CN106953052A - A kind of preparation method of lithium ion battery separator - Google Patents
A kind of preparation method of lithium ion battery separator Download PDFInfo
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- CN106953052A CN106953052A CN201710156849.1A CN201710156849A CN106953052A CN 106953052 A CN106953052 A CN 106953052A CN 201710156849 A CN201710156849 A CN 201710156849A CN 106953052 A CN106953052 A CN 106953052A
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- ion battery
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- 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
-
- 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
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of preparation method of lithium ion battery separator, it is main to include coating nano inoganic particle in polyethylene surface with Nano sol, then it is film-made using blending technology, first, a kind of by the compound of the silicon that can be hydrolyzed, titanium, aluminium and zirconium is configured to the solution that mass concentration is 8%~20%, is placed in ultrasound environments, water is slowly added dropwise in regulation pH value thereto, polyethylene particle is added to stir, and 3~8h of back flow reaction at 50~60 DEG C；Reaction removes microwave environment after terminating, and coupling agent is added into solution, continues to stir 12~24h, is filtrated to get after polyethylene particle and is film-made using blending technology.Nano-particle yardstick is small in barrier film duct obtained by the present invention and is uniformly dispersed, with good thermal stability and excellent permeability, is suitable for preparing high-energy-density lithium battery.
Description
Technical field
The present invention relates to a kind of technical field of new energies, more particularly to a kind of battery diaphragm preparation method.
Background technology
Barrier film is one of layer assembly in key in lithium ion battery structure, and it is to separate negative electrode to prevent short with anode that it, which is acted on,
Road, isolation electronics, allow electrolyte ion to pass through again.Barrier film is typically a kind of thin cellular insulant material, with good saturating
The property crossed, mechanical strength and solvent resistance.Traditional lithium ion battery separator is that polyolefin such as polypropylene or polyethylene pass through dry method
It is prepared by (stripping) or wet method (extraction) technique.Consumption-orientation lithium ion battery separator is needed toward thickness is thinner, porosity is higher, heat-resisting
Temperature is higher, uniformity is more preferable etc., and direction is developed.
As lithium battery diaphragm material, itself has microcellular structure, and distribution of the micropore in whole diaphragm material should be equal
It is even.The too small increase resistance in aperture, aperture too great Yi contacts both positive and negative polarity or pierces through short circuit by dendrite.Through performance can be used in certain
Under time and pressure, by the amount of diaphragm gas number characterize, mainly reflect the patency that lithium ion passes through barrier film.One
As for, barrier film is thicker, and its mechanical strength is bigger, and the possibility punctured in cell assembling processes is just smaller, but same template
Number battery, the active material that can be added thereto is then fewer；On the contrary, it is less to be taken up space using relatively thin barrier film, then add
Active material is just more, the capacity and specific capacity of battery can be improved simultaneously, the same impedance of thin barrier film is relatively low.Therefore in intensity
On the premise of qualified, high porosity barrier film is one of following developing direction.Presently commercially available high porosity barrier film is most badly in need of solving
Be thermal stability problems, because electrokinetic cell is typically all used under the conditions of high-power, long-time, be easier heating.When
During barrier film heat shrinkable, both positive and negative polarity will be contacted and set off an explosion, so requiring that the high-temperature shrinkage of barrier film is as small as possible now.Mesh
Before, generally solved the above problems using two methods, it is a kind of to coat one layer of ceramics in membrane surface, formed with porous and had
The barrier film of excellent heat stability.But the shortcoming of technique is：The thickness of barrier film is added, ceramics have dry linting phenomenon, needed simultaneously
A coating line is further added by meet process requirements.Another method is blending technology, i.e., by inorganic nanoparticles, poly- second
Alkene and paraffin oil three mix, and are fed by measuring pump in extruder.Although the technique can meet high hole simultaneously
Rate and good thermal stability, and hardly increase production cost, it is current study hotspot, but this realizes the technique
One difficult point is：Although the primary particle diameter of inorganic particle of manufacturer's design is nanoscale, by storage, transport, only by machine
Tool stirring is difficult to be broken up back Nano grade, even if primary particle diameter is the inorganic particulate of Nano grade, but is added in system
When also at least 10 μm of particle diameter.
The content of the invention
For above-mentioned prior art, the present invention provides a kind of preparation method of lithium ion battery separator, can be by nanoparticle
Son is incorporated into system, i.e. colloidal sol reaction is carried out under ultrasound condition, and the nano-particle inside colloidal sol is adsorbed onto into polyethylene
On grain, while in order to ensure that particle introduces the homogeneity of system, polyethylene particle is added to solution before colloidal sol reaction is carried out
In.
In order to solve the above-mentioned technical problem, the preparation method of a kind of lithium ion battery separator proposed by the present invention, including such as
Lower step：
Step 1: by one kind of the compound of the silicon that can be hydrolyzed, titanium, aluminium and zirconium be configured to mass concentration for 8%~
20% solution, is placed in ultrasound environments, and the pH value of solution is adjusted into 2 to 4 or 8 to 10, water is then slowly added dropwise thereto,
Water is 2.5~6 with the mol ratio of the compound:1, add polyethylene particle and stir, and flowed back at 50~60 DEG C
3~8h is reacted, the mass ratio of nano inoganic particle and polyethylene obtained by synthesis is 0.05~0.5:1；Reaction is removed after terminating
Microwave environment, coupling agent is added into solution, the mass ratio of the coupling agent and polyethylene is 10%~30%, continues to stir 12
~24h, the product being filtrated to get is the polyethylene particle that adsorption has nano inoganic particle, is dried stand-by；
Step 2: the polyethylene particle for being coated with nano inoganic particle that step one is obtained is well mixed with paraffin oil,
Wherein, polyethylene weight degree is 15%~25%, is fed by pump in extruder, and processing temperature is 150 DEG C~240
DEG C, screw speed is 300~500rpm；It is 20~200 μm that the substrate of extrusion obtains thickness after supercooling and biaxial tension
Oil film, draw ratio is 3 × 3~9 × 9, and draft temperature is 100 DEG C~125 DEG C；Oil film is carried out laterally after extraction, again
Stretching and thermal finalization, cross directional stretch ratio are 1.0~1.3:1, heat setting temperature is 120 DEG C~135 DEG C, and gained barrier film is received
Volume.
Wherein, the compound of the silicon hydrolyzed, titanium, aluminium and zirconium be organic alcohols compound, it is halide, organic
Any one of esters.Can be tetraethoxysilane, phenyltrimethoxysila,e, MTES, phenyl three
Ethoxysilane, ethyl trimethoxy silane, ethyltriacetoxysilane, ethyl triethoxysilane, methyl trimethoxy base silicon
Alkane, vinyltrimethoxy silane, the ketoximinosilanes of methyl three, γ-glycidyl ether oxygen propyl trimethoxy silicane, sulfuric acid
Titanium, titanium tetrachloride, metatitanic acid diethylester, the isopropanol of metatitanic acid four, tetraethyl titanate, butyl titanate, tert-butyl alcohol titanium zirconium chloride, zirconium
One kind in sour four butyl esters, zirconium-n-propylate and zirconium tert-butoxide.
By the compound of the silicon that can be hydrolyzed, titanium, aluminium and zirconium it is a kind of be configured to mass concentration for 8%~20% it is molten
The solvent that liquid is added is acetone, chloroform, methanol, ethanol, propyl alcohol, isopropanol, one or more kinds of in n-butanol, preferably its
In alcohols.
The pH value of solution is adjusted to 2 to 4, one kind in oxalic acid, hydrochloric acid, phosphoric acid and sulfuric acid of acid used or or
More than one.Or the pH value of solution is adjusted to 8 to 10, alkali used is in ammoniacal liquor, NaOH, potassium hydroxide etc.
One or more.
The mass ratio of the coupling agent and polyethylene is preferably 15%~25%.
Coupling agent is from any one of chromium complex coupling agent, silane coupler and phthalate coupling agent.
Compared with prior art, the beneficial effects of the invention are as follows：
Preparation method of the present invention is compared with conventional blending technology, and inorganic particulate particle diameter is smaller in system, this
2 μm of the particle diameter ＜ for the inorganic particulate that invention is introduced into system, is significantly better than the 10 μm of particle diameters introduced in current blending technology, prepares
Obtained barrier film inner inorganic nano-particle yardstick is smaller, and it is scattered also evenly, be not only advantageous to the steady of barrier film electrical property
It is qualitative, and because the influence that small particle inorganic particulate is grown up to polyethylene molecular chain is smaller, therefore, also improve separator product
Intensity.Nano-particle yardstick is small in the barrier film that the present invention is prepared, duct and is uniformly dispersed, with good thermal stability and
Excellent permeability, is suitable for preparing high-energy-density lithium battery.
Brief description of the drawings
Fig. 1 is electron microscope of the inorganic particulate absorption after polyethylene particle in the embodiment of the present invention 1；
Fig. 2 is the electron microscope of the finished product barrier film of the present invention；
Fig. 3 is the electron microscope for the barrier film that comparative example 1 is obtained using traditional blending technology.
Embodiment
A kind of preparation method of lithium ion battery separator of the present invention, mainly by synthesizing a kind of Nano sol to polyethylene
Particle cladding is carried out, the Nano sol can be that Ludox, Alumina gel, titanium colloidal sol or zirconium colloidal sol are one or more kinds of；Then,
Polyethylene after cladding is mixed with paraffin oil, extruded, is stretched, is dried, is extracted, horizontal drawing and thermal finalization, finally give
Nano-particle yardstick is small in barrier film duct and is uniformly dispersed, and with good thermal stability and excellent permeability, is suitable for
Prepare high-energy-density lithium battery.The concrete technology of preparation is as follows：
Step 1: by one kind of the compound of the silicon that can be hydrolyzed, titanium, aluminium and zirconium be configured to mass concentration for 8%~
20% solution, is placed in ultrasound environments, and the pH value of solution is adjusted into 2 to 4 or 8 to 10, water is then slowly added dropwise thereto,
Water is 2.5~6 with the mol ratio of the compound:1, add polyethylene particle and stir, and flowed back at 50~60 DEG C
3~8h is reacted, the mass ratio of nano inoganic particle and polyethylene obtained by synthesis is 0.05~0.5:1；Reaction is removed after terminating
Microwave environment, coupling agent is added into solution, the mass ratio of the coupling agent and polyethylene is 10%~30%, continues to stir 12
~24h, the product being filtrated to get is the polyethylene particle that adsorption has nano inoganic particle, is dried stand-by；
Step 2: the preparation of barrier film：The adsorption that step one is obtained have the polyethylene particle of nano inoganic particle with
Paraffin oil is well mixed, wherein, polyethylene weight degree is 15%~25%, is fed by pump in extruder, processing
Temperature is 150 DEG C~240 DEG C, too low to ensure to melt effect, and high then polymer is easily degraded；Screw speed be 300~
500rpm；The substrate of extrusion obtains the oil film that thickness is 20~200 μm after supercooling and biaxial tension, and draw ratio is 3 × 3
~9 × 9, draft temperature is 100 DEG C~125 DEG C；Oil film is after extraction, and paraffin oil leaves the hole that barrier film generation is mutually communicated
Road, extractant can be dichloromethane or fluoroform etc., carry out cross directional stretch and thermal finalization again to the oil film after extraction, horizontal
It is 1.0~1.3 to stretch ratio:1, heat setting temperature is 120 DEG C~135 DEG C, and gained barrier film is wound.
In the present invention, the silicon hydrolyzed, titanium, the compound of aluminium and zirconium be organic alcohols compound, halide,
Any one of organosilane ester.Can be tetraethoxysilane, phenyltrimethoxysila,e, MTES, benzene
Ethyl triethoxy silicane alkane, ethyl trimethoxy silane, ethyltriacetoxysilane, ethyl triethoxysilane, methyl trimethoxy
Base silane, vinyltrimethoxy silane, the ketoximinosilanes of methyl three, γ-glycidyl ether oxygen propyl trimethoxy silicane, sulphur
Sour titanium, titanium tetrachloride, metatitanic acid diethylester, the isopropanol of metatitanic acid four, tetraethyl titanate, butyl titanate, tert-butyl alcohol titanium zirconium chloride,
One kind in tetrabutyl zirconate, zirconium-n-propylate and zirconium tert-butoxide.
It is 8%~20% solution institute by a kind of concentration that is configured to of the compound of the silicon that can be hydrolyzed, titanium, aluminium and zirconium
The solvent of addition is the one or more in acetone, chloroform, methanol, ethanol, propyl alcohol, isopropanol, n-butanol.Preferably wherein
Alcohols.
Acids or bases can be selected when pH value regulation is carried out to solution, if oxalic acid, hydrochloric acid, phosphorus may be selected from acids
One or more of in acid, sulfuric acid, preferable ph is 2~4.If ammoniacal liquor, NaOH and potassium hydroxide may be selected from bases
In it is one or more of, preferable ph be 8~10.
In order to cause synthesis uniform particle absorption, colloidal sol prepare initial stage just polyethylene particles are just added to it is molten
In liquid.Collosol concentration is 8%~20%, and the too high then easy gel of collosol concentration, concentration is too low, is unfavorable for the life of nano particle
Into.The theoretical proportions of nano inoganic particle and polyethylene are 0.05~0.5:1, if because the ratio of nano inoganic particle and polyethylene
Example is less than 0.05：1 hot improvement of reduction, if more than 0.5:1 considerably increases absorption difficulty.
After colloidal sol reaction terminates, adding coupling agent can make primary level inorganic particulate to be attached to polyethylene particle surface simultaneously
Start growth, the addition of coupling agent improves the adhesion of nano inoganic particle and polyethylene surface, provided for cladding processing
May.Coupling agent can use chromium complex coupling agent, silane coupler or phthalate coupling agent etc..
Technical solution of the present invention is described in further detail with specific embodiment below in conjunction with the accompanying drawings, described is specific
Only the present invention is explained for embodiment, is not intended to limit the invention.
The preparation of embodiment 1, lithium ion battery separator, step is as follows：
Step 1: the tetraethoxysilane solution that configuration concentration is 10.5% is (by 100g tetraethoxysilanes and 860g second
Alcohol is mixed) it is placed in ultrasound environments, it is 3 to add salt acid for adjusting pH value, and high purity water is slowly added dropwise.High purity water and tetraethoxysilane
Mol ratio be 6:1, add 70g polyethylene particles and stir, and 7h is heated to reflux at 50 DEG C, synthesize gained silica
It is 0.4 with polyethylene mass ratio:1, reaction adds 15g KH570 silane couplers after terminating, and persistently stirs poly- second after 20h
Alkene particle filtering comes out, and dries stand-by；It can be seen that the product being filtrated to get is substantially to be adsorbed with nano inorganic on surface in Fig. 1
The polyethylene particle of particle.
Step 2: the polyethylene particle after step one is coated is mixed with paraffin oil, the content of wherein polyethylene particle is
16%, 230 DEG C of extruder temperature, 125 DEG C of biaxial tensiones of substrate, 105 DEG C of progress, 1.05 times of cross directional stretch, final 130 after extraction
The barrier film that thickness is 16 μm is obtained after DEG C heat treatment shaping, barrier film is wound.Fig. 2 is the electron microscope for the barrier film that embodiment 1 is obtained.
The preparation of embodiment 2, lithium ion battery separator, step is as follows：
Step 1: configuration concentration is placed in ultrasound environments for 8% butyl titanate-ethanol solution, hydrochloric acid regulation is added
PH value is 4, and high purity water is slowly added dropwise.The mol ratio of high purity water and butyl titanate is 5:1, add 62g polyethylene particles, stirring
Uniformly, and at 50 DEG C 7h is heated to reflux, synthesis gained titanium dioxide is 0.6 with polyethylene mass ratio:1, after reaction terminates
Polyethylene particle is filtered out after adding 12g KH550 silane couplers, stirring 16h, dried stand-by.
Step 2: the polyethylene particle after step one is coated is mixed with paraffin oil, the content of wherein polyethylene particle is
14.5%, 230 DEG C of extruder temperature, 125 DEG C of biaxial tensiones of substrate, 105 DEG C of progress, 1.05 times of cross directional stretch after extraction, finally
The barrier film that thickness is 16 μm is obtained after 130 DEG C of heat treatment shapings, barrier film is wound.
The preparation of embodiment 3, lithium ion battery separator, step is as follows：
Step 1: configuration concentration is placed in ultrasound environments for 10% aluminium isopropoxide-ethanol solution, vinegar acid for adjusting pH is added
It is worth for 4, high purity water is slowly added dropwise.The mol ratio of high purity water and aluminium isopropoxide is 2.5:1,60g polyethylene is added, grain stirring is equal
It is even, and 7h is heated to reflux at 50 DEG C, synthesis gained alundum (Al2O3) is 0.4 with polyethylene mass ratio:1, after reaction terminates
Polyethylene particle is filtered out after adding 18gKH570 silane couplers, stirring 18h, dried stand-by.
Step 2: the polyethylene particle after step one cladding is mixed with paraffin oil, wherein polymerized ethylene content 16%, extruder
230 DEG C of temperature, 125 DEG C of biaxial tensiones of substrate, 105 DEG C of progress, 1.05 times of cross directional stretch, final 130 DEG C of heat treatment shapings after extraction
The barrier film that thickness is 16 μm is obtained afterwards, and barrier film is wound.
The preparation of embodiment 4, lithium ion battery separator, step is as follows：
Step 1: configuration concentration is placed in ultrasound environments for 10% tetraethoxysilane-ethanol solution, adds hydrochloric acid and adjust
It is 3 to save pH value, and high purity water is slowly added dropwise.The mol ratio of high purity water and tetraethoxysilane is 6:1, add 50g polyethylene, grain
Stir, and 7h is heated to reflux at 50 DEG C, synthesis gained silica is 0.15 with polyethylene mass ratio:1, reaction knot
10g KH570 silane couplers are added after beam, polyethylene particle are filtered out after persistently stirring 20h, dried stand-by.
Step 2: the polyethylene particle after step one cladding is mixed with paraffin oil, wherein polymerized ethylene content 17%, extruder
225 DEG C of temperature, 125 DEG C of biaxial tensiones of substrate, 105 DEG C of progress, 1.05 times of cross directional stretch, final 130 DEG C of heat treatment shapings after extraction
The barrier film that thickness is 16 μm is obtained afterwards, and barrier film is wound.
The preparation of embodiment 5, lithium ion battery separator, step is as follows：
Step 1: configuration concentration is placed in ultrasound environments for 8% tetraethoxysilane-ethanol solution, adds hydrochloric acid and adjust
It is 4 to save pH value, and high purity water is slowly added dropwise.The mol ratio of high purity water and tetraethoxysilane is 6:1,80g polyethylene particles are added,
Stir, and 7h is heated to reflux at 50 DEG C, synthesis gained silica is 0.4 with polyethylene mass ratio:1, reaction knot
20gKH570 silane couplers are added after beam, polyethylene particle are filtered out after persistently stirring 20h, dried stand-by.
Step 2: the polyethylene particle after step one cladding is mixed with paraffin oil, wherein polymerized ethylene content 16%, extruder
230 DEG C of temperature, 125 DEG C of biaxial tensiones of substrate, 105 DEG C of progress, 1.05 times of cross directional stretch, final 130 DEG C of heat treatment shapings after extraction
The barrier film that thickness is 16 μm is obtained afterwards, and barrier film is wound.
The preparation of embodiment 6, lithium ion battery separator, step is as follows：
Step 1: configuration concentration is placed in ultrasound environments for 19% tetraethoxysilane-ethanol solution, adds hydrochloric acid and adjust
It is 3 to save pH value, and high purity water is slowly added dropwise.The mol ratio of high purity water and tetraethoxysilane is 6:1, add 100g polyethylene
Grain, stirs, and is heated to reflux 7h at 55 DEG C, and synthesis gained silica is 0.4 with polyethylene mass ratio:1, reaction
30gKH570 silane couplers are added after end, polyethylene particle are filtered out after persistently stirring 20h, dried stand-by.
Step 2: the polyethylene particle after step one cladding is mixed with paraffin oil, wherein polymerized ethylene content 16%, extruder
235 DEG C of temperature, 125 DEG C of biaxial tensiones of substrate, 105 DEG C of progress, 1.05 times of cross directional stretch, final 130 DEG C of heat treatment shapings after extraction
The barrier film that thickness is 16 μm is obtained afterwards, and barrier film is wound.
The preparation of embodiment 7, lithium ion battery separator, step is as follows：
Step 1: the tetraethoxysilane solution that configuration concentration is 10.5% is (by 100g tetraethoxysilanes and 860g second
Alcohol is mixed) it is placed in ultrasound environments, it is 9 to add ammoniacal liquor regulation pH value, and high purity water is slowly added dropwise.High purity water and tetraethoxysilane
Mol ratio be 6:1, add 70g polyethylene particles and stir, and 7h is heated to reflux at 50 DEG C, synthesize gained silica
It is 0.4 with polyethylene mass ratio:1, reaction adds 15g KH570 silane couplers after terminating and persistently stirred poly- second after 20h
Alkene particle filtering comes out, and dries stand-by.
Step 2: the polyethylene particle after step one is coated is mixed with paraffin oil, the content of wherein polyethylene particle is
16%, 230 DEG C of extruder temperature, 125 DEG C of biaxial tensiones of substrate, 105 DEG C of progress, 1.05 times of cross directional stretch, final 130 after extraction
The barrier film that thickness is 16 μm is obtained after DEG C heat treatment shaping, barrier film is wound.
Comparative example 1, the thickness that traditional blending technology is obtained is used for 16 μm, porosity is 60% barrier film.Fig. 3 is pair
The electron microscope for the barrier film that ratio 1 is obtained.Comparison diagram 1 and Fig. 3, it can be seen that the present invention achieves bright in terms of particle dispersiveness is improved
Aobvious progress.
Comparative example 2, thickness are 16 μm, and porosity is 38% PE basement membranes.
The contrast of the performance indications of sample in each embodiment of table 1
According to the related data in table 1, embodiment 4 compared with Example 1, the adsorbance of the inorganic particulate in embodiment 4
When relatively low, supporting role of the inorganic particulate to barrier film is weak.
Embodiment 1,5 is compared with 6, and when collosol concentration is up to close to 20% in embodiment 6, the inorganic particulate particle diameter of production is bright
It is aobvious bigger than normal, though higher porosity can be maintained, the loss of intensity is caused simultaneously.
Embodiment 1,2 is compared with 3, and products obtained therefrom performance is very nearly the same, but considers production cost and security, is used
Tetraethoxysilane in embodiment 1 is optimal selection.
Compare comparative example and embodiment, it can be found that inside the barrier film duct after filling inorganic particulate, the porosity of film by
Significantly raised, thermal shrinkage improves.The present invention is compared to traditional blending technology, and the particle diameter of filling only has original 30%
Left and right, greatly improves the homogeneity of film internal structure, and intensity has 20% or so lifting.
Embodiment 1 is compared with 7, and the present invention is feasible using acid or base catalyst, but in R＆D process of the present invention
It is long-term, substantial amounts of it was found that, the colloidal sol resting period obtained by base catalyst is short, not being suitable for large-scale industry should
With.
By above-mentioned Binding experiment accompanying drawing, invention has been described, but specific implementation case is only that part is real above
Test, be not the practical range for limiting the present invention.The person skilled of this area is according to the present invention or does not depart from this hair
In the case of bright objective, the equivalent deformation and relevant modifications carried out, these are all within the protection of the present invention.
Claims (8)
1. a kind of preparation method of lithium ion battery separator, it is characterised in that comprise the following steps：
Step 1: it is 8%~20% that one kind of the compound of the silicon that can be hydrolyzed, titanium, aluminium and zirconium is configured into mass concentration
Solution, be placed in ultrasound environments, the pH value of solution be adjusted to 2 to 4 or 8 to 10, be then slowly added dropwise water thereto, water with
The mol ratio of the compound is 2.5~6:1, add polyethylene particle and stir, and the back flow reaction 3 at 50~60 DEG C
The mass ratio of~8h, synthesis gained nano inoganic particle and polyethylene is 0.05~0.5:1；Reaction removes microwave ring after terminating
Border, coupling agent is added into solution, the mass ratio of the coupling agent and polyethylene is 10%~30%, continues to stir 12~24h,
The product being filtrated to get is the polyethylene particle that adsorption has nano inoganic particle, is dried stand-by；
Step 2: the preparation of barrier film：The adsorption that step one is obtained has the polyethylene particle and paraffin of nano inoganic particle
Oil is well mixed, wherein, polyethylene weight degree is 15%~25%, is fed by pump in extruder, processing temperature
For 150 DEG C~240 DEG C, screw speed is 300~500rpm；The substrate of extrusion obtains thickness after supercooling and biaxial tension
20~200 μm of oil film, draw ratio is 3 × 3~9 × 9, and draft temperature is 100 DEG C~125 DEG C；Oil film after extraction, then
Secondary progress cross directional stretch and thermal finalization, cross directional stretch ratio are 1.0~1.3:1, heat setting temperature is 120 DEG C~135 DEG C, by institute
Obtain barrier film winding.
2. the preparation method of lithium ion battery separator according to claim 1, it is characterised in that described to hydrolyze
Silicon, titanium, the compound of aluminium and zirconium are any one of organic alcohols compound, halide, organosilane ester.
3. the preparation method of lithium ion battery separator according to claim 2, it is characterised in that described to hydrolyze
Silicon, titanium, the compound of aluminium and zirconium are tetraethoxysilane, phenyltrimethoxysila,e, MTES, the second of phenyl three
TMOS, ethyl trimethoxy silane, ethyltriacetoxysilane, ethyl triethoxysilane, methyltrimethylsilane,
Vinyltrimethoxy silane, the ketoximinosilanes of methyl three, γ-glycidyl ether oxygen propyl trimethoxy silicane, titanium sulfate, four
Titanium chloride, metatitanic acid diethylester, the isopropanol of metatitanic acid four, tetraethyl titanate, butyl titanate, tert-butyl alcohol titanium zirconium chloride, zirconic acid four
One kind in butyl ester, zirconium-n-propylate and zirconium tert-butoxide.
4. the preparation method of lithium ion battery separator according to claim 1, it is characterised in that by the silicon that can be hydrolyzed,
To be configured to the solvent that mass concentration adds by 8%~20% solution be acetone, chlorine by the compound of titanium, aluminium and zirconium a kind of
One or more in imitative, methanol, ethanol, propyl alcohol, isopropanol, n-butanol.
5. the preparation method of lithium ion battery separator according to claim 1, it is characterised in that be adjusted to the pH value of solution
2 to 4, the sour one or more in oxalic acid, hydrochloric acid, phosphoric acid and sulfuric acid used.
6. the preparation method of lithium ion battery separator according to claim 1, it is characterised in that be adjusted to the pH value of solution
8 to 10, the one or more of alkali used in ammoniacal liquor, NaOH and potassium hydroxide.
7. the preparation method of lithium ion battery separator according to claim 1, it is characterised in that coupling agent selects chromium complex
Any one of coupling agent, silane coupler and phthalate coupling agent.
8. the preparation method of lithium ion battery separator according to claim 1, it is characterised in that the coupling agent and polyethylene
Mass ratio be 15%~25%.
Priority Applications (1)
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110190331A (en) * | 2019-06-18 | 2019-08-30 | 郑州中科新兴产业技术研究院 | A kind of electrolyte, preparation and its application on firm lithium ion battery silicon-carbon surface |
| CN110289383A (en) * | 2019-06-18 | 2019-09-27 | 深圳昌茂粘胶新材料有限公司 | A kind of lithium battery power battery high-temperature resistant micropore thin film material and preparation method thereof |
| CN110635090A (en) * | 2019-09-27 | 2019-12-31 | 宁德卓高新材料科技有限公司 | Preparation method of high-heat-resistance vinylidene fluoride polymer mixed coating diaphragm |
| CN112563583A (en) * | 2020-12-10 | 2021-03-26 | 珠海冠宇电池股份有限公司 | Lithium battery |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103066231A (en) * | 2012-12-31 | 2013-04-24 | 中科院广州化学有限公司 | Method for preparing high temperature resistant composite separator by lithium ion battery |
| CN103296240A (en) * | 2013-05-28 | 2013-09-11 | 中科院广州化学有限公司 | High-performance flexible composite nonwoven fabric membrane for lithium ion battery, as well as preparation method and application of membrane |
| CN103943804A (en) * | 2014-04-18 | 2014-07-23 | 中材科技股份有限公司 | Temperature-resistant safe lithium-ion battery diaphragm and preparation method thereof |
| CN105185936A (en) * | 2015-09-28 | 2015-12-23 | 中材科技股份有限公司 | Safe high-performance lithium-ion battery membrane |
-
2017
- 2017-03-16 CN CN201710156849.1A patent/CN106953052A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103066231A (en) * | 2012-12-31 | 2013-04-24 | 中科院广州化学有限公司 | Method for preparing high temperature resistant composite separator by lithium ion battery |
| CN103296240A (en) * | 2013-05-28 | 2013-09-11 | 中科院广州化学有限公司 | High-performance flexible composite nonwoven fabric membrane for lithium ion battery, as well as preparation method and application of membrane |
| CN103943804A (en) * | 2014-04-18 | 2014-07-23 | 中材科技股份有限公司 | Temperature-resistant safe lithium-ion battery diaphragm and preparation method thereof |
| CN105185936A (en) * | 2015-09-28 | 2015-12-23 | 中材科技股份有限公司 | Safe high-performance lithium-ion battery membrane |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110190331A (en) * | 2019-06-18 | 2019-08-30 | 郑州中科新兴产业技术研究院 | A kind of electrolyte, preparation and its application on firm lithium ion battery silicon-carbon surface |
| CN110289383A (en) * | 2019-06-18 | 2019-09-27 | 深圳昌茂粘胶新材料有限公司 | A kind of lithium battery power battery high-temperature resistant micropore thin film material and preparation method thereof |
| CN110289383B (en) * | 2019-06-18 | 2021-12-03 | 深圳昌茂粘胶新材料有限公司 | High-temperature-resistant microporous film material for power battery of lithium battery and preparation method of microporous film material |
| CN110635090A (en) * | 2019-09-27 | 2019-12-31 | 宁德卓高新材料科技有限公司 | Preparation method of high-heat-resistance vinylidene fluoride polymer mixed coating diaphragm |
| CN112563583A (en) * | 2020-12-10 | 2021-03-26 | 珠海冠宇电池股份有限公司 | Lithium battery |
| CN112563583B (en) * | 2020-12-10 | 2022-04-29 | 珠海冠宇电池股份有限公司 | Lithium battery |
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