CN104201310B - Polyolefin/aramid nano-fiber composite membrane and preparation thereof for lithium ion battery - Google Patents
Polyolefin/aramid nano-fiber composite membrane and preparation thereof for lithium ion battery Download PDFInfo
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- CN104201310B CN104201310B CN201410404032.8A CN201410404032A CN104201310B CN 104201310 B CN104201310 B CN 104201310B CN 201410404032 A CN201410404032 A CN 201410404032A CN 104201310 B CN104201310 B CN 104201310B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention belongs to the membrane material preparing technical field of electrochmical power source energy-storage travelling wave tube, disclose a kind of polyolefin for lithium ion battery/aramid nano-fiber composite membrane and preparation method thereof.The method comprises the following steps: after introducing acidic-group on polyolefin porous membrane surface, with base extraction, obtain the polyolefin porous membrane that surface is electronegative；It is immersed in polyelectrolyte solution, is obtained the polyolefin porous membrane that surface is positively charged；It is immersed in again in aramid nano-fiber dispersion liquid, takes out, wash, be dried, obtain polyolefin/aramid nano-fiber composite membrane.The polyolefin of the present invention/aramid nano-fiber composite membrane has low temperature closed pore characteristic and high-temperature stability, it is adaptable to the electrochemical device worked under higher temperature, and the aramid nano-fiber layer of introducing is loose structure, keeps relatively high ionic conductivity；Base film is combined with aramid nano-fiber interlayer electrostatic interaction, it is not easy to the stripping of aramid nano-fiber film and base film occurs, it is ensured that cycle performance of battery.
Description
Technical field
The invention belongs to the membrane material preparing technical field of electrochmical power source energy-storage travelling wave tube, be used for particularly to one
The polyolefin of lithium ion battery/aramid nano-fiber composite membrane and its preparation method and application.
Background technology
Barrier film is a key component in lithium ion battery, plays the effect of isolation both positive and negative polarity, is possible to prevent
Both positive and negative polarity is in direct contact with and causes circuit internal short-circuit together；There is again the effect of lithium ion conducting simultaneously, every
The loose structure of film or because absorbing electrolyte to form gel, make when discharge and recharge lithium ion can pass through every
Film, inside battery conducting forms loop, thus realizes the mutual conversion of chemical energy and electric energy.Although barrier film is not
Participate in the process that relevant energy is changed in battery, but the properties of barrier film to the capacity of battery, service life,
Multiplying power discharging property and safety etc. suffer from critically important impact.
Lithium ion battery separator can be divided into perforated membrane, non-woven membrane, polymer dielectric film, composite membrane etc..
The barrier film of existing commercialization mostly is the perforated membrane with polyolefin as base material.But, polyolefin porous membrane there is also
Weak point, one of them prominent shortcoming is exactly when temperature reaches near the fusing point of its bulk material,
Owing to there is internal stress, barrier film can produce stronger contraction；Temperature reach bulk material fusing point and more than
Time, barrier film even melt fracture, lose the effect of isolation both positive and negative polarity, inside battery will appear from short circuit, thus
Potential safety hazard occurs；Another shortcoming is that film exists " pin hole " phenomenon in microstructure, and i.e. internal is micro-
Hole is direct through barrier film.And lithium ion battery can separate out Li dendrite in the process of discharge and recharge, particularly exist
When overcharging, Li dendrite is easy to deposit on the diaphragm surface and is easy to wear out barrier film, makes both positive and negative polarity
Short circuit.Therefore for the power lithium-ion battery that security requirement is higher, membrane thicknesses used typically can not
Less than 30 μm.It addition, polyalkene diaphragm surface is chemically inert, surface can be smaller, to conventional
The wettability of the organic electrolyte that polarity is bigger is bad comparatively speaking so that battery irrigates electricity in process of production
Solve liquid and need the longer time, reduce the production efficiency of battery.
For the percent thermal shrinkage aspect of reduction polyolefin porous membrane, generally use adhesive such as Kynoar
(PVDF), Kynoar-hexafluoropropene (PVDF-HFP) or styrene-butadiene latex (SBR) etc. are by dioxy
The inorganic nano-particles such as SiClx, aluminium oxide, titanium oxide, Barium metatitanate. be bonded to one of polyolefin porous membrane or
On two surfaces.But inorganic nano-particle is sticked to polyolefin surfaces by the adhesion by adhesive merely
On, due to the capillarity of perforated membrane, adhesive can enter in hole and result in blockage, cause membrane electrical resistance
Increase；And in charge and discharge cycles, the most all can occur swelling in the electrolytic solution due to adhesive, matrix
Being susceptible between film and high-temperaure coating or inorganic nano-particle peel off, its internal resistance can be increased dramatically, electricity
The cycle performance fast decay in pond.
Start research and development both at home and abroad and directly prepared porous septum method by high temperature resistant base material.Some are used to have Gao Rong
The perforated membrane prepared of polymer of point or non-woven membrane.Wherein using aramid fiber as base material prepare lithium ion battery every
Film aspect has substantial amounts of research.Aramid fiber is the polyamide in main chain containing phenyl ring.Its decomposition temperature is high, has
Good solvent resistance, thermostability, anti-flammability and thermal insulation, good mechanical performance, is current mechanical strength
One of the strongest synthesis macromolecule.Below 300 DEG C more stable, thermal contraction will not occur.Only work as temperature
When degree continues to raise, aramid fiber just can be degraded.Some the most external barrier film manufacturers be devoted to develop with
Aramid fiber is base material or the lithium ion battery separator of other base materials with aramid fiber modification, in order to improve the heat-resisting of barrier film
Property, thus ensure the safety of barrier film.But, existing research use technology otherwise preparation process is complicated,
Preparation condition is the harshest, otherwise the film thickness prepared exactly is thick, poor tensile strength, and it cannot be guaranteed that
The fastness that aramid fiber is combined with base film, in charge and discharge cycles, base film is the most peeling-off with aramid fiber to be caused
Interface resistance increases, and makes the chemical property of battery decline.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art with not enough, the primary and foremost purpose of the present invention is to provide a kind of use
Preparation method in the polyolefin/aramid nano-fiber composite membrane of lithium ion battery.
Another object of the present invention is the polyolefin/aramid fiber for lithium ion battery providing said method to prepare
Nano-fiber composite film.
Still a further object of the present invention is to provide above-mentioned polyolefin/aramid nano-fiber for lithium ion battery multiple
Close film application in electrochemical device.
The purpose of the present invention is realized by following proposal:
A kind of preparation method of the polyolefin for lithium ion battery/aramid nano-fiber composite membrane, including with
Lower step:
(1), after introducing acidic-group on polyolefin porous membrane surface, with base extraction, surface band is obtained
The polyolefin porous membrane of negative charge；
(2) it is immersed in the polyelectrolyte solution of the positively charged group of side chain, is obtained surface positively charged
The polyolefin porous membrane of lotus；
(3) polyolefin porous membrane positively charged for surface is immersed in aramid nano-fiber dispersion liquid, takes
Go out, wash, be dried, obtain polyolefin/aramid nano-fiber composite membrane.
The polyolefin porous membrane surface of gained polyolefin/aramid nano-fiber composite membrane has at least one of which aramid fiber
Nanofiber.
The polyolefin of the present invention/aramid nano-fiber composite membrane can by circulation repeat step (3) immersion,
Wash, be dried, thus obtain the polyolefin/aramid nano-fiber composite membrane with multilamellar aramid nano-fiber.
Polyelectrolyte described in step (2) can be for having the quaternary ammonium salt of structure, season shown in lower formula I or formula II
Microcosmic salt, sulfonium salt, or intramolecular has the polyelectrolyte of heteroaromatic cation of armaticity, or poly dimethyl two
Allyl ammonium chloride (PDDA) etc..
In formula I and formula II, A is the atoms such as N, O or S, and B, E are respectively the atoms such as N, P or S,
D is phenylene or methylene.X1 ˉ、X2 ˉIt is respectively electronegative halogen ion (such as Clˉ、Brˉ、
Iˉ), or other electronegative acid ions are (such as SO4 ˉ、PO4 3ˉ、NO3 ˉ) etc..R1、R2
It is respectively H atom or alkyl, such as methyl, ethyl etc., R3、R4Be respectively alkyl, as methyl, ethyl,
Propyl group, butyl, amyl group or hexyl etc..M, n are respectively the natural number of 0～10.When B is that N or P is former
The period of the day from 11 p.m. to 1 a.m, p=3, when B is S atom, p=2.
The molecular weight of polyelectrolyte used by the present invention is preferably 5000～3000000.Polyelectrolyte solution used
Concentration can be adjusted as required, any this area conventional treatment concentration.Be preferably 1～
10%.Described quaternary ammonium salt, quaternary alkylphosphonium salt, sulfonium salt polyelectrolyte under solution state on side chain with quaternary ammonium from
The positive charge groups such as son, quaternary phosphonium ion, sulfonium cation.
The dispersion liquid of the electronegative aramid nano-fiber in surface that the present invention uses, its preparation method specifically can be joined
The document (ACS Nano, 2011,5 (9), pp6945 6954) reported according to M.Yang etc..
The mass concentration scope of the aramid nano-fiber dispersion liquid that the present invention uses is 1 × 10-3%～8%.When
During the excessive concentration of aramid nano-fiber dispersion liquid used, the viscosity of dispersion liquid is relatively big, is unfavorable for that coating is uniformly.
The present invention is it is demonstrated experimentally that in order to make polyolefin porous membrane surface enclose uniform aramid nano-fiber and make institute
The composite membrane of preparation has a preferable ionic conductivity, and the concentration of aramid nano-fiber dispersion liquid preferably 1 ×
10-3～1%, more preferably 1 × 10-2～0.1%.
The aramid fiber that the present invention uses can be containing Si in conventional meta-aramid or p-aramid fiber, or strand
Etc. heteroatomic meta-aramid or p-aramid fiber etc., its molecular weight is 2000～2000000.The form of aramid fiber
Can be monofilament, multifibres, chopped strand, pulp, aramid yarn or aramid fabric etc..
Preferably, the polyolefin porous membrane that the present invention uses can be polyethylene porous membrane, polypropylene porous film
With at least one in the duplicature of polyethylene/polypropylene or multilayer film.
The described acidic-group that introduces on polyolefin porous membrane surface refers to by irradiation grafting or chemical graft
Method realizes.
Described acidic-group can be the groups such as carboxyl, phenolic hydroxyl group, sulfonic group, benzenesulfonic acid base or phosphate.
Alkali liquor described in step (1) is chosen as but is not restricted to KOH, NaOH, LiOH, K2CO3、
Na2CO3、Li2CO3、KHCO3Or NaHCO3Deng alkaline aqueous solution.Alkaline aqueous solution concentration used
Can adjust as required, any this area conventional treatment concentration.It is preferably pH=8～14.
The number of times that described circulation repeats can be between 1～100, thus introduces many at polyolefin porous membrane surface
Layer aramid nano-fiber.Circulation number of operations preferably 1～50, more preferably 1～20.Aramid nano-fiber
When dispersion liquid concentration is the biggest, circulation number of operations should suitably reduce to obtain suitable breathability, makes composite membrane
Possess suitable ionic conductivity and thermostability.
Every time in operation, the time being dipped in aramid nano-fiber dispersion liquid controls in 0.1～20min,
Preferably soak time is 1～3min.After immersion, washing, at 50～100 DEG C, it is dried 1～120min,
Baking temperature preferably 60～90 DEG C, drying time preferably 1～60min.
The present invention obtains, by process, the polyolefin porous membrane that surface is positively charged, then by being soaked in band
In the aramid nano-fiber dispersion liquid of negative charge, utilize electrostatic adsorption, make aramid nano-fiber absorption exist
Polyolefin porous membrane surface, through washing, is dried, obtains polyolefin porous membrane surface and be adsorbed with aramid fiber Nanowire
The composite membrane of dimension, then by repeatedly soaking, utilize hydrogen bond action at aramid nano-fiber surface adsorption multilamellar virtue
Synthetic fibre nanofiber, thus obtain polyolefin porous membrane surface and be adsorbed with the composite membrane of multilamellar aramid nano-fiber.
And can need with the breathability and thermostability controlling composite membrane by controlling the number of times of absorption aramid nano-fiber
In the range of Yaoing.
The polyolefin porous membrane that complex method of the present invention prepares is suitable for the composite membrane of aramid nano-fiber
In various electrochemical devices, especially as the film group of lithium ion battery or other chemical energy storage devices
Part.Owing to polyolefin porous membrane surface is with resistant to elevated temperatures aramid nano-fiber, the thermostability of composite membrane is significantly
Improving, therefore the composite membrane of the present invention is especially suitable for use as the membrane material of power lithium-ion battery.
The present invention, relative to prior art, has such advantages as and beneficial effect:
(1) polyolefin of the present invention/aramid nano-fiber composite membrane combines the low temperature of polyolefin porous membrane and closes
Pore property and the high-temperature stability of aramid fiber, it is adaptable to need in the electrochemical device worked at relatively high temperatures,
As in lithium ion battery, the safety of lithium ion battery can be improved.
(2) exist relatively between the aramid nano-fiber on the polyolefin of the present invention/aramid nano-fiber composite membrane
Many spaces, and do not block the hole of polyolefin porous membrane, utilize adhesive compound poly-relative to prior art
Alkene perforated membrane and the composite membrane of aramid fiber gained, have the ionic conductivity significantly improved.
(3) polyolefin of the present invention/aramid nano-fiber composite membrane is with improved polyalkene perforated membrane as matrix
Film, adsorption multi-layer aramid nano-fiber layer on it, polyolefin layer and aramid nano-fiber layer are electrostatic force absorption
Effect, and between aramid nano-fiber layer, it is hydrogen bond action, adhesion is strong, is not easy in charge and discharge cycles
Peeling-off with base film, interface resistance increases with circulating battery number of times and the most significantly increases, and effectively carries
The cycle performance of high battery.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention do not limit
In this.
Embodiment 1
A kind of polyolefin/aramid nano-fiber composite membrane, is prepared by following methods:
(1) preparation method of aramid nano-fiber dispersion liquid can refer to the document (ACS that Yang etc. is reported
Nano,2011,5(9),pp6945–6954).With the system that mass fraction is 2% aramid nano-fiber dispersion liquid
As a example by Bei, its preparation method is: aramid yarn (the Kevlar fiber of E.I.Du Pont Company) is cut into below 1cm
Chopped strand, the most in mass ratio, by 2 parts of chopped aramid yarns, 2 parts of KOH (or t-BuOK) and
The dimethyl sulfoxide of 96 parts joins in the container of sealing, stirs 3～10 days, can be prepared by virtue under room temperature
Synthetic fibre nanofiber dispersion liquid.
The aramid nano-fiber dispersion liquid of other concentration can be with the aramid nano-fiber dispersion liquid of 2wt% with two
Methyl sulfoxide dilution obtains, or uses said method to prepare.
(2) with benzoin dimethylether as initiator, existed by the method for uv photo initiated grafting with acrylic acid for monomer
It is grafted carboxyl on polypropylene porous film (the Celgard2500 film that Celgard company of the U.S. produces) surface.
Then the KOH aqueous solution of the polypropylene porous film pH=10 of surface grafting carboxyl is processed 3min and make carboxylic
Base is converted into COO—, the film after then processing is the poly dimethyl allyl of 1% at mass fraction
Ammonium chloride (PDDA, is shown in formula III, is purchased from Aladdin, the aqueous solution dilution that mass concentration is 20% obtain)
Aqueous solution soaking 3min, makes film pass through the upper positively charged PDDA of electrostatic interaction absorption, so that poly-third
Become positively charged on alkene porous film surface lotus.Polypropylene porous film positively charged for surface is immersed in mass concentration
It is 1 × 10-23min in the aramid nano-fiber dispersion liquid of %, then takes out, washes, does at 80 DEG C
Dry 10min, so circulation 5 times, prepares the composite membrane of the attached aramid nano-fiber that is of five storeys in surface.
Embodiment 2
A kind of polyolefin/aramid nano-fiber composite membrane, is prepared by following methods:
(1) preparation method of aramid nano-fiber dispersion liquid is with embodiment 1.
(2) polypropylene porous membrane surface carboxyl grafting method is with embodiment 1, then by surface grafting carboxyl
Polypropylene porous film pH=10 KOH aqueous solution process 3min make converting carboxylate groups be COO—,
Then at the PDDA that mass fraction is 1%, (PDDA, is shown in the film after processing
Formula III, is purchased from Aladdin, the aqueous solution dilution that mass concentration is 20% obtain) aqueous solution soaking 3min,
Film is made to pass through the upper positively charged PDDA of electrostatic interaction absorption, so that bringing on polypropylene porous membrane surface
Positive charge.It is 1 × 10 that polypropylene porous film positively charged for surface is immersed in mass concentration-2The aramid fiber of %
3min in nanofiber dispersion liquid, then takes out, washes, is dried 10min at 80 DEG C, so circulate
10 times, prepare the surface composite membrane with 10 layers of aramid nano-fiber.
Embodiment 3
A kind of polyolefin/aramid nano-fiber composite membrane, is prepared by following methods:
(1) preparation method of aramid nano-fiber dispersion liquid is with embodiment 1.
(2) polypropylene porous membrane surface carboxyl grafting method is with embodiment 1, then by surface grafting carboxyl
Polypropylene porous film pH=10 KOH aqueous solution process 3min make converting carboxylate groups be COO—,
Then at the PDDA that mass fraction is 1%, (PDDA, is shown in the film after processing
Formula III, is purchased from Aladdin, the aqueous solution dilution that mass concentration is 20% obtain) aqueous solution soaking 3min,
Film is made to pass through the upper positively charged PDDA of electrostatic interaction absorption, so that bringing on polypropylene porous membrane surface
Positive charge.It is 1 × 10 that polypropylene porous film positively charged for surface is immersed in mass concentration-2The aramid fiber of %
3min in nanofiber dispersion liquid, then takes out, washes, is dried 10min at 80 DEG C, so circulate
15 times, prepare the surface composite membrane with 15 layers of aramid nano-fiber.
Embodiment 4
A kind of polyolefin/aramid nano-fiber composite membrane, is prepared by following methods:
(1) preparation method of aramid nano-fiber dispersion liquid is with embodiment 1.
(2) polypropylene porous membrane surface carboxyl grafting method is with embodiment 1, then by surface grafting carboxyl
Polypropylene porous film pH=10 KOH aqueous solution process 3min make converting carboxylate groups be COO—,
Then at the PDDA that mass fraction is 1%, (PDDA, is shown in the film after processing
Formula III, is purchased from Aladdin, the aqueous solution dilution that mass concentration is 20% obtain) aqueous solution soaking 3min,
Film is made to pass through the upper positively charged PDDA of electrostatic interaction absorption, so that bringing on polypropylene porous membrane surface
Positive charge.It is 1 × 10 that polypropylene porous film positively charged for surface is immersed in mass concentration-2The aramid fiber of %
3min in nanofiber dispersion liquid, then takes out, washes, is dried 10min at 80 DEG C, so circulate
20 times, prepare the surface composite membrane with 20 layers of aramid nano-fiber.
Embodiment 5
A kind of polyolefin/aramid nano-fiber composite membrane, is prepared by following methods:
(1) preparation method of aramid nano-fiber dispersion liquid is with embodiment 1.
(2) polypropylene porous membrane surface carboxyl grafting method is with embodiment 1, then by surface grafting carboxyl
Polypropylene porous film pH=10 KOH aqueous solution process 3min make converting carboxylate groups be COO—,
Then at the PDDA that mass fraction is 1%, (PDDA, is shown in the film after processing
Formula III, is purchased from Aladdin, the aqueous solution dilution that mass concentration is 20% obtain) aqueous solution soaking 3min,
Film is made to pass through the upper positively charged PDDA of electrostatic interaction absorption, so that bringing on polypropylene porous membrane surface
Positive charge.Polypropylene porous film positively charged for surface is immersed in the aramid fiber nanometer that mass concentration is 0.1%
3min in fiber dispersion, then takes out, washes, is dried 10min, so circulation 5 times at 80 DEG C,
Prepare the composite membrane of the attached aramid nano-fiber that is of five storeys in surface.
Embodiment 6
A kind of polyolefin/aramid nano-fiber composite membrane, is prepared by following methods:
(1) preparation method of aramid nano-fiber dispersion liquid is with embodiment 1.
(2) polypropylene porous membrane surface carboxyl grafting method is with embodiment 1, then by surface grafting carboxyl
Polypropylene porous film pH=10 KOH aqueous solution process 3min make converting carboxylate groups be COO—,
Then at the PDDA that mass fraction is 1%, (PDDA, is shown in the film after processing
Formula III, is purchased from Aladdin, the aqueous solution dilution that mass concentration is 20% obtain) aqueous solution soaking 3min,
Film is made to pass through the upper positively charged PDDA of electrostatic interaction absorption, so that bringing on polypropylene porous membrane surface
Positive charge.Polypropylene porous film positively charged for surface is immersed in the aramid fiber nanometer that mass concentration is 0.5%
3min in fiber dispersion, then takes out, washes, is dried 10min, so circulation 5 times at 80 DEG C,
Prepare the composite membrane of the attached aramid nano-fiber that is of five storeys in surface.
Embodiment 7
A kind of polyolefin/aramid nano-fiber composite membrane, is prepared by following methods:
(1) preparation method of aramid nano-fiber dispersion liquid is with embodiment 1.
(2) polypropylene porous membrane surface carboxyl grafting method is with embodiment 1, then by surface grafting carboxyl
Polypropylene porous film pH=10 KOH aqueous solution process 3min make converting carboxylate groups be COO—,
Then at the PDDA that mass fraction is 1%, (PDDA, is shown in the film after processing
Formula III, is purchased from Aladdin, the aqueous solution dilution that mass concentration is 20% obtain) aqueous solution soaking 3min,
Film is made to pass through the upper positively charged PDDA of electrostatic interaction absorption, so that bringing on polypropylene porous membrane surface
Positive charge.Polypropylene porous film positively charged for surface is immersed in the aramid fiber Nanowire that mass concentration is 1%
3min in dimension dispersion liquid, then takes out, washes, is dried 10min, so circulation 5 times at 80 DEG C,
Prepare the composite membrane of the attached aramid nano-fiber that is of five storeys in surface.
Embodiment 8
A kind of polyolefin/aramid nano-fiber composite membrane, is prepared by following methods:
(1) preparation method of aramid nano-fiber dispersion liquid is with embodiment 1.
(2) use the report such as Myung-Hyun Ryou method (see: Adv.Mater., 2011,23,
3066 3070) utilize dopamine in the Tris-HCl buffer solution of pH=8.5 under room temperature autohemagglutination thus
Phenolic hydroxyl group is introduced on polypropylene porous film (the Celgard2500 film that Celgard company of the U.S. produces) surface.
Then by the K of the polypropylene porous film pH=8 of surface band phenolic hydroxyl group2CO3Solution makes phenolic hydroxyl group be converted into phenol
Negative oxygen ion, the film after then processing is at poly-(N, N, N-trimethyl-3-(2-methallyl acylamino-)-1-chlorine
Change the third ammonium) (PMAPTAC, is shown in formula IV, CAS:68039-13-4, is purchased from the Wuxi Sunyu limited public affairs of chemical industry
Department) 1wt% aqueous solution soaks 5min, make film pass through electrostatic interaction absorption upper the most positively charged
PMAPTAC, so that the lotus that becomes positively charged on polypropylene porous membrane surface.By positively charged for surface poly-third
It is 1 × 10 that alkene perforated membrane is immersed in mass concentration-23min in % aramid nano-fiber dispersion liquid, then take out,
Washing, be dried, so circulation totally 5 times, prepares the composite membrane of the attached aramid nano-fiber that is of five storeys in surface.
Embodiment 9
A kind of polyolefin/aramid nano-fiber composite membrane, is prepared by following methods:
(1) preparation method of aramid nano-fiber dispersion liquid is with embodiment 1.
(2) the sulfonic polypropylene porous film of surface band, polypropylene porous membrane surface grafting sulphur are first prepared
Acidic group method is with embodiment 1, and simply changing grafted monomers is to vinylbenzenesulfonic acid, then by surface band sulphur
The KHCO of the polypropylene porous film pH=8 of acidic group3Aqueous solution soaking 3min makes sulfonic group be converted into sulphur
Acid radical anion, the film after then processing is at poly-(4-vinyl-N-benzyltrimethylammonium chloride)
(PVBTMAC, is shown in formula V, CAS:9017-80-5, is purchased from Scientific Polymer Product, Inc.)
1wt% aqueous solution soaks 3min, makes film pass through the upper positively charged PMAPTAC of electrostatic interaction absorption,
The lotus so that becoming positively charged on polypropylene porous membrane surface.Polypropylene porous film positively charged for surface is soaked
It is 1 × 10 in mass concentration-23min in % aramid nano-fiber dispersion liquid, then takes out, washes, is dried,
So circulation totally 5 times, prepares the composite membrane of the attached aramid nano-fiber that is of five storeys in surface.
Embodiment 10
A kind of polyolefin/aramid nano-fiber composite membrane, is prepared by following methods:
(1) preparation method of aramid nano-fiber dispersion liquid is with embodiment 1.
(2) polypropylene porous membrane surface grafting phenolic hydroxyl group method is with embodiment 8, the most just surface band phenol
The KHCO of the polypropylene porous film pH=8 of hydroxyl3Aqueous solution soaking 3min makes phenolic hydroxyl group be converted into phenol
Negative oxygen ion, the film after then processing is at poly-(4-vinyl-N-benzyltrimethylammonium chloride)
(PVBTMAC, is shown in formula V, CAS:9017-80-5, is purchased from Scientific Polymer Product, Inc.)
1wt% aqueous solution soaks 3min, makes film pass through the upper positively charged PMAPTAC of electrostatic interaction absorption,
The lotus so that becoming positively charged on polypropylene porous membrane surface.Polypropylene porous film positively charged for surface is soaked
It is 1 × 10 in mass concentration-23min in % aramid nano-fiber dispersion liquid, then takes out, washes, is dried,
So circulation totally 5 times, prepares the composite membrane of the attached aramid nano-fiber that is of five storeys in surface.
Embodiment 11
A kind of polyolefin/aramid nano-fiber composite membrane, is prepared by following methods:
(1) preparation method of aramid nano-fiber dispersion liquid is with embodiment 1.
(2) polyethylene porous of surface band phenolic hydroxyl group is first prepared, polyethylene porous membrane (thickness 16 μm,
Porosity is 40%, is purchased from Targray) surface grafting phenolic hydroxyl group method is with embodiment 8, then by surface
The K of the polyethylene porous membrane pH=8 with phenolic hydroxyl group2CO3Solution makes phenolic hydroxyl group be converted into phenol negative oxygen ion,
Then the film after processing is at poly-(N, N, N-trimethyl-3-(2-methallyl acylamino-)-1-chlorination the third ammonium)
(PMAPTAC, is shown in formula IV, CAS:68039-13-4, is purchased from Wuxi Chemical Co., Ltd. of Sunyu) 1wt%
Aqueous solution soaks 5min, makes film pass through the upper positively charged PMAPTAC of electrostatic interaction absorption, thus
Make to become positively charged on polyethylene porous membrane surface lotus.Polyethylene porous membrane positively charged for surface is immersed in matter
Amount concentration is 1 × 10-23min in % aramid nano-fiber dispersion liquid, then takes out, washes, is dried, as
This circulation totally 5 times, prepares the composite membrane of the attached aramid nano-fiber that is of five storeys in surface.
Embodiment 12
A kind of polyolefin/aramid nano-fiber composite membrane, is prepared by following methods:
(1) preparation method of aramid nano-fiber dispersion liquid is with embodiment 1.
(2) polyethylene porous membrane of surface grafting sulfonate radical, polyethylene porous membrane (thickness 16 are first prepared
μm, porosity is 40%, is purchased from Targray) surface grafting sulfonic group method with embodiment 1, then will
The KHCO of surface band sulfonic polyethylene porous membrane pH=83Aqueous solution soaking 3min makes sulfonic group
Being converted into sulfonate radical anion, the film after then processing is at poly-(4-vinyl-N-benzyltrimethylammonium chloride)
(PVBTMAC, is shown in formula V, CAS:9017-80-5, is purchased from Scientific Polymer Product, Inc.)
1wt% aqueous solution soaks 3min, makes film pass through the upper positively charged PMAPTAC of electrostatic interaction absorption,
The lotus so that becoming positively charged on polyethylene porous membrane surface.Polyethylene porous membrane positively charged for surface is soaked
It is 1 × 10 in mass concentration-23min in % aramid nano-fiber dispersion liquid, then takes out, washes, is dried,
So circulation totally 5 times, prepares the composite membrane of the attached aramid nano-fiber that is of five storeys in surface.
Embodiment 13
A kind of polyolefin/aramid nano-fiber composite membrane, is prepared by following methods:
(1) preparation method of aramid nano-fiber dispersion liquid is with embodiment 1.
(2) polyethylene porous membrane of surface grafting sulfonate radical, polyethylene porous membrane (thickness 16 are first prepared
μm, porosity is 40%, is purchased from Targray) grafting sulfonic groups method is with embodiment 1, the most just table
Wear the KHCO of sulfonic polyethylene porous membrane pH=83Aqueous solution soaking 3min makes sulfonic group turn
Turning to sulfonate radical anion, the film after then processing is at poly-(4-vinyl-N-benzyltrimethylammonium chloride)
(PVBTMAC, is shown in formula V, CAS:9017-80-5, is purchased from Scientific Polymer Product, Inc.)
1wt% aqueous solution soaks 3min, makes film pass through the upper positively charged PMAPTAC of electrostatic interaction absorption,
The lotus so that becoming positively charged on polyethylene porous membrane surface.Polyethylene porous membrane positively charged for surface is soaked
It is 1 × 10 in mass concentration-23min in % aramid nano-fiber dispersion liquid, then takes out, washes, is dried,
So circulation totally 5 times, prepares the composite membrane of the attached aramid nano-fiber that is of five storeys in surface.
Embodiment 14: comparative example 1
So that without the Celgard2500 polypropylene porous film of any process, (thickness is 25 μm, and porosity is
55%, it is purchased from Celgard company) it is comparative film, test its Gurley value, MacMullin number
And percent thermal shrinkage.The results are shown in Table 1.
Embodiment 15: comparative example 2
With the PE perforated membrane (thickness 16 μm, porosity is 40%, is purchased from Targray) without any process
For comparative film, test its Gurley value, to the pick up of electrolyte and percent thermal shrinkage.
Embodiment 16: the performance indications evaluation methodology of polyolefin/aramid nano-fiber composite membrane:
The air penetrability of composite membrane as prepared by following way measures embodiment 1～15, MacMullin
Number and percent thermal shrinkage, thus evaluate the performance of composite membrane.
(1) method of testing of Gurley value
In the present invention, the breathability Gurley4110N Permeability gauge of film is tested.The breathability of film
Weigh with Gurley value.Gurley value is defined as a certain amount of gas and arrives the another of film by the side of film
Time required for side.In the present invention using the air of 100cc by the time required for film as Gurley
Value, carrys out timing with stopwatch.Its Gurley value of composite membrane prepared by the present invention and the Gurley value of comparative film
It is shown in Table 1.
(2)MacMullin Number
In the present invention, prepared composite diaphragm perforating press is washed into the disk of a diameter of 16mm, so
After film is placed in LiPF6Concentration is the ethylene carbonate (EC) of 1mol/L: Ethyl methyl carbonate (EMC)=
The solution of 2:1 (volume ratio) soaks more than 1min, then takes out, film is fixed on stainless steel electrode,
(beautiful with 1287 electrochemical interfaces (Solartron company of Britain) and 4294A precise impedance analyser
Agilent) measure composite membrane at 1kHz, ambient temperature be impedance when 25 ± 1 DEG C, calculate film with this
Ionic conductivity.Measure the ionic conductivity of electrolyte simultaneously.MacMullin number (Nm) is fixed
Justice is the ratio of the ionic conductivity after barrier film wetting electrolytic liquid and electrolyte body ionic conductivity, test result
It is shown in Table 1.
(3) method of testing of percent thermal shrinkage
The dimensional stability of film is one of embodiment of important practical of the present invention.In the present embodiment, with thermal contraction
Rate weighs the dimensional stability of film.Prepared composite diaphragm is cut into the lamellar of 5 × 5cm, then puts
In thermal station, maintain 30min at 150 DEG C and 170 DEG C respectively, calculate the percent thermal shrinkage of film.Percent thermal shrinkage
For:
A1For the film area when room temperature, A2For maintaining the area of 30min caudacoria at 150 DEG C or 170 DEG C.
Test result is shown in Table 1.
From table 1, the polyolefin that the present invention prepares/aramid nano-fiber composite membrane, keeping good
While good breathability and ionic conductivity performance, significantly improving thermostability, percent thermal shrinkage significantly reduces,
Combine the low temperature closed pore characteristic of polyolefin porous membrane and the thermostability that aramid fiber is good, be suitably applied needs and exist
Separate under higher temperature in the electrochemical device of both positive and negative polarity.Especially, it is adaptable in lithium ion battery, permissible
Improve the safety of lithium ion battery.
The performance indications of table 1 polyolefin/aramid nano-fiber composite membrane
Remarks: a. thermostability test condition is maintenance 30min at 130 DEG C.
B. shrink the strongest, it is difficult to accurately measure.
Represent and be not measured.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not by above-mentioned reality
Execute the restriction of example, the change made under other any spirit without departing from the present invention and principle, modification,
Substitute, combine, simplify, all should be the substitute mode of equivalence, within being included in protection scope of the present invention.
Claims (10)
1. being used for a preparation method for the polyolefin/aramid nano-fiber composite membrane of lithium ion battery, it is special
Levy and be to comprise the following steps:
(1), after introducing acidic-group on polyolefin porous membrane surface, with base extraction, surface band is obtained
The polyolefin porous membrane of negative charge；
(2) it is immersed in the polyelectrolyte solution of the positively charged group of side chain, is obtained surface positively charged
The polyolefin porous membrane of lotus；
(3) polyolefin porous membrane positively charged for surface is immersed in aramid nano-fiber dispersion liquid, takes
Go out, wash, be dried, obtain polyolefin/aramid nano-fiber composite membrane.
Polyolefin for lithium ion battery the most according to claim 1/aramid nano-fiber composite membrane
Preparation method, it is characterised in that: the polyelectrolyte described in step (2) is for having lower formula I or formula II institute
Show the quaternary ammonium salt of structure, quaternary alkylphosphonium salt, sulfonium salt, or intramolecular has the poly-electricity of heteroaromatic cation of armaticity
Xie Zhi, or PDDA:
In formula I and formula II, A is N, O or S atom, and B, E are respectively N, P or S atom, D
For phenylene or methylene；X1 -、X2 -It is respectively electronegative halogen ion or other electronegative acid
Radical ion；R1、R2It is respectively H atom or alkyl；R3、R4It is respectively alkyl；M, n be respectively 0～
The natural number of 10；When B is N or the P atomic time, p=3；When B is S atom, p=2.
Polyolefin for lithium ion battery the most according to claim 1/aramid nano-fiber composite membrane
Preparation method, it is characterised in that: the mass concentration of aramid nano-fiber dispersion liquid used is 1 × 10-3%～
8%；Described aramid fiber is containing the heteroatomic meta-aramid of Si in meta-aramid or p-aramid fiber, or strand
Or p-aramid fiber.
Polyolefin for lithium ion battery the most according to claim 1/aramid nano-fiber composite membrane
Preparation method, it is characterised in that: the polyolefin porous membrane described in step (1) be polyethylene porous membrane,
At least one in polypropylene porous film and polyethylene/polypropylene multilayer film.
Polyolefin for lithium ion battery the most according to claim 1/aramid nano-fiber composite membrane
Preparation method, it is characterised in that: the acidic-group described in step (1) is carboxyl, phenolic hydroxyl group, sulfonic acid
Base, benzenesulfonic acid base or phosphate.
Polyolefin for lithium ion battery the most according to claim 1/aramid nano-fiber composite membrane
Preparation method, it is characterised in that: the alkali liquor described in step (1) is KOH, NaOH, LiOH, K2CO3、
Na2CO3、Li2CO3、KHCO3Or NaHCO3Alkaline aqueous solution.
Polyolefin for lithium ion battery the most according to claim 1/aramid nano-fiber composite membrane
Preparation method, it is characterised in that by circulation repeat step (3) immersion, wash, be dried, preparation
Obtain the polyolefin/aramid nano-fiber composite membrane of multilamellar aramid fiber.
Polyolefin for lithium ion battery the most according to claim 1/aramid nano-fiber composite membrane
Preparation method, it is characterised in that: the soak time described in step (3) is 0.1～20min；Described
It is dried and refers to be dried at 50～100 DEG C 1～120min.
9. polyolefin/aramid nano-fiber the composite membrane for lithium ion battery, it is characterised in that according to
The polyolefin for lithium ion battery described in any one of claim 1～8/aramid nano-fiber composite membrane
Preparation method obtains.
Polyolefin/aramid nano-fiber for lithium ion battery the most according to claim 9 is combined
Film application in electrochemical device.
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| CN105185940B (en) * | 2015-10-23 | 2018-10-09 | 旭成（福建）科技股份有限公司 | The preparation method and applications of polyolefin/nano crystal fibre element composite diaphragm |
| CN105932197A (en) * | 2016-05-23 | 2016-09-07 | 北京理工大学 | Preparation method of poly (p-phenylene terephthalamide) porous membrane |
| CN109385928B (en) * | 2018-11-02 | 2021-04-06 | 陕西科技大学 | Nano cellulose/aramid nano fiber film composite nano paper and preparation method thereof |
| CN109830632B (en) * | 2019-01-22 | 2022-07-15 | 上海化工研究院有限公司 | Aramid fiber coated lithium ion battery diaphragm |
| CN110620205B (en) * | 2019-10-08 | 2022-08-12 | 山东精恒科技有限公司 | Preparation method of para-aramid/PP non-woven fabric lithium ion battery diaphragm |
| CN111244366B (en) * | 2020-01-20 | 2022-08-09 | 哈尔滨工业大学 | Preparation method of lithium-sulfur battery diaphragm based on multilayer aramid nanofibers |
| CN111584802A (en) * | 2020-04-29 | 2020-08-25 | 西安理工大学 | Aramid nanofiber composite lithium ion battery diaphragm and preparation method thereof |
| CN115224438B (en) * | 2022-07-28 | 2023-07-25 | 哈尔滨工业大学无锡新材料研究院 | Preparation method of composite coated lithium ion battery polyethylene diaphragm |
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