CN107170942A - A kind of high-temperature resistant aramid fiber lithium ion battery composite separation membrane and preparation method thereof - Google Patents
A kind of high-temperature resistant aramid fiber lithium ion battery composite separation membrane and preparation method thereof Download PDFInfo
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- CN107170942A CN107170942A CN201710405931.3A CN201710405931A CN107170942A CN 107170942 A CN107170942 A CN 107170942A CN 201710405931 A CN201710405931 A CN 201710405931A CN 107170942 A CN107170942 A CN 107170942A
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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
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/491—Porosity
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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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- 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
- H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
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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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- 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
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Abstract
The invention discloses a kind of high-temperature resistant aramid fiber lithium ion battery composite separation membrane and preparation method thereof, belong to the technical field of lithium ion battery material.The present invention includes basement membrane and the coating for being coated on basement membrane unilateral or bilateral, and coating is aramid fiber coating, and aramid fiber coating is prepared from by the raw material of following weight percentage：Aramid fiber 1 6%, pore former 5 12%, inorganic ceramic particle 0.5 5%, organic solvent 77 93.5%；The aramid fiber content that aramid fiber is derived from aramid fiber condensate, aramid fiber condensate is 10 30% according to weight.The coating and basement membrane interface binding force of the present invention is good, coating is difficult for drop-off under long-time and high intensity use condition, ventilative value and aperture are adjustable, and heat resistance, electrolyte wellability and puncture strength are effectively improved, and improve the security performance of lithium ion battery separator；The present invention causes phase inversion method gel film forming using non-solvent, and technique is simply controllable, it is easy to batch and continuous production.
Description
Technical field
The invention belongs to the technical field of lithium ion battery material, particularly relate to a kind of high-temperature resistant aramid fiber lithium ion battery and answer
Close barrier film and preparation method thereof.
Background technology
Lithium ion battery is widely used in mobile electronic device the advantages of its high-energy-density and long circulation life
In power set, however, the lithium ion battery security incident frequently occurred causes the extensive concern of people.Wherein, barrier film
One of important component as lithium ion battery, it is possible to provide lithium ion transport passage, also, prevent positive and negative electrode contact hair
Raw short circuit, has very important influence to the security of lithium ion battery, therefore, the property of the development of lithium ion battery to barrier film
There can be higher requirement.
Polyalkene diaphragm is current most popular lithium ion battery separator, and still, polyalkene diaphragm has thermal contraction
The problem of rate too high and electrolyte wellability is not enough.The widest polyalkene diaphragm of current application is polyethylene (PE) and polypropylene
(PP), it just occurs softening transform more than 100 DEG C.It is main at present in order to improve the heat endurance and wellability of polyalkene diaphragm
The solution wanted is the single or double applying coating in polyalkene diaphragm, and this coating has higher heat endurance, by
The security performance of this thermal contraction performance that can improve barrier film and lithium ion battery.
When the conventional coating method of Front-coating mirror has two kinds, one kind is to dissolve Kynoar (PVDF) in acetone, will
It is coated on polyolefin base material, is gone out solvent by drying and volatilizing, is obtained the heat resistant polymer coating with microcellular structure；
Such a method can improve barrier film heat resistance, electrolyte wellability and the caking property with electrode；But, this PVDF coatings
Because using low boiling point organic solvents such as acetone, as pore creating material, security risk is big；Meanwhile, this method is more micro- to heat-resistant polymer
The thickness and pattern of aperture layer are difficult accurately to be controlled, and require harsh to ambient humidity, once ambient humidity is varied from easily making
Into phenomenons such as holes, ceasmas, or it is easily formed dense film.Another be coated on polyalkene diaphragm one layer it is heat-resisting inorganic
Coating, the inorganic particulate of conventional coating has aluminum oxide (Al2O3), zirconium dioxide (ZrO2), silica (SiO2) etc.；Such a side
Method can effectively improve barrier film resistance to elevated temperatures, electrolyte affinity, puncture strength and fusing-off temperature, reduce Li dendrite pierce through every
The risk of film, improves the overall security of barrier film；But, this ceramic coated exist with base material binding ability difference and easily fall
The problem of powder, and increasing adhesion by binding agent can cause barrier film gas permeability to be deteriorated；Meanwhile, the strong absorptive of ceramic particle
Made troubles for lithium ion battery production, only needing 80 DEG C of condition drying to meet before the battery core fluid injection of polyalkene diaphragm assembling will
Ask, and the battery core of ceramic diaphragm assembling needs more than 110 DEG C of temperature drying to meet fluid injection requirement, adds lithium-ion electric
Pond manufacturer production cost.
Aramid fiber has the premium properties such as superhigh intensity, high-modulus, high temperature resistant, resistant to chemical etching, and its heat decomposition temperature can reach
To 400-430 DEG C, the heat resistance and security performance of lithium ion battery can be greatly improved.Chinese patent (CN101872852A) is with super
Based on short aramid fiber, manufactured paper with pulp with addition of aramid fiber fibrid and prepare the battery diaphragm of aramid fiber；This use papermaking process institute
Obtained membrane thicknesses are larger, and pore size and pore size distribution is larger, and homogeneity is poor, and self discharge effect is big, be difficult to 3C lithiums from
Sub- battery.Chinese patent (CN104993089A) will be made up of dissolving aramid fiber liquid, emulsifier solution and polymer adhesive
Aramid fiber slurry be coated on basement membrane, a kind of lithium ion battery separator of aramid fiber coating is obtained after immersion, drying, the method is adopted
Lysate is made with dissolving aramid fiber, course of dissolution can cause aramid fiber to decompose, molecular weight degradation, loses aramid fiber coating
Energy.Aramid fiber condensate and emulsifying agent, adhesive are mixed into slurry by Chinese patent (CN104979515A), in high humidity after coating
Steam pre- consolidated is carried out in 90% environment, then aramid fiber coating lithium ion battery separator is obtained through washing；It is newborn in the method
Agent, adhesive and solvent must be added separately to, and increase course of dissolution, while the adhesive added can cause the saturating of coat
Gas declines, and reduces the cycle performance of lithium ion mobility speed and battery.Chinese patent (CN103531736A) uses polarity
The mixture of two kinds of solvents composition less than 5 is pre- by volatilizing in atmosphere after being dissolved together with aramid fiber as pore creating material
Pore-creating, washing obtains aramid fiber coating lithium ion battery separator；It is also that lysate is made using dissolving aramid fiber in the method, it is molten
Solution preocess can cause aramid fiber to decompose, molecular weight degradation, aramid fiber paintability be lost, while the coating obtained by such a method
Layer cohesive force is poor, easily comes off, is unfavorable for processing and fabricating and recycling of the barrier film in battery.Chinese patent
(CN103824988A) aramid nano-fiber film is then prepared using electrostatic spinning, then prepares composite nano fiber lithium ion battery
Barrier film；This electrostatic spinning process is complicated, and governing factor is more, low production efficiency, and equipment cost is high, and product uniform stability compared with
Difference, industrialization is more difficult.
The content of the invention
The present invention provides a kind of high-temperature resistant aramid fiber lithium ion battery composite separation membrane and its preparation for above-mentioned problem
Method, composite diaphragm of the invention had both improved the interfacial bond property of coating and base material, while also significantly improving barrier film
Puncture resistance, thermal contraction performance and to electrolyte wellability etc., improve the security during lithium ion battery is used for a long time, this
The preparation method of invention has the advantages that simple preparation technology, membrane configuration and performance are easy to regulation and control, can realize industrialization.
A kind of high-temperature resistant aramid fiber lithium ion battery composite separation membrane of the present invention, it is mainly subject to by the following technical programs
Realize：Including basement membrane and the coating for being coated on the basement membrane unilateral or bilateral, the coating is aramid fiber coating, and the aramid fiber is applied
Layer is prepared from by the raw material of following weight percentage：Aramid fiber 1-6%, pore former 5-12%, inorganic ceramic particle 0.5-
5%, organic solvent 77-93.5%；The aramid fiber is derived from aramid fiber content in aramid fiber condensate, the aramid fiber condensate according to weight
Amount percentage composition is calculated as 10-30%.
The present invention is from aramid fiber as organic material, and aramid fiber is added in the polymeric form of aramid fiber, does not contain gluing
The processing aids such as agent, the interfacial stress between gained aramid fiber coating and basement membrane is small, and contact is good, difficult for drop-off, when long
Between and high intensity under it is easy to fall off using also not allowing；The ventilative value of gained aramid fiber coating and aperture are adjustable, are widely used, thermal contraction is low,
It is heat-resist, effectively improve the problem of basement membrane is poor to electrolyte wellability, improve the puncture strength of basement membrane, improve lithium from
The usage safety performance of sub- battery diaphragm.
As a kind of preferred embodiment, the aramid fiber is one or both of meta-aramid or p-aramid fiber, institute
The molecular weight for stating aramid fiber is 5000-200000Da.The present invention is directly using the aramid fiber in aramid fiber condensate, the virtue of this intermediate
Synthetic fibre function admirable, is not in aramid fiber decomposition, molecular weight degradation and the loss aramid fiber caused by dissolving aramid fiber process
The phenomenon of paintability.
As a kind of preferred embodiment, the pore former is any one in Inorganic pore forming agents or organic pore former
Or two kinds, the Inorganic pore forming agents are any one or a few in lithium chloride, sodium chloride, magnesium chloride, calcium carbonate or calcium chloride,
The organic pore former is methanol, ethanol, propyl alcohol, glycerine, polyethylene glycol, acetone, acetic acid, tetrahydrofuran, polyvinyl pyrrole
Any one or a few in alkanone, ethyl acetate or petroleum ether.In the present invention, polyethylene glycol can be from different molecular weight
Polyethylene glycol, for example：PEG, Mw：200-4000Da；Pore former can also use organic pore former using Inorganic pore forming agents
Or Inorganic pore forming agents and the mixture of organic pore former, coating can be effectively improved by adjusting the addition species and content of pore former
Membrane pore structure and aperture, adjust the gas permeability and chemical property of the composite diaphragm.
As a kind of preferred embodiment, the inorganic ceramic particle is aluminum oxide, silica, titanium dioxide, two
Any one or a few in zirconium oxide, magnesia, zinc oxide, barium monoxide, the average grain diameter of the inorganic ceramic particle is 10-
100nm.The addition of inorganic ceramic particle reduce further the heat-shrinkable of aramid fiber coating, improve the heat resistance of composite diaphragm
Energy；Also, the addition of this nanometer or micro inorganic ceramic particle does not influence the binding ability of aramid fiber and base material, is not in fall
The phenomenon of powder, it is not necessary to add binder, will not also extend the manufacture craft of barrier film, will not increase the life of lithium ion battery producer
Produce cost.The addition of inorganic ceramic particle improves the lyophily, paracentesis resistance energy and thermal contraction performance of barrier film.
As a kind of preferred embodiment, the organic solvent be DMA, 1-METHYLPYRROLIDONE,
N,N-dimethylformamide, one kind of repefral or any a variety of.DMA abbreviation DMAc, N-
Methyl pyrrolidone abbreviation NMP, DMF abbreviation DMF, repefral abbreviation DMP, these are organic
Solvent is good to the solubility property of aramid fiber, and aramid fiber, inorganic ceramic particle and pore former can be made to dissolve and be dispersed in organic well
In solvent, homogeneous composite diaphragm is advantageously formed.
As a kind of preferred embodiment, the basement membrane is porous basement membrane, the porous basement membrane be 5-40 μm of thickness and
Porosity 30-80% polyalkene diaphragm, the polyalkene diaphragm is polyethylene lithium ion battery separator, polypropylene lithium-ion electric
Any one in pond barrier film, three layers of polypropylene, polyethylene/polypropylene or multi-layer co-extruded composite lithium ion cell barrier film.It is this
Porous basement membrane is matched with aramid fiber coating, and the original gas permeability of porous basement membrane is not interfered with substantially, moreover, its ventilative value is adjustable, thoroughly
Gas is controllable.
As a kind of preferred embodiment, the thickness of the aramid fiber coating is 0.5-10 μm.By aramid fiber coating in base
The film that a layer thickness is 0.5-10 μm is formed on film, the heat-shrinkable of basement membrane is not only increased, moreover, effectively increasing basement membrane
Puncture strength, improve the security performance of lithium ion battery separator.
A kind of preparation method of high-temperature resistant aramid fiber lithium ion battery composite separation membrane of the present invention, it mainly passes through following skill
Art scheme is realized：Comprise the following steps：(1) preparation of aramid fiber casting solution：Take aramid fiber, pore former, inorganic ceramic particle
With organic solvent mixing, at 50-80 DEG C, stirring is completely dissolved aramid fiber and pore former, obtains casting solution；(2) deaeration：Will step
Suddenly casting solution obtained by (1) is at 50-80 DEG C, deaeration 5-60min, until without bubble；(3) non-solvent causes phase inversion method film forming：
Basement membrane is taken, the casting solution after one layer of deaeration of coating on base films stops 5-60s, is placed in coagulating bath and solidified, coagulating bath is
After solvent and non-solvent coagulating bath or water vapour coagulating bath, solidification 1-10min, the basement membrane with aramid fiber is taken, immersion is placed in water
10-60min, takes out；(4) dry：At 40-80 DEG C, dry 10-60min, obtain high-temperature resistant aramid fiber lithium ion battery it is compound every
Film.
The present invention by aramid fiber, pore former, inorganic ceramic particle and organic solvent mix, dissolving and deaeration after, using non-molten
Agent causes phase inversion method film forming, is obtained by drying, gained aramid fiber coating and basement membrane adhesion are good, it is possible to achieve more micro- to aramid fiber
The aperture of aperture layer, the accurate control of porosity, meanwhile, the performance that composite diaphragm adsorbs electrolyte is improved, is substantially increased multiple
Close the lyophily and liquid-keeping property of barrier film；This non-solvent causes phase inversion to have, and technological process is short, controllable (such as casting solution group of condition
Can efficient combination into adjustment, filming technology is easy to), reaction is gentle, production efficiency is high, it is excellent to be easy to batch and continuous production etc.
Point, with larger practical value.
As a kind of preferred embodiment, in solvent and the non-solvent coagulating bath, non-solvent is water, and solvent is N, N-
It is any one in dimethyl acetamide, 1-METHYLPYRROLIDONE, N,N-dimethylformamide, repefral or ethanol
Plant or several, the concentration of volume percent of solvent is 10-90% in solvent and the non-solvent coagulating bath；The water vapour solidification
The environment temperature of bath is 40-60 DEG C, and relative humidity is 60-90%.Phase inversion method film forming is caused using non-solvent, in solvent and non-molten
Under effective mating reaction of agent, the film top layer that is formed under film top layer and internal membrane microcellular structure, this environment is formed and interior
Preferably, Stability Analysis of Structures, condition is controllable, and using effect is good for the pore homogeneity of portion's membrane micropore.
As a kind of preferred embodiment, in the step (2), the viscosity of the casting solution after deaeration is 20-1000cP.
The viscosity of casting solution effectively after control deaeration can be such that casting solution preferably sticks on basement membrane, increase casting solution and basement membrane
Adhesive force, the control simultaneously for viscosity can improve the mobility of casting solution, so as to select various coating method.
Compared with prior art, the beneficial effects of the invention are as follows：The present invention is from aramid fiber as organic material, and aramid fiber is with virtue
The polymeric form of synthetic fibre is added, and does not contain the processing aids such as adhesive, and the interface between gained aramid fiber coating and basement membrane should
Power is small, and contact is good, difficult for drop-off, easy to fall off using also not allowing under long-time and high intensity；Gained aramid fiber coating is saturating
Gas value is in 300-1000s/in2Controllable in the range of ﹒ 100cc ﹒ 1.22Kpa, is widely used, thermal contraction is low, heat-resist, effectively
The problem of basement membrane is poor to electrolyte wellability is improved, the puncture strength of basement membrane is improved, improves lithium ion battery separator
Usage safety performance.Meanwhile, the preparation method of composite diaphragm of the invention has short technological process, mild condition, production efficiency
It is high, the advantages of be easy to batch and continuous production, it is adaptable to extension production.
Brief description of the drawings
In order to illustrate the embodiments of the present invention more clearly or technique effect of the prior art, below in conjunction with embodiment or
The accompanying drawing used required in description of the prior art is briefly described, it should be apparent that, drawings in the following description are only
The part accompanying drawing of some embodiments of the present invention, for those of ordinary skill in the art, is not paying creative work
Under the premise of, other accompanying drawings can also be obtained according to these accompanying drawings.
Fig. 1 is PE basement membranes in the present invention and electrolyte contacts angle measurement result figure；
Fig. 2 is the gained composite diaphragm of embodiment one in the present invention and electrolyte contacts angle measurement result figure；
Fig. 3 is cycle performance test result of the different barrier films in lithium ion battery；
Fig. 4 is the surface scan electron microscope of the composite diaphragm of the present invention；
In Fig. 3：■-PE basement membranes；●-composite diaphragm.
Embodiment
Technical scheme is clearly and completely described below in conjunction with the specific embodiment of the present invention, shown
So, described embodiment is only a part of embodiment of the present invention, rather than whole embodiments.Based in the present invention
Embodiment, the every other embodiment that those of ordinary skill in the art are obtained under the premise of creative work is not made, all
Belong to the scope of protection of the invention.
A kind of high-temperature resistant aramid fiber lithium ion battery composite separation membrane of the present invention, including basement membrane and to be coated on the basement membrane unilateral
Or the coating of bilateral, the coating is aramid fiber coating, and the aramid fiber coating is prepared from by the raw material of following weight percentage：
Aramid fiber 1-6%, pore former 5-12%, inorganic ceramic particle 0.5-5%, organic solvent 77-93.5%；The aramid fiber is derived from aramid fiber
Aramid fiber content in condensate, the aramid fiber condensate is 10-30% according to weight.
Further, the aramid fiber is one or both of meta-aramid or p-aramid fiber, the molecular weight of the aramid fiber
For 5000-200000Da.
Preferably, the pore former is any one in Inorganic pore forming agents or organic pore former or two kinds, described inorganic
Pore former is any one or a few in lithium chloride, sodium chloride, magnesium chloride, calcium carbonate or calcium chloride, the organic pore former
For methanol, ethanol, propyl alcohol, glycerine, polyethylene glycol, acetone, acetic acid, tetrahydrofuran, polyvinylpyrrolidone, ethyl acetate or
Any one or a few in petroleum ether.
Preferably, the inorganic ceramic particle is aluminum oxide, silica, titanium dioxide, zirconium dioxide, magnesia, oxygen
Change zinc, any one or a few in barium monoxide, the average grain diameter of the inorganic ceramic particle is 10-100nm.
Preferably, the organic solvent is DMA, 1-METHYLPYRROLIDONE, N, N- dimethyl formyls
Amine, repefral any one or a few.
Specifically, the basement membrane is porous basement membrane, and the porous basement membrane is the poly- of 5-40 μm of thickness and porosity 30-80%
Alkene barrier film, the polyalkene diaphragm is polyethylene lithium ion battery separator, polypropylene lithium ion battery separator, polypropylene/poly-
Any one in three layers of ethylene/polypropylene or multi-layer co-extruded composite lithium ion cell barrier film.It is highly preferred that the porous basement membrane
Thickness be 10-25 μm, the porosity of the porous basement membrane is 50-70%.
Further, the thickness of the aramid fiber coating is 0.5-10 μm.
A kind of preparation method of high-temperature resistant aramid fiber lithium ion battery composite separation membrane of the present invention, comprises the following steps：(1) it is fragrant
The preparation of synthetic fibre casting solution：Aramid fiber, pore former, inorganic ceramic particle and organic solvent mixing are taken, at 50-80 DEG C, stirring makes virtue
Synthetic fibre and pore former are completely dissolved, and obtain casting solution；(2) deaeration：By casting solution obtained by step (1) at 50-80 DEG C, deaeration 5-
60min, until without bubble；(3) non-solvent causes phase inversion method film forming：Basement membrane is taken, the casting after one layer of deaeration of coating on base films
Film liquid, stop 5-60s, be placed in coagulating bath and solidified, coagulating bath be solvent and non-solvent coagulating bath or water vapour coagulating bath,
Solidify after 1-10min, take the basement membrane with aramid fiber, be placed in water immersion or running water overflow 10-60min, take out；(4) dry：
At 40-80 DEG C, 10-60min is dried, high-temperature resistant aramid fiber lithium ion battery composite separation membrane is obtained.
Preferably, in solvent and the non-solvent coagulating bath, non-solvent is water, and solvent is DMA, N-
One or more in methyl pyrrolidone, DMF, repefral or ethanol, the solvent and
The concentration of volume percent of solvent is 10-90% in non-solvent coagulating bath；The environment temperature of the water vapour coagulating bath is 40-60
DEG C, relative humidity is 60-90%.
Further, in the step (2), the viscosity of the casting solution after deaeration is 20-1000cP.Preferably 50-
800cP.It is further preferred that the step (1) is in stirring, step (2) deaeration at 60-80 DEG C, the casting after deaeration at 60-80 DEG C
It is Best-Effort request film, spin-coating, dip-coating, spraying, scraper, coating bar or nick roller that film liquid, which is coated on epilamellar method,
Any one in coating, the step (3) stops 10-30s in atmosphere, solidifies in 1-5min, water and soaks 10-30min.
Embodiment one
By 5g aramid fibers, 1.25g glycerine, 1.25g polyvinylpyrrolidones, 0.25g alumina particles (average grain diameter 10nm),
42.25g DMAc are mixed, and aramid fiber is derived from aramid fiber condensate here, and the solid content of aramid fiber is 10% wherein in the aramid fiber condensate,
Mechanical agitation is carried out in 50 DEG C of oil bath, until aramid fiber and pore former dissolving are complete, the casting solution of aramid fiber is obtained；Stop stirring
Afterwards, in 50 DEG C of oil baths, deaeration 5min；It is smooth on clean glass plate to complete 20 μm of PE basement membranes, the hole of the PE basement membranes
Rate is 30%, the casting solution on PE basement membranes after appropriate deaeration, and knifing is carried out with bar, is stopped in atmosphere after 5s, slowly
In the coagulating bath at the uniform velocity immersing DMAc at room temperature and water, film forming after 1min, takes the PE films with aramid fiber off, is placed in water immersion
10min, takes out；In 40 DEG C of baking ovens, dry after 60min, take out.
Lithium ion battery composite separation membrane in the present embodiment is by 1% aramid fiber, 5% pore former, 0.5% inorganic pottery
What porcelain particle and 93.5% organic solvent were prepared from.
Embodiment two
By 4.54g aramid fibers, 1g acetone, 1.5g polyvinylpyrrolidones, 0.5g silica dioxide granules (average grain diameter 30nm),
42.46g DMF are mixed, and aramid fiber is derived from aramid fiber condensate here, and the solid content of aramid fiber is 22% wherein in the aramid fiber condensate, virtue
Synthetic fibre is p-aramid fiber, and the molecular weight of aramid fiber is 5000-10000Da, and mechanical agitation is carried out in 60 DEG C of oil bath, until aramid fiber and
Pore former dissolving is complete, obtains the casting solution of aramid fiber；Stop after stirring, in 60 DEG C of oil baths, deaeration 10min；In clean glass
Smooth in glass plate to complete 20 μm of PE basement membranes, the porosity of the PE basement membranes is 30%, is coated by the way of dip-coating, in air
Middle stop 15s, in the coagulating bath for slowly at the uniform velocity immersing DMF at room temperature and water, film forming after 3min, takes the PE films with aramid fiber off,
It is placed in water after immersion 20min, takes out；In 60 DEG C of baking ovens, dry after 45min, take out.
Lithium ion battery composite separation membrane in the present embodiment is by 2% aramid fiber, 5% pore former, 1% inorganic ceramic
What particle and 92% organic solvent were prepared from.
Embodiment three
By 9.08g aramid fibers, 2.5g magnesium chlorides, 2.5g polyvinylpyrrolidones, 1g silica dioxide granule (average grain diameters
50nm), 34.92g NMP are mixed, and aramid fiber is derived from aramid fiber condensate here, and wherein the solid content of aramid fiber is in the aramid fiber condensate
22%, mechanical agitation is carried out in 80 DEG C of oil bath, until aramid fiber and pore former dissolving are complete, the casting solution of aramid fiber is obtained；Stop
After only stirring, in 80 DEG C of oil baths, deaeration 20min；It is smooth on clean glass plate to complete 20 μm of PE basement membranes, the PE bases
The porosity of film is 30%, and the casting solution on PE basement membranes after appropriate deaeration carries out knifing with scraper, stopped in atmosphere
After 30s, in the coagulating bath for slowly at the uniform velocity immersing NMP at room temperature and water, film forming after 5min, is taken the PE films with aramid fiber off, is placed in
Soak after 30min, take out in water；In 80 DEG C of baking ovens, dry after 10min, take out.
Lithium ion battery composite separation membrane in the present embodiment is by 4% aramid fiber, 10% pore former, 2% inorganic pottery
What porcelain particle and 84% organic solvent were prepared from.
Example IV
By 26.4g aramid fibers, 7.2g calcium chloride, 6g polyvinylpyrrolidones, 5.5g alumina particles (average grain diameter 10nm),
34.9g DMAc and 30gDMF are mixed, and aramid fiber is derived from aramid fiber condensate here, the solid content of aramid fiber wherein in the aramid fiber condensate
For 25%, aramid fiber is meta-aramid, and the molecular weight of aramid fiber is 10000-100000Da, and machinery is carried out in 80 DEG C of oil bath and is stirred
Mix, until aramid fiber and pore former dissolving are complete, obtain the casting solution of aramid fiber；Stop after stirring, in 80 DEG C of oil baths, deaeration
30min；Smooth on clean glass plate to complete 20 μm of PE basement membranes, the porosity of the PE basement membranes is 30%, on PE basement membranes
Casting solution after appropriate deaeration, knifing is carried out with bar, in atmosphere stop 60s after, slowly at the uniform velocity immerse at room temperature DMAc,
In the coagulating bath of DMF and water, film forming after 10min, takes the PE films with aramid fiber off, is placed in water after immersion 45min, takes out；
In 80 DEG C of baking ovens, dry after 30min, take out.
Lithium ion battery composite separation membrane in the present embodiment is by 6% aramid fiber, 12% pore former, 5% inorganic pottery
What porcelain particle and 77% organic solvent were prepared from.
Embodiment five
By 22g aramid fibers, 3g PEG2000,2.5g polyvinylpyrrolidone, 1.3g titanium dioxide granule (average grain diameters
10nm), 2g alumina particles (average grain diameter 10nm), 79.2g DMAc mixing, aramid fiber is derived from aramid fiber condensate here, wherein should
The solid content of aramid fiber is 30% in aramid fiber condensate, and mechanical agitation is carried out in 80 DEG C of oil bath, until aramid fiber and pore former are molten
Solution is complete, obtains the casting solution of aramid fiber；Stop after stirring, the deaeration 60min in 80 DEG C of oil baths；It is smooth on clean glass plate
Complete 20 μm of PE basement membranes, the porosity of the PE basement membranes is 30%, the casting solution on PE basement membranes after appropriate deaeration, with scraping
Knife carries out knifing, stops in atmosphere after 60s, in the coagulating bath for slowly at the uniform velocity immersing ethanol at room temperature and water, film forming, 3min
Afterwards, the PE films with aramid fiber are taken off, is placed in water after immersion 60min, takes out；In 60 DEG C of baking ovens, dry after 60min, take out.
Lithium ion battery composite separation membrane in the present embodiment is by 6% aramid fiber, 5% pore former, 3% inorganic ceramic
What particle and 86% organic solvent were prepared from.
Embodiment six
By 4.54g aramid fibers, 2.5g acetic acid, 2.5g polyvinylpyrrolidones, 0.25g alumina particle (average grain diameters
10nm), 40.21g DMAc are mixed, and aramid fiber is derived from aramid fiber condensate here, and wherein the solid content of aramid fiber is in the aramid fiber condensate
22%, aramid fiber is meta-aramid, and the molecular weight of aramid fiber is 100000-200000Da, and mechanical agitation is carried out in 80 DEG C of oil bath,
Until aramid fiber and pore former dissolving are complete, the casting solution of aramid fiber is obtained；Stop after stirring, in 80 DEG C of oil baths, deaeration 30min；
Smooth on clean glass plate to complete 16 μm of PE basement membranes, the porosity of the PE basement membranes is 50%, appropriate on PE basement membranes
Casting solution after deaeration, knifing is carried out with scraper, is stopped in atmosphere after 20s, slowly at the uniform velocity immerses the solidifying of DMP at room temperature and water
Gu in bath, film forming after 3min, takes the PE films with aramid fiber off, it is placed in water after immersion 60min, takes out；In 60 DEG C of baking ovens,
Dry after 60min, take out.
Lithium ion battery composite separation membrane in the present embodiment be by 2% aramid fiber, 10% pore former, 0.5% it is inorganic
What ceramic particle and 92.5% organic solvent were prepared from.
Embodiment seven
By 4.54g aramid fibers, 2.5g PEG2000,2.5g polyvinylpyrrolidone, 0.25g titanium dioxide granules (average grain
Footpath 100nm), 40.21g DMAc mixing, aramid fiber is derived from aramid fiber condensate here, and wherein consolidating for aramid fiber contains in the aramid fiber condensate
Measure as 22%, aramid fiber is p-aramid fiber, and the molecular weight of aramid fiber is 10000-100000Da, and machinery is carried out in 80 DEG C of oil bath and is stirred
Mix, until aramid fiber and pore former dissolving are complete, obtain the casting solution of aramid fiber；Stop after stirring, in 80 DEG C of oil baths, deaeration
30min；Smooth on clean glass plate to complete 16 μm of PE basement membranes, the porosity of the PE basement membranes is 50%, on PE basement membranes
Casting solution after appropriate deaeration, knifing is carried out with scraper, is stopped in atmosphere after 20s, is slowly at the uniform velocity immersed DMAc at room temperature
With in the coagulating bath of water, film forming after 3min, takes the PE films with aramid fiber off, be placed in water after immersion 60min, take out, at 60 DEG C
In baking oven, dry after 60min, take out.
Lithium ion battery composite separation membrane in the present embodiment be by 2% aramid fiber, 10% pore former, 0.5% it is inorganic
What ceramic particle and 87.5% organic solvent were prepared from.
Embodiment eight
By 4.54g aramid fibers, 2.5g calcium carbonate, 2.5g polyvinylpyrrolidones, 0.25g silica dioxide granule (average grain diameters
30nm), 40.21g DMAc are mixed, and aramid fiber is derived from aramid fiber condensate here, and wherein the solid content of aramid fiber is in the aramid fiber condensate
22%, mechanical agitation is carried out in 80 DEG C of oil bath, until aramid fiber and pore former dissolving are complete, the casting solution of aramid fiber is obtained；Stop
After only stirring, in 80 DEG C of oil baths, deaeration 30min；It is smooth on clean glass plate to complete 16 μm of PE basement membranes, the PE bases
The porosity of film is 50%, and the casting solution on PE basement membranes after appropriate deaeration carries out knifing with bar, stopped in atmosphere
After 10s, in the coagulating bath for slowly at the uniform velocity immersing DMAc at room temperature and water, film forming after 3min, is taken the PE films with aramid fiber off, put
After Yu Shuizhong immersions 60min, take out；In 60 DEG C of baking ovens, dry after 60min, take out.
Lithium ion battery composite separation membrane in the present embodiment be by 2% aramid fiber, 10% pore former, 0.5% it is inorganic
What ceramic particle and 87.5% organic solvent were prepared from.
Embodiment nine
By 4.54g aramid fibers, 2.5g lithium chlorides, 2.5g polyvinylpyrrolidones, 0.25g silica dioxide granule (average grain diameters
50nm), 40.21g DMAc are mixed, and aramid fiber is derived from aramid fiber condensate here, and wherein the solid content of aramid fiber is in the aramid fiber condensate
22%, aramid fiber is meta-aramid, and the molecular weight of aramid fiber is 100000-200000Da, and mechanical agitation is carried out in 80 DEG C of oil bath,
Until aramid fiber and pore former dissolving are complete, the casting solution of aramid fiber is obtained；Stop after stirring, in 80 DEG C of oil baths, deaeration 60min；
Smooth on clean glass plate to complete 16 μm of PE basement membranes, the porosity of the PE basement membranes is 50%, appropriate on PE basement membranes
Casting solution after deaeration, knifing is carried out with scraper, is stopped in steam bath after 2min, is at the uniform velocity immersed and is carried out into room-temperature water bath
Film, is placed in water after immersion 60min, takes out；In 60 DEG C of baking ovens, dry after 60min, take out.
Lithium ion battery composite separation membrane in the present embodiment be by 2% aramid fiber, 10% pore former, 0.5% it is inorganic
What ceramic particle and 87.5% organic solvent were prepared from.
Comparative example one
2.3g DMF is weighed, 0.05g polyethylene glycol is added, stirs to being completely dissolved, 6g is added into above-mentioned lysate
Meta-aramid condensate, aramid fiber active ingredient 20%, aramid fiber molecular weight 0.5-2.0 ten thousand, after stirring, while stirring successively
1.5g dichloromethane and 0.15g vinyl pyrrolidone and vinyl acetate (PVP-VA) copolymerization adhesive are added, is disperseed
Aramid fiber slurry is uniformly made；The polyethylene based film of 20 μ m thicks is chosen, porosity is 30%, using slit coating method by virtue
Synthetic fibre slurry is coated on the bilateral of basement membrane, and application rate is 30m/min.The pre- consolidated 3s in the environment of 95% humidity, washes 15s,
Dried using three-level baking oven, oven temperatures at different levels are respectively 60 DEG C, 60 DEG C, 55 DEG C, aramid fiber polymer coated is obtained after drying
Lithium ion battery separator, obtain control sample one.
Comparative example two
2g DMAc is weighed, 0.1g Sodium Polyacrylate is added, stirring is added to being completely dissolved into above-mentioned lysate
4.4g meta-aramid condensate, aramid fiber content 10%, aramid fiber molecular weight 8-10 ten thousand after stirring, adds successively while stirring
Plus 3.35g isopropanol and 0.05g vinyl pyrrolidones and vinyl acetate (PVP-VA) copolymerization adhesive, the system of being uniformly dispersed
Obtain aramid fiber slurry；The polyethylene based film of 16 μ m thicks is chosen, and porosity is 50%, aramid fiber slurry is applied using plate gravure coating method
The one side of basement membrane is distributed in, application rate is 15m/min；The pre- consolidated 10s in the environment of 90% humidity, washes 10s, uses three-level
Baking oven is dried, and oven temperatures at different levels are respectively 55 DEG C, 60 DEG C, 70 DEG C, and the lithium ion of aramid fiber polymer coated is obtained after drying
Battery diaphragm, obtains control sample two.
By the embodiment of the present invention one to nine kinds of lithium ion battery composite separation membranes of the gained of embodiment nine, control sample one and control sample
Two carry out the test of thickness, intensity, ventilative value and heat-shrinkable respectively, and take the polyethylene based film of same thickness and porosity
The test of thickness, intensity, ventilative value and heat-shrinkable is carried out in the same manner, wherein, the present embodiment one to embodiment five
Basement membrane used is 20 μm of polyethylene based films, and the basement membrane of the selection of control sample one is also 20 μm of polyethylene based films, and with 20 μm
Polyethylene based film is as control sample three, and the basement membrane used in the present embodiment six to embodiment nine is 16 μm of polyethylene based films, control sample
Two selections are also 16 μm of polyethylene based films, and using 16 μm of polyethylene based film as control sample four, test result is included in table 1 respectively
In table 2, in Tables 1 and 2, thickness is tested according to method as defined in GB/T6672-2001,
Tensile strength is tested according to method as defined in GB/13022-91, and puncture strength is according to GB/T21302-2007
Defined method is tested, and ventilative value is tested according to method as defined in GB/1038, and thermal contraction is according to GB/T12027-
Method is tested as defined in 2004.
The aramid fiber coating of the present invention of table 1 the performance test results in 20 μm of polyethylene based films contrast situation
As can be seen from Table 1, the embodiment of the present invention one to the gained high-temperature resistant aramid fiber lithium ion battery of embodiment five it is compound every
The thickness of film is between 21.9-28.9 μm, and more corresponding polyethylene based film (i.e. control sample three) substantially increases 0.8-7.9 μm,
The thickness of the lithium ion battery separator (i.e. control sample one) with aramid fiber coating with being prepared using existing method is basically identical；
The embodiment of the present invention one to the gained high-temperature resistant aramid fiber lithium ion battery composite separation membrane of embodiment five tensile strength MD with it is existing
The tensile strength MD of lithium ion battery separator (i.e. control sample one) with aramid fiber coating prepared by method is also basically identical；But
It is that the puncture strength of the embodiment of the present invention one to the gained high-temperature resistant aramid fiber lithium ion battery composite separation membrane of embodiment five is 635.9-
682.2g, this is also applied apparently higher than polyethylene based film (i.e. control sample three) apparently higher than prepared by existing method with aramid fiber
The lithium ion battery separator (i.e. control sample one) of layer；Also, the embodiment of the present invention one is to the gained high-temperature resistant aramid fiber lithium of embodiment five
The ventilative value of ion battery composite diaphragm is in 360.5-453.2s/in2In the range of ﹒ 100cc ﹒ 1.22Kpa；The embodiment of the present invention one
Placed to the gained high-temperature resistant aramid fiber lithium ion battery composite separation membrane of embodiment five in 90 DEG C of baking ovens after 1h, its horizontal and vertical heat
Shrinkage value is 0, is placed in 105 DEG C of baking ovens after 1h, its horizontal and vertical Heat Shrinkage value is<0.5%, put in 120 DEG C of baking ovens
Put after 1h, its horizontal and vertical Heat Shrinkage value<5%；This is significantly better than corresponding polyethylene based film (i.e. control sample three) and now
Lithium ion battery separator (i.e. control sample one) with aramid fiber coating prepared by some methods.
The aramid fiber coating of the present invention of table 2 the performance test results in 16 μm of polyethylene based films contrast situation
As can be seen from Table 2, the embodiment of the present invention six to the gained high-temperature resistant aramid fiber lithium ion battery of embodiment nine it is compound every
The thickness of film is between 17.21-17.94 μm, and more corresponding polyethylene based film (i.e. control sample four) substantially increases 0.78-1.51
μm, the thickness of the lithium ion battery separator (i.e. control sample two) with aramid fiber coating prepared with existing method is basically identical；
The embodiment of the present invention six to the gained high-temperature resistant aramid fiber lithium ion battery composite separation membrane of embodiment nine tensile strength MD with it is existing
The tensile strength MD of lithium ion battery separator (i.e. control sample two) with aramid fiber coating prepared by method is also basically identical；But
It is that the puncture strength of the embodiment of the present invention six to the gained high-temperature resistant aramid fiber lithium ion battery composite separation membrane of embodiment nine is 634.1-
655.7g, this is also applied apparently higher than polyethylene based film (i.e. control sample four) apparently higher than prepared by existing method with aramid fiber
The lithium ion battery separator (i.e. control sample two) of layer；Also, the embodiment of the present invention six is to the gained high-temperature resistant aramid fiber lithium of embodiment nine
The ventilative value of ion battery composite diaphragm is in 314.4-379.5s/in2Adjustable between ﹒ 100cc ﹒ 1.22Kpa, this is substantially better than existing
Lithium ion battery separator (i.e. control sample two) with aramid fiber coating prepared by some methods；The embodiment of the present invention six is to embodiment
Nine gained high-temperature resistant aramid fiber lithium ion battery composite separation membranes are placed after 1h in 90 DEG C of baking ovens, and its horizontal and vertical Heat Shrinkage value is
0, placed in 105 DEG C of baking ovens after 1h, its horizontal and vertical Heat Shrinkage value is<0.5%, placed in 120 DEG C of baking ovens after 1h, its
Horizontal and vertical Heat Shrinkage value<4%；This is significantly better than its corresponding polyethylene based film (i.e. control sample four) and existing method
The lithium ion battery separator (i.e. control sample two) with aramid fiber coating prepared.
High-temperature resistant aramid fiber lithium ion battery composite separation membrane prepared by the embodiment of the present invention one to embodiment nine is corresponding
Polyethylene based film be respectively placed in electrolyte, in Ke Lvshi scientific instrument (Shanghai) Co., Ltd. produce DSA25 optics connect
The measure of contact angle is carried out on feeler measuring instrument；Experimental result is found, is existed as the PE barrier films of basement membrane and the contact angle of electrolyte
30-36.5 °, and the contact angle of the composite diaphragm of the present invention and electrolyte is 10-25 °.And by the embodiment of the present invention one to implementation
After high-temperature resistant aramid fiber lithium ion battery composite separation membrane and its corresponding polyethylene based film prepared by example nine is respectively placed in electrolyte
Its pick up before and after immersion is determined, finally, is loaded into lithium ion battery and carries out capacity holding and cycle performance test.
The pick up of the composite diaphragm and its basement membrane of the present invention of table 3 in the electrolytic solution
Accompanying drawing 1 and accompanying drawing 2 list respectively the preparation of the embodiment of the present invention one high-temperature resistant aramid fiber lithium ion battery it is compound every
The test temperature of contact angle in the measurement result of the contact angle of film and its corresponding polyethylene based film and electrolyte, accompanying drawing 1 and accompanying drawing 2
Spend for 20 DEG C, liquid is water, the contact it can be seen from accompanying drawing 1 and accompanying drawing 2 as 20 μm of PE barrier films of basement membrane with electrolyte
Angle is 36.4 °, and the contact angle of the composite diaphragm of the present invention and electrolyte is 20.9 °.Table 3 lists the system of the embodiment of the present invention one
Standby high-temperature resistant aramid fiber lithium ion battery composite separation membrane and its corresponding polyethylene based film and imbibition of the electrolyte before and after immersion
Rate situation, as can be seen from Table 3, PE basement membrane pick ups only have 76.35%, and the pick up of control sample one is 94.95%, and passes through this
The pick up of high-temperature resistant aramid fiber lithium ion battery composite separation membrane prepared by the method for invention is up to 122.27%, it is therefore seen that of the invention
With electrolyte affinity more preferably, pick up is high for the aramid fiber composite diaphragm of preparation, can have in lithium ion battery use preferable
Lyophily protects fluidity, so as to improve discharge capacity of the cell and cycle performance.Accompanying drawing 3 lists the resistance to height of the preparation of the embodiment of the present invention one
The capacity that warm aramid fiber lithium ion battery composite separation membrane and its corresponding polyethylene based film load after lithium ion battery keeps and circulated
Performance test, it can be seen from accompanying drawing 3 after 40 primary cell charge and discharge cycles, the specific discharge capacity of polyethylene based film from
76.54mAh/g is down to 62.85mAh/g, and capability retention is 82%, and the high-temperature resistant aramid fiber lithium ion battery of the present invention is combined
The specific discharge capacity of barrier film is only down to 73.74mAh/g from 78.21mAh/g, and capability retention is 94.28%, with preferable appearance
Conservation rate and cycle performance are measured, battery is effectively improved.
Therefore, composite diaphragm of the invention improves a lot to the wellability of electrolyte, and aramid fiber is coated in polyolefin base membrane
Surface can be effectively improved the problem of polyolefin is poor to electrolyte wellability, and electrolyte pick up is greatly improved, and also changes
The capacity for being apt to lithium ion battery is kept and cycle life.
High-temperature resistant aramid fiber lithium ion battery composite separation membrane prepared by the embodiment of the present invention one to embodiment nine is respectively at moral
It is scanned in the EVO/MA10 SEM that state's Zeiss is produced, is prepared by the embodiment of the present invention one to embodiment nine
High-temperature resistant aramid fiber lithium ion battery composite separation membrane is on the CHI660E electrochemical workstations that Shanghai Chen Hua Instrument Ltd. produces
Testing impedance is carried out, composite diaphragm is is made for half-cell by method of testing, i.e., by stainless steel substrates, composite diaphragm, stainless steel substrates
It is sequentially loaded into button cell shell, injects appropriate electrolyte, AC impedance spectroscopy, impedance are obtained by electrochemical workstation
The intersection point of spectrogram upper curve and real axis is diaphragm impedance, is calculated using formula and obtains ionic conductivity.
Accompanying drawing 4 lists the high-temperature resistant aramid fiber lithium ion battery composite separation membrane electron-microscope scanning of the preparation of the embodiment of the present invention one
Figure, the high-temperature resistant aramid fiber lithium ion battery composite separation membrane of the present invention has stable microcellular structure, hole it can be seen from accompanying drawing 4
Footpath is uniform in size consistent, with good permeability.Testing impedance test result indicates that, lithium particle battery of the invention it is compound every
The diaphragm impedance of film is less than 5 ohm, and ionic conductivity is in 0.2-1.0mS ﹒ cm-1Between；Therefore, composite diaphragm impedance of the invention
Small, ionic conductivity is big, and this ion shown in electrolyte more easily propagates through the composite diaphragm of the present invention, so that the present invention
Composite diaphragm has more excellent battery performance.
Therefore, compared with prior art, the beneficial effects of the invention are as follows：The present invention is used as organic material, virtue from aramid fiber
Synthetic fibre is added in the polymeric form of aramid fiber, the processing aids such as adhesive is not contained, between gained aramid fiber coating and basement membrane
Interfacial stress is small, and contact is good, difficult for drop-off, easy to fall off using also not allowing under long-time and high intensity；Gained aramid fiber
The ventilative value of coating is in 300-1000s/in2Controllable in the range of ﹒ 100cc ﹒ 1.22Kpa, is widely used, thermal contraction is low, heat resistance
It is good, the problem of basement membrane is poor to electrolyte wellability is effectively improved, the puncture strength of basement membrane is improved, improves lithium ion battery
The usage safety performance of barrier film.Meanwhile, the preparation method of composite diaphragm of the invention has short technological process, mild condition, effect
Rate is high, it is easy in batches with continuous production the advantages of, it is adaptable to extension production.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
God is with principle, and any modification, equivalent substitution and improvements made etc. should be included in the scope of the protection.
Claims (10)
1. a kind of high-temperature resistant aramid fiber lithium ion battery composite separation membrane, including basement membrane and the painting for being coated on the basement membrane unilateral or bilateral
Layer, the coating is aramid fiber coating, it is characterised in that：The aramid fiber coating by following weight percentage raw material prepare and
Into：
Aramid fiber 1-6%, pore former 5-12%, inorganic ceramic particle 0.5-5%, organic solvent 77-93.5%；
The aramid fiber content that the aramid fiber is derived from aramid fiber condensate, the aramid fiber condensate is 10- according to weight
30%.
2. high-temperature resistant aramid fiber lithium ion battery composite separation membrane according to claim 1, it is characterised in that：
The aramid fiber is one or both of meta-aramid or p-aramid fiber, and the molecular weight of the aramid fiber is 5000-
200000Da。
3. high-temperature resistant aramid fiber lithium ion battery composite separation membrane according to claim 1, it is characterised in that：
The pore former is any one in Inorganic pore forming agents or organic pore former or two kinds, and the Inorganic pore forming agents are chlorination
Any one or a few in lithium, sodium chloride, magnesium chloride, calcium carbonate or calcium chloride, the organic pore former be methanol, ethanol,
Appointing in propyl alcohol, glycerine, polyethylene glycol, acetone, acetic acid, tetrahydrofuran, polyvinylpyrrolidone, ethyl acetate or petroleum ether
Meaning is one or more of.
4. high-temperature resistant aramid fiber lithium ion battery composite separation membrane according to claim 1, it is characterised in that：
The inorganic ceramic particle is aluminum oxide, silica, titanium dioxide, zirconium dioxide, magnesia, zinc oxide or barium monoxide
In any one or a few, the average grain diameter of the inorganic ceramic particle is 10-100nm.
5. high-temperature resistant aramid fiber lithium ion battery composite separation membrane according to claim 1, it is characterised in that：
The organic solvent is DMAC N,N' dimethyl acetamide, 1-METHYLPYRROLIDONE, N,N-dimethylformamide or O-phthalic
Any one or a few in dimethyl phthalate.
6. high-temperature resistant aramid fiber lithium ion battery composite separation membrane according to claim 1, it is characterised in that：
The basement membrane is porous basement membrane, and the porous basement membrane is 5-40 μm of thickness and porosity 30-80% polyalkene diaphragm, institute
Polyalkene diaphragm is stated for polyethylene lithium ion battery separator, polypropylene lithium ion battery separator, polypropylene, polyethylene/polypropylene
Any one in three layers or multi-layer co-extruded composite lithium ion cell barrier film.
7. high-temperature resistant aramid fiber lithium ion battery composite separation membrane according to claim 1, it is characterised in that：
The thickness of the aramid fiber coating is 0.5-10 μm.
8. the preparation method of the high-temperature resistant aramid fiber lithium ion battery composite separation membrane according to any one in claim 1-7,
It is characterized in that：Comprise the following steps：
(1) preparation of aramid fiber casting solution：Aramid fiber, pore former, inorganic ceramic particle and organic solvent mixing are taken, at 50-80 DEG C,
Stirring, is completely dissolved aramid fiber and pore former, obtains casting solution；
(2) deaeration：By casting solution obtained by step (1) at 50-80 DEG C, deaeration 5-60min, until without bubble；
(3) non-solvent causes phase inversion method film forming：Basement membrane is taken, the casting solution after one layer of deaeration of coating on base films stops 5-60s,
It is placed in coagulating bath and is solidified, coagulating bath is solvent and non-solvent coagulating bath or water vapour coagulating bath, is solidified after 1-10min,
The basement membrane with aramid fiber is taken, immersion 10-60min is placed in water, takes out；
(4) dry：At 40-80 DEG C, 10-60min is dried, high-temperature resistant aramid fiber lithium ion battery composite separation membrane is obtained.
9. the preparation method of high-temperature resistant aramid fiber lithium ion battery composite separation membrane according to claim 8, it is characterised in that：
In solvent and the non-solvent coagulating bath, non-solvent is water, and solvent is DMA, N- crassitudes
Any one or a few in ketone, DMF, repefral or ethanol, the solvent and non-solvent
The concentration of volume percent of solvent is 10-90% in coagulating bath；
The environment temperature of the water vapour coagulating bath is 40-60 DEG C, and relative humidity is 60-90%.
10. the preparation method of high-temperature resistant aramid fiber lithium ion battery composite separation membrane according to claim 8, it is characterised in that：
In the step (2), the viscosity of the casting solution after deaeration is 20-1000cP.
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