CN104201310A - Polyolefin/aramid nano-fiber composite membrane applied to lithium ion battery and preparation of polyolefin/aramid nano-fiber composite membrane - Google Patents
Polyolefin/aramid nano-fiber composite membrane applied to lithium ion battery and preparation of polyolefin/aramid nano-fiber composite membrane Download PDFInfo
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- 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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- 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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- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
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- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
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Abstract
The invention belongs to the technical field of preparation of membrane materials for chemical power source energy storage elements and discloses a polyolefin/aramid nano-fiber composite membrane applied to a lithium ion battery and a preparation method of the polyolefin/aramid nano-fiber composite membrane. The preparation method of the polyolefin/aramid nano-fiber composite membrane comprises the following steps: introducing acidic groups to the surface of a polyolefin porous membrane and treating by using alkaline liquid to obtain a polyolefin porous membrane with negative charge on the surface; soaking the polyolefin porous membrane with a polyelectrolyte solution to obtain a polyolefin porous membrane with positive charge on the surface; and then soaking the polyolefin porous membrane with aramid nano-fiber dispersion liquid, taking the polyolefin porous membrane out, washing and drying to obtain the polyolefin/aramid nano-fiber composite membrane. The polyolefin/aramid nano-fiber composite membrane has low-temperature pore closing property and high-temperature resistance and is applicable to electrochemical devices working at relatively high temperature; an introduced aramid nano-fiber layer is of a porous structure, so that relatively high ionic conductivity can be kept; by virtue of electrostatic combination between a base membrane and the aramid nano-fiber layer, the aramid nano-fiber membrane is unlikely to be peeled from the base membrane, so that the cycle performance of the battery is guaranteed.
Description
Technical field
The invention belongs to the membrane material preparing technical field of chemical power source energy-storage travelling wave tube, particularly a kind of polyolefin/aramid nano-fiber composite membrane for lithium ion battery 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, can prevent from that both positive and negative polarity is in direct contact with to cause together inside circuit short circuit; Have again the effect of lithium ion conducting, the loose structure of barrier film or form gel because absorbed electrolyte makes lithium ion can see through barrier film when discharging and recharging simultaneously, inside battery conducting formation loop, thus realize the mutual conversion of chemical energy and electric energy.Although barrier film does not participate in the process of relevant power conversion in battery, the properties of barrier film has very important impact to the capacity of battery, useful life, multiplying power discharging property and fail safe etc.
Lithium ion battery separator can be divided into perforated membrane, non-woven membrane, polymer dielectric film, composite membrane etc.Existing commercial barrier film mostly is take the perforated membrane that polyolefin is base material.But polyolefin porous membrane also exists weak point, one of them outstanding shortcoming is exactly that owing to there is internal stress, barrier film can produce stronger contraction when temperature reaches near the fusing point of its bulk material; In temperature, reach bulk material fusing point and when above, barrier film is melt fracture even, lose the effect of isolation both positive and negative polarity, will there is short circuit in inside battery, thereby occur potential safety hazard; Another shortcoming is that film exists " pin hole " phenomenon in microstructure, and inner micropore is directly to connect barrier film.And lithium ion battery can be separated out Li dendrite in the process discharging and recharging, particularly, when overcharging, Li dendrite is easy to be deposited on membrane surface and is easy to wear out barrier film, makes both positive and negative polarity short circuit.Therefore for the higher power lithium-ion battery of security requirement, membrane thicknesses used generally can not be lower than 30 μ m.In addition, polyalkene diaphragm surface is chemically inert, and surface can be smaller, bad to the wetability of the larger organic electrolyte of conventional polarity comparatively speaking, make battery pour in process of production the time that electrolyte need to be longer, reduced the production efficiency of battery.
For the percent thermal shrinkage aspect that reduces polyolefin porous membrane, conventionally adopt adhesive the inorganic nano-particles such as silicon dioxide, aluminium oxide, titanium oxide, barium titanate to be bonded on one or two surface of polyolefin porous membrane as Kynoar (PVDF), Kynoar-hexafluoropropylene (PVDF-HFP) or styrene-butadiene latex (SBR) etc.But the adhesion by adhesive sticks to inorganic nano-particle on polyolefin surfaces merely, and due to the capillarity of perforated membrane, adhesive can enter into hole and result in blockage, cause barrier film resistance to increase; And in charge and discharge cycles, because adhesive generally all swelling can occur in electrolyte, between base film and high-temperaure coating or inorganic nano-particle, easily peel off, barrier film internal resistance meeting sharply increases, and the cycle performance of battery fails fast.
Start research and development both at home and abroad and directly prepare porous septum method by high temperature resistant base material.Adopt some to there is perforated membrane or non-woven membrane prepared by dystectic polymer.The aramid fiber of wherein usining is prepared lithium ion battery separator aspect as base material a large amount of research.Aramid fiber is the polyamide that contains phenyl ring in main chain.Its decomposition temperature is high, has good solvent resistance, thermal endurance, anti-flammability and thermal insulation, and good mechanical performance is one of synthetic macromolecule that current mechanical strength is the strongest.More stable below 300 ℃, can there is not thermal contraction.Only have when temperature continues to raise, aramid fiber just can be degraded.Therefore some external barrier film manufacturers are devoted to exploitation and take aramid fiber as base material or with the lithium ion battery separator of other base materials of aramid fiber modification, in order to improve the thermal endurance of barrier film, thereby guarantee the fail safe of barrier film.But, the technology that existing research adopts otherwise preparation process is complicated, preparation condition is comparatively harsh, otherwise be exactly that the film thickness for preparing is thick, poor tensile strength, and can not guarantee aramid fiber and the membrane-bound fastness of matrix, in charge and discharge cycles, base film is easily peeled off and is caused interface resistance increase with aramid fiber, makes the chemical property decline of battery.
Summary of the invention
In order to overcome the shortcoming and deficiency of above-mentioned prior art, primary and foremost purpose of the present invention is to provide a kind of preparation method of the polyolefin/aramid nano-fiber composite membrane for lithium ion battery.
Polyolefin/aramid nano-fiber the composite membrane for lithium ion battery that provides said method to prepare is provided another object of the present invention.
Still a further object of the present invention is to provide the application of above-mentioned polyolefin/aramid nano-fiber composite membrane for lithium ion battery at electrochemical device.
Object of the present invention realizes by following proposal:
A preparation method for polyolefin/aramid nano-fiber composite membrane of lithium ion battery, comprises the following steps:
(1) on polyolefin porous membrane surface, introduce after acidic-group, with alkali lye, process, obtain the polyolefin porous membrane of surface band negative electrical charge;
(2) be immersed in the polyelectrolyte solution of the positively charged group of side chain, obtained the polyolefin porous membrane of surface band positive charge;
(3) polyolefin porous membrane of surface band positive charge is immersed in aramid nano-fiber dispersion liquid, takes out, wash, dry, obtain polyolefin/aramid nano-fiber composite membrane.
The polyolefin porous membrane surface of gained polyolefin/aramid nano-fiber composite membrane has at least one deck aramid nano-fiber.
Polyolefin/aramid nano-fiber composite membrane of the present invention can be by being cycled to repeat the immersion, washing, dry of step (3), thereby obtain the polyolefin/aramid nano-fiber composite membrane with multilayer aramid nano-fiber.
The described polyelectrolyte of step (2) can be quaternary ammonium salt, quaternary alkylphosphonium salt, the sulfonium salt with structure shown in following formula I or formula II, or in molecule, has the polyelectrolyte of the fragrant heterocycle cation of armaticity, or PDDA (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, and D is phenylene or methylene.X
1 --, X
2 --be respectively electronegative halogen ion (as Cl
--, Br
--, I
--), or other electronegative acid ions are (as SO
4 --, PO
4 3-, NO
3 --) etc.R
1, R
2be respectively H atom or alkyl, as methyl, ethyl etc., R
3, R
4be respectively alkyl, as methyl, ethyl, propyl group, butyl, amyl group or hexyl etc.M, n are respectively 0～10 natural number.When B is N or P atomic time, p=3, when B is the S atomic time, p=2.
The molecular weight of the present invention's polyelectrolyte used is preferably 5000～3000000.The concentration of polyelectrolyte solution used can be adjusted as required, arbitrarily this area conventional treatment working concentration.Be preferably 1～10%.The polyelectrolyte of described quaternary ammonium salt, quaternary alkylphosphonium salt, sulfonium salt under solution state on side chain with positive charge groups such as quaternary ammonium ion, quaternary phosphonium ion, sulfonium cations.
The dispersion liquid of the surface band negative electrical charge aramid nano-fiber that the present invention uses, the document (ACS Nano, 2011,5 (9), pp6945 – 6954) that its preparation method specifically can be reported with reference 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 the excessive concentration of aramid nano-fiber dispersion liquid used, the viscosity of dispersion liquid is larger, is unfavorable for applying evenly.The present invention experiment showed, in order to make polyolefin porous membrane surface enclose uniform aramid nano-fiber and to make prepared composite membrane have good ionic conductivity, 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 conventional meta-aramid or p-aramid fiber, or in strand, contains the heteroatomic meta-aramids such as Si or p-aramid fiber etc., and its molecular weight is 2000～2000000.The form of aramid fiber can be monofilament, multifibres, chopped strand, pulp, aramid yarn or aramid fiber cloth etc.
Preferably, the polyolefin porous membrane that the present invention uses can be the duplicature of polyethylene porous membrane, polypropylene porous film and polyethylene/polypropylene or at least one in multilayer film.
The described acidic-group of introducing on polyolefin porous membrane surface refers to realize by the method for irradiation grafting or chemical graft.
Described acidic-group can be the groups such as carboxyl, phenolic hydroxyl group, sulfonic group, benzene sulfonic acid base or phosphate.
The described alkali lye of step (1) is chosen as but is not restricted to KOH, NaOH, LiOH, K
2cO
3, Na
2cO
3, Li
2cO
3, KHCO
3or NaHCO
3deng alkaline aqueous solution.Alkaline aqueous solution concentration used can be adjusted as required, arbitrarily this area conventional treatment working concentration.Be preferably pH=8～14.
The described number of times being cycled to repeat can be between 1～100, thereby introduces multilayer aramid nano-fiber at polyolefin porous membrane surface.Cycling number of times preferably 1～50, more preferably 1～20.When the dispersion liquid concentration of aramid nano-fiber is larger, cycling number of times should suitably reduce to obtain suitable gas permeability, makes composite membrane possess suitable ionic conductivity and thermal endurance.
In each operation, the time being dipped in aramid nano-fiber dispersion liquid is controlled in 0.1～20min, and preferably soak time is 1～3min.After soaking, washing, dry 1～120min at 50～100 ℃, preferably 60～90 ℃ of baking temperatures, drying time is 1～60min preferably.
The present invention obtains the polyolefin porous membrane of surface band positive charge by processing, again by being soaked in electronegative aramid nano-fiber dispersion liquid, utilize electrostatic adsorption, make aramid nano-fiber be adsorbed on polyolefin porous membrane surface, through washing, dry, obtaining polyolefin porous membrane surface absorption has the composite membrane of aramid nano-fiber, again by repeatedly soaking, utilize hydrogen bond action at aramid nano-fiber adsorption multilayer aramid nano-fiber, thereby obtain the composite membrane that polyolefin porous membrane surface absorption has multilayer aramid nano-fiber.And the number of times that can adsorb aramid nano-fiber by control is to control the gas permeability of composite membrane and thermal endurance in the scope of needs.
The polyolefin porous membrane that complex method of the present invention prepares and the composite membrane of aramid nano-fiber are applicable in various electrochemical devices, are especially used as the membrane module of lithium ion battery or other chemical energy storage devices.Because polyolefin porous membrane surface is with resistant to elevated temperatures aramid nano-fiber, the thermal endurance of composite membrane improves greatly, and therefore composite membrane of the present invention is especially suitable for use as the membrane material of power lithium-ion battery.
The present invention, with respect to prior art, has following advantage and beneficial effect:
(1) polyolefin/aramid nano-fiber composite membrane of the present invention combines the low temperature closed pore characteristic of polyolefin porous membrane and the high-temperature stability of aramid fiber, in the electrochemical device that is applicable to work under higher temperature, as for lithium ion battery, can improve the fail safe of lithium ion battery.
(2) between the aramid nano-fiber on polyolefin/aramid nano-fiber composite membrane of the present invention, there is more space, and do not stop up the hole of polyolefin porous membrane, with respect to prior art, utilize the composite membrane of adhesive compound polyolefin perforated membrane and aramid fiber gained, the ionic conductivity that tool is significantly improved.
(3) polyolefin/aramid nano-fiber composite membrane of the present invention be take improved polyalkene perforated membrane as base film, adsorption multi-layer aramid nano-fiber layer on it, polyolefin layer and aramid nano-fiber layer are electrostatic force suction-operated, and between aramid nano-fiber layer, be hydrogen bond action, adhesion is strong, in charge and discharge cycles, be not easy to peel off with base film, interface resistance increases and does not have significantly to increase with circulating battery number of times, effectively improves the cycle performance of battery.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1
Polyolefin/aramid nano-fiber composite membrane, is prepared by following methods:
(1) document (ACS Nano, 2011,5 (9), pp6945 – 6954) that the preparation method of aramid nano-fiber dispersion liquid can report with reference to Yang etc.The example that is prepared as that the mass fraction of take is 2% aramid nano-fiber dispersion liquid, its preparation method is: aramid yarn (the Kevlar fiber of E.I.Du Pont Company) is cut into the chopped strand below 1cm, then in mass ratio, the 2 parts short dimethyl sulfoxide (DMSO)s of cutting aramid yarn, 2 parts of KOH (or t-BuOK) and 96 parts are joined in the container of sealing, under room temperature, stir 3～10 days, can make aramid nano-fiber dispersion liquid.
The aramid nano-fiber dispersion liquid of other concentration can obtain with dimethyl sulfoxide (DMSO) dilution with the aramid nano-fiber dispersion liquid of 2wt%, or adopts said method to prepare.
(2) take method that benzoin dimethylether passes through uv photo initiated grafting as monomer as initator, the acrylic acid of take carboxyl in grafting on polypropylene porous film (the Celgard2500 film that U.S. Celgard company produces) surface.Then the polypropylene porous film of surface grafting carboxyl is processed to 3min with the KOH aqueous solution of pH=10 and make be converted into-COO of carboxyl
-then PDDA (the PDDA that is 1% by the film after processing at mass fraction, see formula III, be purchased from Aladdin, the aqueous solution that is 20% by mass concentration dilution obtains) aqueous solution soaking 3min, make film adsorb positively charged PDDA by electrostatic interaction, thereby make to become positively charged on polypropylene porous membrane surface lotus.It is 1 * 10 that the polypropylene porous film of surface band positive charge is immersed in to mass concentration
-23min in the aramid nano-fiber dispersion liquid of %, then takes out, washes, at 80 ℃, is dried 10min, so circulates 5 times, makes the composite membrane of the attached aramid nano-fiber that is of five storeys in surface.
Embodiment 2
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, with embodiment 1, is then processed 3min by the polypropylene porous film of surface grafting carboxyl with the KOH aqueous solution of pH=10 and is made be converted into-COO of carboxyl
-then PDDA (the PDDA that is 1% by the film after processing at mass fraction, see formula III, be purchased from Aladdin, the aqueous solution that is 20% by mass concentration dilution obtains) aqueous solution soaking 3min, make film adsorb positively charged PDDA by electrostatic interaction, thereby make to become positively charged on polypropylene porous membrane surface lotus.It is 1 * 10 that the polypropylene porous film of surface band positive charge is immersed in to mass concentration
-23min in the aramid nano-fiber dispersion liquid of %, then takes out, washes, at 80 ℃, is dried 10min, so circulates 10 times, makes surface with the composite membrane of 10 layers of aramid nano-fiber.
Embodiment 3
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, with embodiment 1, is then processed 3min by the polypropylene porous film of surface grafting carboxyl with the KOH aqueous solution of pH=10 and is made be converted into-COO of carboxyl
-then PDDA (the PDDA that is 1% by the film after processing at mass fraction, see formula III, be purchased from Aladdin, the aqueous solution that is 20% by mass concentration dilution obtains) aqueous solution soaking 3min, make film adsorb positively charged PDDA by electrostatic interaction, thereby make to become positively charged on polypropylene porous membrane surface lotus.It is 1 * 10 that the polypropylene porous film of surface band positive charge is immersed in to mass concentration
-23min in the aramid nano-fiber dispersion liquid of %, then takes out, washes, at 80 ℃, is dried 10min, so circulates 15 times, makes surface with the composite membrane of 15 layers of aramid nano-fiber.
Embodiment 4
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, with embodiment 1, is then processed 3min by the polypropylene porous film of surface grafting carboxyl with the KOH aqueous solution of pH=10 and is made be converted into-COO of carboxyl
-then PDDA (the PDDA that is 1% by the film after processing at mass fraction, see formula III, be purchased from Aladdin, the aqueous solution that is 20% by mass concentration dilution obtains) aqueous solution soaking 3min, make film adsorb positively charged PDDA by electrostatic interaction, thereby make to become positively charged on polypropylene porous membrane surface lotus.It is 1 * 10 that the polypropylene porous film of surface band positive charge is immersed in to mass concentration
-23min in the aramid nano-fiber dispersion liquid of %, then takes out, washes, at 80 ℃, is dried 10min, so circulates 20 times, makes surface with the composite membrane of 20 layers of aramid nano-fiber.
Embodiment 5
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, with embodiment 1, is then processed 3min by the polypropylene porous film of surface grafting carboxyl with the KOH aqueous solution of pH=10 and is made be converted into-COO of carboxyl
-then PDDA (the PDDA that is 1% by the film after processing at mass fraction, see formula III, be purchased from Aladdin, the aqueous solution that is 20% by mass concentration dilution obtains) aqueous solution soaking 3min, make film adsorb positively charged PDDA by electrostatic interaction, thereby make to become positively charged on polypropylene porous membrane surface lotus.It is 3min in 0.1% aramid nano-fiber dispersion liquid that the polypropylene porous film of surface band positive charge is immersed in to mass concentration, then take out, wash, at 80 ℃ dry 10min, so circulate 5 times, make the composite membrane of the attached aramid nano-fiber that is of five storeys in surface.
Embodiment 6
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, with embodiment 1, is then processed 3min by the polypropylene porous film of surface grafting carboxyl with the KOH aqueous solution of pH=10 and is made be converted into-COO of carboxyl
-then PDDA (the PDDA that is 1% by the film after processing at mass fraction, see formula III, be purchased from Aladdin, the aqueous solution that is 20% by mass concentration dilution obtains) aqueous solution soaking 3min, make film adsorb positively charged PDDA by electrostatic interaction, thereby make to become positively charged on polypropylene porous membrane surface lotus.It is 3min in 0.5% aramid nano-fiber dispersion liquid that the polypropylene porous film of surface band positive charge is immersed in to mass concentration, then take out, wash, at 80 ℃ dry 10min, so circulate 5 times, make the composite membrane of the attached aramid nano-fiber that is of five storeys in surface.
Embodiment 7
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, with embodiment 1, is then processed 3min by the polypropylene porous film of surface grafting carboxyl with the KOH aqueous solution of pH=10 and is made be converted into-COO of carboxyl
-then PDDA (the PDDA that is 1% by the film after processing at mass fraction, see formula III, be purchased from Aladdin, the aqueous solution that is 20% by mass concentration dilution obtains) aqueous solution soaking 3min, make film adsorb positively charged PDDA by electrostatic interaction, thereby make to become positively charged on polypropylene porous membrane surface lotus.It is 3min in 1% aramid nano-fiber dispersion liquid that the polypropylene porous film of surface band positive charge is immersed in to mass concentration, then take out, wash, at 80 ℃ dry 10min, so circulate 5 times, make the composite membrane of the attached aramid nano-fiber that is of five storeys in surface.
Embodiment 8
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) adopt the method for the reports such as Myung-Hyun Ryou (referring to Adv.Mater., 2011,23,3066 – 3070) thus utilize dopamine autohemagglutination introducing phenolic hydroxyl group on polypropylene porous film (U.S. Celgard company produce Celgard2500 film) surface under room temperature in the Tris-HCl of pH=8.5 cushioning liquid.Then the polypropylene porous film of surface band phenolic hydroxyl group is used to the K of pH=8
2cO
3solution makes phenolic hydroxyl group be converted into phenol negative oxygen ion, then by the film after processing at poly--(N, N, N-trimethyl-3-(2-methyl acrylyl is amino)-1-chlorination the third ammonium) (PMAPTAC, see formula IV, CAS:68039-13-4, is purchased from Wuxi Chemical Co., Ltd. of Sunyu) soak 5min in the 1wt% aqueous solution, make film adsorb positively charged PMAPTAC by electrostatic interaction, thereby make to become positively charged on polypropylene porous membrane surface lotus.It is 1 * 10 that the polypropylene porous film of surface band positive charge is immersed in to mass concentration
-23min in % aramid nano-fiber dispersion liquid, then takes out, washes, is dried, and so circulation is totally 5 times, makes the composite membrane of the attached aramid nano-fiber that is of five storeys in surface.
Embodiment 9
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) first prepare the sulfonic polypropylene porous film of surface band, polypropylene porous membrane surface grafting sulfonic group method, with embodiment 1, just changes grafted monomers for to vinylbenzenesulfonic acid, then the sulfonic polypropylene porous film of surface band is used to the KHCO of pH=8
3aqueous solution soaking 3min makes sulfonic group be converted into sulfonate radical anion, then by the film after processing at poly--(4-vinyl-N-benzyltrimethylammonium chloride) (PVBTMAC, see formula V, CAS:9017-80-5, be purchased from Scientific Polymer Product, Inc.) in the 1wt% aqueous solution, soak 3min, make film adsorb positively charged PMAPTAC by electrostatic interaction, thereby make to become positively charged on polypropylene porous membrane surface lotus.It is 1 * 10 that the polypropylene porous film of surface band positive charge is immersed in to mass concentration
-23min in % aramid nano-fiber dispersion liquid, then takes out, washes, is dried, and so circulation is totally 5 times, makes the composite membrane of the attached aramid nano-fiber that is of five storeys in surface.
Embodiment 10
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, then the KHCO of pH=8 for the polypropylene porous film of surface band phenolic hydroxyl group just
3aqueous solution soaking 3min makes phenolic hydroxyl group be converted into phenol negative oxygen ion, then by the film after processing at poly--(4-vinyl-N-benzyltrimethylammonium chloride) (PVBTMAC, see formula V, CAS:9017-80-5, be purchased from Scientific Polymer Product, Inc.) in the 1wt% aqueous solution, soak 3min, make film adsorb positively charged PMAPTAC by electrostatic interaction, thereby make to become positively charged on polypropylene porous membrane surface lotus.It is 1 * 10 that the polypropylene porous film of surface band positive charge is immersed in to mass concentration
-23min in % aramid nano-fiber dispersion liquid, then takes out, washes, is dried, and so circulation is totally 5 times, makes the composite membrane of the attached aramid nano-fiber that is of five storeys in surface.
Embodiment 11
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) first prepare the polyethylene porous of surface band phenolic hydroxyl group, polyethylene porous membrane (thickness 16 μ m, porosity is 40%, is purchased from Targray) surface grafting phenolic hydroxyl group method is with embodiment 8, the K with pH=8 by the polyethylene porous membrane of surface band phenolic hydroxyl group then
2cO
3solution makes phenolic hydroxyl group be converted into phenol negative oxygen ion, then by the film after processing at poly--(N, N, N-trimethyl-3-(2-methyl acrylyl is amino)-1-chlorination the third ammonium) (PMAPTAC, see formula IV, CAS:68039-13-4, is purchased from Wuxi Chemical Co., Ltd. of Sunyu) soak 5min in the 1wt% aqueous solution, make film adsorb positively charged PMAPTAC by electrostatic interaction, thereby make to become positively charged on polyethylene porous membrane surface lotus.It is 1 * 10 that the polyethylene porous membrane of surface band positive charge is immersed in to mass concentration
-23min in % aramid nano-fiber dispersion liquid, then takes out, washes, is dried, and so circulation is totally 5 times, makes the composite membrane of the attached aramid nano-fiber that is of five storeys in surface.
Embodiment 12
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) first prepare the polyethylene porous membrane of surface grafting sulfonate radical, polyethylene porous membrane (thickness 16 μ m, porosity is 40%, is purchased from Targray) surface grafting sulfonic group method is with embodiment 1, the KHCO with pH=8 by the sulfonic polyethylene porous membrane of surface band then
3aqueous solution soaking 3min makes sulfonic group be converted into sulfonate radical anion, then by the film after processing at poly--(4-vinyl-N-benzyltrimethylammonium chloride) (PVBTMAC, see formula V, CAS:9017-80-5, be purchased from Scientific Polymer Product, Inc.) in the 1wt% aqueous solution, soak 3min, make film adsorb positively charged PMAPTAC by electrostatic interaction, thereby make to become positively charged on polyethylene porous membrane surface lotus.It is 1 * 10 that the polyethylene porous membrane of surface band positive charge is immersed in to mass concentration
-23min in % aramid nano-fiber dispersion liquid, then takes out, washes, is dried, and so circulation is totally 5 times, makes the composite membrane of the attached aramid nano-fiber that is of five storeys in surface.
Embodiment 13
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) first prepare the polyethylene porous membrane of surface grafting sulfonate radical, polyethylene porous membrane (thickness 16 μ m, porosity is 40%, is purchased from Targray) grafting sulfonic group method is with embodiment 1, the KHCO of pH=8 for the sulfonic polyethylene porous membrane of surface band just then
3aqueous solution soaking 3min makes sulfonic group be converted into sulfonate radical anion, then by the film after processing at poly--(4-vinyl-N-benzyltrimethylammonium chloride) (PVBTMAC, see formula V, CAS:9017-80-5, be purchased from Scientific Polymer Product, Inc.) in the 1wt% aqueous solution, soak 3min, make film adsorb positively charged PMAPTAC by electrostatic interaction, thereby make to become positively charged on polyethylene porous membrane surface lotus.It is 1 * 10 that the polyethylene porous membrane of surface band positive charge is immersed in to mass concentration
-23min in % aramid nano-fiber dispersion liquid, then takes out, washes, is dried, and so circulation is totally 5 times, makes the composite membrane of the attached aramid nano-fiber that is of five storeys in surface.
Embodiment 14: comparative example 1
Take without the Celgard2500 polypropylene porous film (thickness is 25 μ m, and porosity is 55%, is purchased from Celgard company) of any processing is comparative film, tests 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 without any processing (thickness 16 μ m, porosity is 40%, is purchased from Targray), be comparative film, test its Gurley value, to the pick up of electrolyte and percent thermal shrinkage.
Embodiment 16: the performance index evaluation method of polyolefin/aramid nano-fiber composite membrane:
By following way, measure air penetrability, MacMullin Number and the percent thermal shrinkage of the prepared composite membrane of embodiment 1～15, thus the performance of evaluation composite membrane.
(1) method of testing of Gurley value
In the present invention, the gas permeability of film is tested with Gurley4110N Permeability gauge.The gas permeability of film is weighed with Gurley value.Gurley value is defined as a certain amount of gas and by a side of film, arrives the needed time of opposite side of film.In the present invention, using the air of 100cc by the needed time of film as Gurley value, with stopwatch, carry out timing.Its Gurley value of composite membrane that the present invention is prepared and the Gurley value of comparative film are listed in table 1.
(2)MacMullin?Number
In the present invention, prepared composite diaphragm is washed into the disk that diameter is 16mm with perforating press, then film is placed in to LiPF
6concentration is the ethylene carbonate (EC) of 1mol/L: more than soaking 1min in the solution of methyl ethyl carbonate (EMC)=2:1 (volume ratio), then take out, film is fixed on stainless steel electrode, with the accurate electric impedance analyzer of 1287 electrochemical interfaces (Britain Solartron company) and 4294A (beautiful Agilent) measure composite membrane at 1kHz place, the impedance of ambient temperature while being 25 ± 1 ℃, with this, calculate the ionic conductivity of film.Measure the ionic conductivity of electrolyte simultaneously.MacMullin number (Nm) is defined as the ratio of ionic conductivity after the wetting electrolyte of barrier film and electrolyte body ionic conductivity, and test result is 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 percent thermal shrinkage, weigh the dimensional stability of film.Prepared composite diaphragm is cut into the sheet of 5 * 5cm, is then placed on hot platform, at 150 ℃ and 170 ℃, maintain 30min respectively, calculate the percent thermal shrinkage of film.Percent thermal shrinkage is:
A
1for the area of film when the room temperature, A
2for at 150 ℃ or 170 ℃ of areas that maintain 30min caudacoria.Test result is in Table 1.
From table 1, polyolefin/aramid nano-fiber composite membrane that the present invention prepares, in maintenance good gas permeability and ionic conductivity performance, significantly improved thermal endurance, percent thermal shrinkage significantly reduces, the low temperature closed pore characteristic and the good thermal endurance of aramid fiber that combine polyolefin porous membrane, be applicable to being applied to needs and separate in the electrochemical device of both positive and negative polarity under higher temperature.Especially, be applicable in lithium ion battery, can improve the fail safe of lithium ion battery.
The performance index of table 1 polyolefin/aramid nano-fiber composite membrane
Remarks: a. thermal endurance test condition is to maintain 30min at 130 ℃.
B. contraction is comparatively strong, is difficult to Measurement accuracy.
---represent not measure.
Above-described embodiment is preferably execution mode of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under Spirit Essence of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (10)
1. for a preparation method for polyolefin/aramid nano-fiber composite membrane of lithium ion battery, it is characterized in that comprising the following steps:
(1) on polyolefin porous membrane surface, introduce after acidic-group, with alkali lye, process, obtain the polyolefin porous membrane of surface band negative electrical charge;
(2) be immersed in the polyelectrolyte solution of the positively charged group of side chain, obtained the polyolefin porous membrane of surface band positive charge;
(3) polyolefin porous membrane of surface band positive charge is immersed in aramid nano-fiber dispersion liquid, takes out, wash, dry, obtain polyolefin/aramid nano-fiber composite membrane.
2. the preparation method of the polyolefin/aramid nano-fiber composite membrane for lithium ion battery according to claim 1, it is characterized in that: the described polyelectrolyte of step (2) can be quaternary ammonium salt, quaternary alkylphosphonium salt, the sulfonium salt with structure shown in following formula I or formula II, or in molecule, there is the polyelectrolyte of the fragrant heterocycle cation of armaticity or PDDA:
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, and D is phenylene or methylene; X
1 --, X
2 --be respectively electronegative halogen ion or other electronegative acid ions; R
1, R
2be respectively H atom or alkyl; R
3, R
4be respectively alkyl; M, n are respectively 0～10 natural number; When B is N or P atomic time, p=3; When B is the S atomic time, p=2.
3. the preparation method of the polyolefin/aramid nano-fiber composite membrane for lithium ion battery according to claim 1, is characterized in that: the mass concentration of aramid nano-fiber dispersion liquid used is 1 * 10
-3%～8%; Described aramid fiber is meta-aramid or p-aramid fiber, or in strand, contains heteroatomic meta-aramid or the p-aramid fibers such as Si.
4. the preparation method of the polyolefin/aramid nano-fiber composite membrane for lithium ion battery according to claim 1, is characterized in that: the described polyolefin porous membrane of step (1) is the duplicature of polyethylene porous membrane, polypropylene porous film and polyethylene/polypropylene or at least one in multilayer film.
5. the preparation method of the polyolefin/aramid nano-fiber composite membrane for lithium ion battery according to claim 1, is characterized in that: the described acidic-group of step (1) is carboxyl, phenolic hydroxyl group, sulfonic group, benzene sulfonic acid base or phosphate.
6. the preparation method of the polyolefin/aramid nano-fiber composite membrane for lithium ion battery according to claim 1, is characterized in that: the described alkali lye of step (1) is KOH, NaOH, LiOH, K
2cO
3, Na
2cO
3, Li
2cO
3, KHCO
3or NaHCO
3alkaline aqueous solution.
7. the preparation method of the polyolefin/aramid nano-fiber composite membrane for lithium ion battery according to claim 1, it is characterized in that immersion, washing, dry by being cycled to repeat step (3), prepare polyolefin/aramid nano-fiber composite membrane of multilayer aramid fiber.
8. the preparation method of the polyolefin/aramid nano-fiber composite membrane for lithium ion battery according to claim 1, is characterized in that: the soak time described in step (3) is 0.1～20min; Described dry finger is dry 1～120min at 50～100 ℃.
9. for polyolefin/aramid nano-fiber composite membrane of lithium ion battery, it is characterized in that obtaining according to the preparation method of the polyolefin/aramid nano-fiber composite membrane for lithium ion battery described in claim 1～8 any one.
10. polyolefin/aramid nano-fiber the composite membrane for lithium ion battery according to claim 9 is in the application of electrochemical device.
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| CN105932197A (en) * | 2016-05-23 | 2016-09-07 | 北京理工大学 | Preparation method of poly (p-phenylene terephthalamide) porous membrane |
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| CN110620205A (en) * | 2019-10-08 | 2019-12-27 | 山东精恒科技有限公司 | Preparation method of para-aramid/PP non-woven fabric lithium ion battery diaphragm |
| CN111244366A (en) * | 2020-01-20 | 2020-06-05 | 哈尔滨工业大学 | Preparation method of lithium-sulfur battery diaphragm based on multilayer aramid nanofibers |
| 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 |
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