganic silicon dioxide nano particle
PET forms the film of one layer of a little micron thickness in matrix surface, and surface structure is from ESEM it is seen that a volume
The rock-steady structure to be formed is knitted, deduction is a single layer structure that can be stabilized, therefore the modification of inorganic oxide nanoparticles
PET itself forms stable single layer structure；And the ion milling high score of the fiber coat of gained polyolefin lithium electric separator
Distinguish transmission electron microscope photo as shown in Figure 2, it can be seen that nano SiO 2 particle is evenly distributed in PET.
In embodiment 1 and following other embodiments, the coating stripping of lithium electric separator is measured using universal material stretching-machine
Power, fracture strength, puncture strength；Porosity is measured using Gurley Permeability gauges；Use powdered LiFePO4 for positive electrode,
Delanium is that negative pole assembles button cell, is heated up in environmental test chamber with 0.1 DEG C/min speed, using electrochemical operation
Temperature when measurement short circuit of standing occurs.The various aspects of performance index of the gained polyolefin lithium electric separator of embodiment 1 is as shown in table 1, together
When table 1 in also enclose the various aspects of performance index of matrix itself used by the present embodiment.
Table 1
Embodiment 2
A kind of polyolefin lithium electric separator, polypropylene lithium electric separator (50 μm, porosity 39vol%) is drawn as base so that dry method is double
Body, the bilateral electrospinning of the polyalkene diaphragm have modified polyethylene terephthalate (PET) fiber coat, and modified is poly-
The thickness of ethylene glycol terephthalate (PET) fiber coat is 5 μm；The polyethylene terephthalate of described modification
(PET) fiber is the fiber that nano SiO 2 particle and polyethylene terephthalate are combined.
The preparation method of said polyolefins lithium electric separator, is comprised the following steps that：
1) terephthalic acid (TPA), tetraethoxysilane are dispersed in ethylene glycol and stir 1h, terephthalic acid (TPA), tetraethoxy-silicane
The weight of alkane and ethylene glycol ratio is 1：0.01：3；Then, continue to be slowly added into the hydrochloric acid that concentration is 20wt% under stirring
For the aqueous solution as hydrolyst, control, which adds speed, makes solution system pH be maintained between 0.5~0.7, continues stirring 3h and fills
Divide hydrolysis；After the completion of hydrolysis, heated solution system to solution temperature rises to 190 DEG C under agitation, and distillation removes free
Inorganic acid and low boiling aqueous solvent, are subsequently cooled to room temperature, obtain the dispersion liquid of nano SiO 2 particle；
2) dispersion liquid of nano SiO 2 particle obtained by step 1) is added in reactor, 230 is warming up to 4 DEG C/min
DEG C, insulation 35min makes ethylene glycol and terephthalic acid (TPA) that esterification and polycondensation reaction occur, and it is compound to obtain nano SiO 2 particle
PET dispersion liquids；
3) isopropanol will be added in the compound PET dispersion liquids of nano SiO 2 particle obtained by step 2) and is diluted regulation
It is 2100~2200mPa.S to viscosity, as spinning slurry, the wherein addition of isopropanol is phthalic acid weight in step 1)
8 times；Then by spinning slurry by nanofiber spinning-drawing machine dry method it is double draw polypropylene lithium electric separators (50 μm, porosity
Two-sided electrostatic spinning 39vol%) is carried out on matrix, spinning environment temperature control is 25 DEG C, humid control 60RH%, and spinning is just
Voltage 40kV, negative voltage are -20kV, and spinning layer thickness control is 5 μm；After the completion of spinning, gained film is positioned over 95 DEG C of baking ovens
Middle drying 8 hours, obtain the compound polyolefin lithium electric separator of modified PET fiber.
The various aspects of performance index of the gained polyolefin lithium electric separator of embodiment 2 is as shown in table 2, while this is also enclosed in table 2
The various aspects of performance index of matrix itself used by embodiment.
Table 2
| Performance indications | The gained lithium electric separator of embodiment 2 | Matrix |
| Porosity % | 45 | 39 |
| Air penetrability s/100mL | 533 | 517 |
| Puncture strength, gf | 807 | 792 |
| Longitudinal tensile strength, MPa | 146 | 153 |
| Coating strip force Nm-1 | 37.4 | / |
| Short-circuit temperature DEG C | 252 | 173 |
Embodiment 3
A kind of polyolefin lithium electric separator, with wet method polyethylene lithium electric separator (12 μm, 46vol%) for matrix, the polyene
The unilateral electrospinning of hydrocarbon barrier film has modified polyethylene terephthalate (PET) fiber coat, modified poly terephthalic acid
The thickness of glycol ester (PET) fiber coat is 10 μm；Polyethylene terephthalate (PET) fiber of described modification is
The fiber that titania nanoparticles and polyethylene terephthalate are combined.
The preparation method of said polyolefins lithium electric separator, is comprised the following steps that：
1) terephthalic acid (TPA), tetraethyl titanate are dispersed in ethylene glycol and stir 2h, terephthalic acid (TPA), tetraethyl titanate and second two
The weight ratio of alcohol is 1：0.1：5；Then, continue to be slowly added into the aqueous hydrochloric acid solution conduct that concentration is 30wt% under stirring
Hydrolyst, control, which adds speed, makes solution system pH be maintained between 1.6~2, continues stirring 4h and is fully hydrolyzed；Hydrolyze
Cheng Hou, under agitation heated solution system to solution temperature rise to 193 DEG C, distillation removes free inorganic acid and low boiling
Aqueous solvent, room temperature is subsequently cooled to, obtains the dispersion liquid of nano SiO 2 particle；
2) dispersion liquid of nano SiO 2 particle obtained by step 1) is added in reactor, 240 is warming up to 5 DEG C/min
DEG C, insulation 40min makes ethylene glycol and terephthalic acid (TPA) that esterification and polycondensation reaction occur, and it is compound to obtain nano SiO 2 particle
PET dispersion liquids；
3) isopropanol will be added in the compound PET dispersion liquids of nano SiO 2 particle obtained by step 2) and is diluted regulation
It is 1000~1200mPa.S to viscosity, as spinning slurry, the wherein addition of isopropanol is phthalic acid weight in step 1)
10 times；Then by spinning slurry by nanofiber spinning-drawing machine in wet method polyethylene lithium electric separator (12 μm, 46vol%) matrix
Upper progress one side electrostatic spinning, spinning environment temperature control is 30 DEG C, humid control 70RH%, spinning positive voltage 50kV, is born
Voltage is -30kV, and spinning layer thickness control is 10 μm；After the completion of spinning, it is small that gained film is positioned in 100 DEG C of baking ovens dry 10
When, obtain the compound polyolefin lithium electric separator of modified PET fiber.
The various aspects of performance index of the gained polyolefin lithium electric separator of embodiment 3 is as shown in table 3, while this is also enclosed in table 3
The various aspects of performance index of matrix itself used by embodiment.
Table 3
| Performance indications | The gained lithium electric separator of embodiment 3 | Matrix |
| Porosity % | 52 | 46 |
| Air penetrability s/100mL | 174 | 167 |
| Puncture strength, gf | 335 | 326 |
| Longitudinal tensile strength, MPa | 146 | 153 |
| Coating strip force Nm-1 | 42.5 | / |
| Short-circuit temperature DEG C | 246 | 135 |
Embodiment 4
A kind of polyolefin lithium electric separator, polypropylene lithium electric separator (15 μm, 46vol%) is drawn as matrix with dry method list, it is described
The unilateral electrospinning of polyalkene diaphragm has modified polyethylene terephthalate (PET) fiber coat, and modified is poly- to benzene two
The thickness of formic acid glycol ester (PET) fiber coat is 3 μm；The polyethylene terephthalate (PET) of described modification is fine
Dimension is the fiber that aluminium dioxide nano particle and polyethylene terephthalate are combined.
The preparation method of said polyolefins lithium electric separator, is comprised the following steps that：
The preparation method of said polyolefins lithium electric separator, is comprised the following steps that：
1) terephthalic acid (TPA), aluminium isopropoxide are dispersed in ethylene glycol and stir 1h, terephthalic acid (TPA), aluminium isopropoxide and second two
The weight ratio of alcohol is 1：0.03：4；Then, continue to be slowly added into the aqueous solution of nitric acid work that concentration is 30wt% under stirring
For hydrolyst, control, which adds speed, makes solution system pH be maintained between 0.1~0.12, continues stirring 3h and is fully hydrolyzed；
After the completion of hydrolysis, heated solution system to solution temperature rises to 190 DEG C under agitation, distillation remove free inorganic acid and
Low boiling aqueous solvent, is subsequently cooled to room temperature, obtains the dispersion liquid of nano SiO 2 particle；
2) dispersion liquid of nano SiO 2 particle obtained by step 1) is added in reactor, 222 is warming up to 3 DEG C/min
DEG C, insulation 40min makes ethylene glycol and terephthalic acid (TPA) that esterification and polycondensation reaction occur, and it is compound to obtain nano SiO 2 particle
PET dispersion liquids；
3) isopropanol will be added in the compound PET dispersion liquids of nano SiO 2 particle obtained by step 2) and is diluted regulation
It is 2200~2400mPa.S to viscosity, as spinning slurry, the wherein addition of isopropanol is phthalic acid weight in step 1)
7 times；Then spinning slurry is drawn into polypropylene lithium electric separator (15 μm, 46vol%) by nanofiber spinning-drawing machine in dry method list
One side electrostatic spinning is carried out on matrix, spinning environment temperature control is 20 DEG C, humid control 70RH%, spinning positive voltage
50kV, negative voltage are -30kV, and spinning layer thickness control is 3 μm；After the completion of spinning, gained film is positioned in 100 DEG C of baking ovens and done
Dry 7 hours, obtain the compound polyolefin lithium electric separator of modified PET fiber.
The various aspects of performance index of the gained polyolefin lithium electric separator of embodiment 4 is as shown in table 4, while this is also enclosed in table 4
The various aspects of performance index of matrix itself used by embodiment.
Table 4
| Performance indications | The gained lithium electric separator of embodiment 4 | Matrix |
| Porosity % | 51 | 46 |
| Air penetrability s/100mL | 193 | 185 |
| Puncture strength, gf | 342 | 336 |
| Longitudinal tensile strength, MPa | 141 | 146 |
| Coating strip force Nm-1 | 38.4 | / |
| Short-circuit temperature DEG C | 247 | 165 |
As shown in table 1~4, the porosity of polyolefin lithium electric separator is high prepared by the present invention, and gas permeability is good, puncture strength and
Longitudinal tensile strength, shrinkage factor are suitable, and short-circuit temperature has good high temperature integrity at 243~252 DEG C, can be significantly
Improve the thermal safety of battery.Wherein, relative to respective matrix, because the high porosity of electrospinning fibre layer is to the hole of barrier film
Rate, gas permeability etc. do not influence significantly.
Described above is only the preferred embodiment of the present invention, it is noted that is come for one of ordinary skill in the art
Say, without departing from the concept of the premise of the invention, some modifications and variations can also be made, these belong to the present invention's
Protection domain.
Claims (10)
- A kind of 1. polyolefin lithium electric separator, using porous polyolefin barrier film as matrix, it is characterised in that the list of the polyalkene diaphragm Side or two-sided coatings have modified pet fiber coating, the poly terephthalic acid second two of described modification The fiber that alcohol ester fiber is inorganic oxide nanoparticles and polyethylene terephthalate is combined.
- A kind of 2. polyolefin lithium electric separator according to claim 1, it is characterised in that described porous polyolefin barrier film is thick Spend for 6~50 μm, porosity is 35~50vol%；The thickness of modified pet fiber coating be 2~ 10μm。
- A kind of 3. polyolefin lithium electric separator according to claim 1, it is characterised in that described porous polyolefin barrier film base Material is mainly selected from any one in dry method list drawing polypropylene, the double drawing polypropylene of dry method or wet method polyethylene lithium electric separator；It is described Inorganic oxide is mainly selected from silica, alundum (Al2O3), titanium dioxide.
- 4. a kind of preparation method of polyolefin lithium electric separator, it is characterised in that its main process is：The first step, in the mixed solution of terephthalic acid (TPA) and ethylene glycol, inorganic oxide precursor body is using electrostatic self-assembled Method synthesizes inorganic oxide nanoparticles, obtains the dispersion liquid of inorganic oxide nanoparticles, i.e., the dispersion liquid is with to benzene two Formic acid and ethylene glycol are solvent, using inorganic oxide nanoparticles as solute；Second step, the dispersion liquid of inorganic oxide nanoparticles obtained by the first step is heated, make ethylene glycol therein and right Esterification and polycondensation reaction occur for phthalic acid, obtain inorganic oxide nanoparticles compound polyethylene terephthalate point Dispersion liquid；3rd step, the compound polyethylene terephthalate dispersion liquid of inorganic oxide nanoparticles obtained by second step is diluted Afterwards, as spinning slurry；Then spinning slurry is subjected to one side or two-sided electrostatic spinning in porous polyolefin barrier film, changed The property compound polyolefin lithium electric separator of pet fiber.
- 5. the preparation method of a kind of polyolefin lithium electric separator according to claim 4, it is characterised in that in the first step, to benzene The weight ratio of dioctyl phthalate, inorganic oxide precursor body and ethylene glycol is 1：0.01~0.1：2~5.
- A kind of 6. preparation method of polyolefin lithium electric separator according to claim 4, it is characterised in that in the first step, electrostatic The reaction condition of self assembly is：For inorganic acid as hydrolyst, pH is 0.1~2, and reaction system pH controls are 0.1~2, instead It is 1~4h between seasonable.
- A kind of 7. preparation method of polyolefin lithium electric separator according to claim 4, it is characterised in that in the first step, synthesis The step of also including Disacidifying and dewatering after the step of inorganic oxide nanoparticles.
- A kind of 8. preparation method of polyolefin lithium electric separator according to claim 4, it is characterised in that in second step, esterification Condition with polycondensation reaction is incubated 30-40min to be heated to 220-240 DEG C.
- A kind of 9. preparation method of polyolefin lithium electric separator according to claim 4, it is characterised in that in the 3rd step, dilution To viscosity between 1000~3000mPa.S, preferably isopropanol is as diluent.
- 10. the preparation method of a kind of polyolefin lithium electric separator according to claim 4, it is characterised in that quiet in the 3rd step The environment temperature control of Electrospun is 10~30 DEG C, humid control is 50~70RH%；30~50kV of spinning positive voltage, negative voltage For -30~-10kV, spinning layer thickness control is 2~10 μm.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108777284A (en) * | 2018-06-11 | 2018-11-09 | 佛山腾鲤新能源科技有限公司 | A kind of preparation method of lithium ion battery composite separation membrane |
| CN110875452A (en) * | 2018-09-03 | 2020-03-10 | 三星Sdi株式会社 | Separator for rechargeable lithium battery and rechargeable lithium battery including the same |
| CN111710816A (en) * | 2020-06-23 | 2020-09-25 | 深圳市德立新材料科技有限公司 | Preparation method of nanoscale PET material applied to lithium battery non-woven fabric diaphragm |
| CN112531292A (en) * | 2020-12-11 | 2021-03-19 | 宁波启新精合新能源研究院有限公司 | Lithium ion battery diaphragm prepared from inorganic-organic composite material |
| CN112787042A (en) * | 2020-04-24 | 2021-05-11 | 深圳市劢全新材料科技有限责任公司 | Lithium battery diaphragm and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102629679A (en) * | 2012-04-28 | 2012-08-08 | 中国科学院理化技术研究所 | Nanometer fiber lithium ion battery diaphragm material with composite structure and preparation method of nanometer fiber lithium ion battery diaphragm material |
| CN102779964A (en) * | 2012-08-08 | 2012-11-14 | 龙能科技（苏州）有限公司 | Method for preparing multilayer composite membrane for secondary battery by using electrostatic spinning coating method |
| CN102931370A (en) * | 2012-10-24 | 2013-02-13 | 江苏大学 | Organic/inorganic composite nanofiber membrane of lithium ion power battery and preparation method of organic/inorganic composite nanofiber membrane |
-
2017
- 2017-09-11 CN CN201710812779.0A patent/CN107742688B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102629679A (en) * | 2012-04-28 | 2012-08-08 | 中国科学院理化技术研究所 | Nanometer fiber lithium ion battery diaphragm material with composite structure and preparation method of nanometer fiber lithium ion battery diaphragm material |
| CN102779964A (en) * | 2012-08-08 | 2012-11-14 | 龙能科技（苏州）有限公司 | Method for preparing multilayer composite membrane for secondary battery by using electrostatic spinning coating method |
| CN102931370A (en) * | 2012-10-24 | 2013-02-13 | 江苏大学 | Organic/inorganic composite nanofiber membrane of lithium ion power battery and preparation method of organic/inorganic composite nanofiber membrane |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108777284A (en) * | 2018-06-11 | 2018-11-09 | 佛山腾鲤新能源科技有限公司 | A kind of preparation method of lithium ion battery composite separation membrane |
| CN110875452A (en) * | 2018-09-03 | 2020-03-10 | 三星Sdi株式会社 | Separator for rechargeable lithium battery and rechargeable lithium battery including the same |
| US11843091B2 (en) | 2018-09-03 | 2023-12-12 | Samsung Sdi Co., Ltd. | Separator for rechargeable lithium battery and rechargeable lithium battery including the same |
| CN112787042A (en) * | 2020-04-24 | 2021-05-11 | 深圳市劢全新材料科技有限责任公司 | Lithium battery diaphragm and preparation method thereof |
| CN111710816A (en) * | 2020-06-23 | 2020-09-25 | 深圳市德立新材料科技有限公司 | Preparation method of nanoscale PET material applied to lithium battery non-woven fabric diaphragm |
| CN111710816B (en) * | 2020-06-23 | 2022-08-30 | 深圳市德立新材料科技有限公司 | Preparation method of nanoscale PET material applied to lithium battery non-woven fabric diaphragm |
| CN112531292A (en) * | 2020-12-11 | 2021-03-19 | 宁波启新精合新能源研究院有限公司 | Lithium ion battery diaphragm prepared from inorganic-organic composite material |
| CN112531292B (en) * | 2020-12-11 | 2023-03-31 | 宁波启新精合新能源研究院有限公司 | Lithium ion battery diaphragm prepared from inorganic-organic composite material |
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Denomination of invention: A polyolefin lithium diaphragm and its preparation method Effective date of registration: 20220622 Granted publication date: 20200804 Pledgee: Bank of China Limited Wuhan Jianghan sub branch Pledgor: HUIQIANG (WUHAN) NEW ENERGY MATERIAL TECHNOLOGY CO.,LTD. Registration number: Y2022420000176 |