CN105070862B - Non-woven type power lithium battery diaphragm and preparation method thereof - Google Patents
Non-woven type power lithium battery diaphragm and preparation method thereof Download PDFInfo
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- CN105070862B CN105070862B CN201510413145.9A CN201510413145A CN105070862B CN 105070862 B CN105070862 B CN 105070862B CN 201510413145 A CN201510413145 A CN 201510413145A CN 105070862 B CN105070862 B CN 105070862B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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Abstract
The invention belongs to the technical field of battery diaphragm materials, and discloses a non-woven type power lithium battery diaphragm and a preparation method thereof. The preparation method comprises the following steps: modifying silicon dioxide with a silane coupling agent, forming double bonds on the silicon dioxide, initiating methyl methacrylate (MMA) polymerization, grafting and coating the silicon dioxide with polymethyl methacrylate (PMMA) and forming core-shell particles with good heat stability and good wettability on electrolyte; preparing a suspension liquid from the prepared core-shell particles, adding polyethylene glycol dimethacrylate as a fixing agent, immersing non-woven fabrics into the solution, and taking out and drying the non-woven fabrics to obtain a porous diaphragm; and immersing the diaphragm into a poly(vinylidene fluoride)-hexafluoropropene (PVDF-HFP) solution, volatilizing the solvent and baking the diaphragm at a high temperature of 120-140 DEG C, carrying out thermo-crosslinking on the polyethylene glycol dimethacrylate, and drying the polyethylene glycol dimethacrylate to obtain the non-woven type power lithium battery diaphragm. The diaphragm disclosed by the invention has the advantages of excellent heat stability and electrochemical property and has a good application prospect.
Description
Technical field
The invention belongs to battery diaphragm material technical field, and in particular to a kind of non-woven fabric type power lithium battery diaphragm and its
Preparation method.
Background technology
Lithium battery diaphragm is a kind of perforated membrane, and its effect is the positive pole and negative pole for separating lithium battery, prevents both positive and negative polarity from connecing
Touch and cause short circuit, while the hole in barrier film provides the passage of migration to electrolyte and lithium ion so that in charge and discharge process lithium from
Son can mutually be migrated between both positive and negative polarity.Lithium battery diaphragm directly determine the internal resistance of lithium battery, cycle performance, security performance,
A series of important performances such as high rate performance.It is technology ranked first in lithium battery, cost ranked second critical material.Battery diaphragm
Preparation method it is business-like mainly have two kinds, one kind is dry method tension membrane formation process, the polypropylene screen of such as celgard；It is another
It is thermally induced phase separation to plant, such as polyethylene film.In order to increase the performance of battery diaphragm, generally all PP films and PE films can be combined
The composite membrane of the structure that sandwiches.But polyolefin film is poor to the absorbability of electrolyte, ionic conductivity is caused to obtain
Bigger lifting so that the performance of battery is very restricted, is that this non-woven fabric type lithium battery diaphragm starts to be subject to increasingly
Many concerns, based on electrostatic spinning non-woven fabrics and wet nonwoven fabricss.But the current cost of electrostatic spinning is too high, work is realized
Industryization or a permanent problem.
In 2014 researchs for comparing new, Pingting Yang are prepared by coating PMMA to silica surface
The core-shell particles of excellent performance, and by the core-shell particles of preparation be applied to PE lithium battery diaphragms it is modified in, drastically increase
The wettability of barrier film, ionic conductivity and heat stability, and for the research of modification nonwoven cloth lithium battery diaphragm was in Ju- in 2011
Start to occur in the article of Hyun Cho, Ju-Hyun Cho mainly by by the particle-filled non-woven fabrics to PET of PMMA making
Standby lithium battery diaphragm.On the one hand also do not occur at present for silicon dioxide-PMMA inorganic-organic compound particles being filled into PET nonwovens
The report of lithium battery diaphragm is prepared in cloth, the barrier film that on the other hand existing core-shell particles or PMMA particles are processed all has appearance
The problem of easy dry linting, and the anti-puncture intensity of barrier film is not high.
The content of the invention
In order to solve the shortcoming and defect part of above prior art, the primary and foremost purpose of the present invention is to provide a kind of nonwoven
The preparation method of cloth type power lithium battery diaphragm.
Another object of the present invention is to provide a kind of non-woven fabric type dynamic lithium battery prepared by said method
Barrier film.
The object of the invention is achieved through the following technical solutions：
A kind of preparation method of non-woven fabric type power lithium battery diaphragm, including following preparation process：
(1) silicon dioxide is modified：Silicon dioxide, solvent and silane coupler containing vinyl are added to into reactor
In, ultrasonic disperse is uniform, then in stirring condition Deca ammonia, mix homogeneously, is warming up to 65～75 DEG C of 4～6h of reaction, product
Separate, be dried, obtain double bond improved silica；
(2) preparation of core-shell particles：Double bond improved silica, polyvinylpyrrolidone (PVP) prepared by step (1)
It is added in reactor with deionized water, ultrasonic disperse is uniform, adds methyl methacrylate monomer, is uniformly mixing to obtain white
Emulsion, is subsequently adding persulfate aqueous solution, and the logical nitrogen deoxygenation of stirring is warming up to 65～80 DEG C and is reacted, after the completion of reaction,
Product is separated, is dried, obtain core-shell particles；
(3) preparation of modification liquid：The core-shell particles of step (2) are added in deionized water, ultrasonic disperse is prepared into matter
Amount concentration is 4.5%～9% milk-white coloured suspension；By polyethylene glycol dimethacrylate (PEGDMA) with after ethanol dissolving
In being added to above-mentioned suspension, milky modification liquid is obtained after homogenizing；
(4) preparation of non-woven fabric type power lithium battery diaphragm：Non-woven fabrics are immersed in into the modification liquid prepared by step (3)
In, drying is taken out after 3～5min, obtain uniform core-shell particles Modified Membrane；Then Modified Membrane is immersed in into 4wt%～8wt%
Kynoar-hexafluoropropylene copolymer (PVDF-HFP) solution in, solvent is volatilized after taking-up, be subsequently placed in 125～
10～20min is baked in 140 DEG C of baking oven, is vacuum dried, obtain non-woven fabric type power lithium battery diaphragm.
Preferably, the silicon dioxide described in step (1) refers to the silicon dioxide that particle diameter is 10～100nm；Described is molten
Agent refers to methanol, and the addition of solvent is 20～30ml/g with the volume mass ratio of silicon dioxide.
Preferably, the described silane coupler containing vinyl refers to γ-(methacryloxypropyl) propyl trimethoxy silicon
Alkane (KH570), the addition of the silane coupler containing vinyl is the 5%～12% of silicon dioxide quality.
Preferably, the K values of polyvinylpyrrolidone described in step (2) are 30～40；The addition of polyvinylpyrrolidone
Measure as the 4%～28% of double bond improved silica quality；The addition of the methyl methacrylate monomer is modified for double bond
1～7 times of silicon dioxide quality；The addition of the potassium peroxydisulfate is the 1%～3% of methyl methacrylate monomer quality.
Drying described in step (1) and step (2) to be referred to and be vacuum dried 12h at 50 DEG C.
Preferably, the number-average molecular weight of polyethylene glycol dimethacrylate described in step (3) is 300～750, poly- second
The addition of diol dimethacrylate is the 2%～6% of core-shell particles quality；Described homogenizing refers to equal using homogenizer
3～5min of matter.
Preferably, the non-woven fabrics described in step (4) include polypropylene non-woven fabric, cellulose fibre non-woven fabrics or poly- to benzene
Naphthalate non-woven fabrics；The thickness of non-woven fabrics is 10～30 μm, mean porosities are 50%～80%.
The solvent that described PVDF-HFP solution is used includes acetone, N,N-dimethylformamide, tetrahydrofuran or two
Methylacetamide.
A kind of non-woven fabric type power lithium battery diaphragm, is prepared by above method.
The present invention preparation principle be：Use silane coupler modified nano silicon so that with double on silicon dioxide
Key, then causes MMA polymerizations by potassium peroxydisulfate so that silicon dioxide by PMMA grafting and coatings, formed heat stability it is good, to electricity
The good core-shell particles of solution liquid wettability.Prepared core-shell particles are configured to into certain density suspension and are added a certain amount of
Polyethylene glycol dimethacrylate is immersed in non-woven fabrics in above-mentioned solution as fixative, takes out drying and obtains white
Porous septum.For the macropore further modified in barrier film, the nonwoven cloth diaphragm of above-mentioned preparation is immersed in into Kynoar and is total to
In the solution of polymers (PVDF-HFP), 120-140 DEG C of high temperature bakes certain hour after the dry solvent that volatilizees, and makes Polyethylene Glycol dimethyl
Acrylate heat cross-linking, the non-woven fabric type power lithium battery of heat stability, excellent electrochemical performance is obtained Jing after 60 DEG C of vacuum drying
Pond barrier film.
The preparation method and resulting product of the present invention has the advantage that and beneficial effect：
(1) core-shell particles of the invention become more stable after the solidification of PEGDMA in film, it is heat-treated after
The membrane surface of preparation it is bright and clean it is smooth there is no dry linting phenomenon substantially, and hole is uniform；
(2) core-shell particles of the invention PMMA particles compared to existing technology have higher heat stability, improve indirectly
The resistance to elevated temperatures of film, improves the safety of film；
(3) the middle non-woven fabrics for core-shell particles filling, both sides are adopted to improve barrier film for the structure of PVDF-HFP
Porosity improve the mechanical property of film again, it is well more many than the mechanical property merely with particle-filled non-woven fabrics；
(4) size that not only can further reduce fenestra by the both sides dip-coating PVDF-HFP in non-woven fabrics can also make
PVDF-HFP plays certain encapsulation effect, while the hole for ensureing film surface is uniform, compound particle is encapsulated in into non-woven fabrics
It is interior, so as not to drop out；
(5) introducing of core-shell particles causes barrier film to have preferable absorbent concurrently, makes the electrical property of battery diaphragm than general
The electrical property of barrier film improve a lot.
Description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of the core-shell particles Modified Membrane that the embodiment of the present invention 1 is obtained；
Fig. 2 is the scanning electron microscope (SEM) photograph of the core-shell particles Modified Membrane that the embodiment of the present invention 2 is obtained；
Fig. 3 is the scanning electron microscope (SEM) photograph of the core-shell particles Modified Membrane that the embodiment of the present invention 3 is obtained.
Specific embodiment
With reference to embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited
In this.
The ionic conductivity method of testing of the battery diaphragm described in following examples is as follows：
Anode cover/rustless steel/barrier film/electrolyte/rustless steel/spring leaf/negative electrode casing is assembled into the battery diaphragm for preparing
CR2032 type button cells, the size of stainless steel electrode is 15.8mm, and electrolyte consists of 1M LiPF6It is dissolved in EC/DMC
(1:1, V/V), then fitted by ZVIEW softwares by the AC impedance of CHI660D types electrochemical workstation test battery
The impedance R of battery diaphragmb, equivalent circuit adopt R (C (CR)), calculate the ionic conductivity of battery finally by below equation：
Wherein σ is ionic conductivity；L is the thickness of barrier film；A for electrode area, RbFor the impedance of battery diaphragm.
Embodiment 1
(1) silicon dioxide is modified：1g silicon dioxide is weighed in round-bottomed flask, 30ml methanol is added, is accounted for silicon dioxide
The γ of mass fraction 10%-(methacryloxypropyl) propyl trimethoxy silicane (KH570), ultrasonic disperse is uniform, in 1000r/
Under the mechanical agitation of min, 1.0ml ammonia is added dropwise over, rotating speed is adjusted to into 60r/min after stirring 1h, in the bar of condensing tube backflow
Under part, 70 DEG C of reaction 5h are warming up to, by the product with methylalcohol centrifuge washing that obtains three times, 50 DEG C of vacuum drying 12h obtain white
Powder double bond improved silica；
(2) preparation of core-shell particles：The double bond improved silica that 1g steps (1) are obtained and 0.08g PVP-K30 are super
Sound is dispersed in 55ml deionized waters, and above-mentioned solution is transferred in round-bottomed flask the methacrylic acid for adding 2g vacuum distillations
Methyl ester, plugs condensing tube and opening magnetic stirrer 15min makes solution stirring be formed uniformly milky emulsion, will
Potassium peroxydisulfate after 0.033g recrystallization is dissolved in 15ml deionized waters and is added in round-bottomed flask, and nitrogen is led to while stirring
Gas 30min, is warmed up to 75 DEG C and reacts 6h under nitrogen atmosphere, and by the product deionized water centrifuge washing that obtains 3 times, 50 DEG C true
Sky is dried 12h, obtains core-shell particles；
(3) preparation of modification liquid：The above-mentioned core-shell particles ultrasound 30min of 0.5g are well dispersed in 5ml deionized waters, will
0.01g polyethylene glycol dimethacrylates are dissolved in 0.8ml ethanol and are added in above-mentioned dispersion liquid, and are stirred with high speed homogenization
Mix device to stir, the corase particleses in solution are fallen with filtered through gauze, obtain milky modification liquid；
(4) preparation of non-woven fabric type power lithium battery diaphragm：PET non-woven fabrics are immersed in above-mentioned modification liquid and are taken after 3min
Go out drying, obtain uniform core-shell particles Modified Membrane；Then Modified Membrane is immersed in the acetone soln of the PVDF-HFP of 6wt%
In, barrier film is taken out from solution and by slit control thickness, film is placed in 130 DEG C of baking oven after the dry solvent that volatilizees is dried
14min, is placed in 60 DEG C of vacuum drying ovens after taking-up and is dried 12h, obtains PET non-woven fabric type power lithium battery diaphragms.
The scanning electron microscope (SEM) photograph of gained core-shell particles Modified Membrane by Fig. 1 as shown in figure 1, can be seen in the present embodiment step (4)
Go out：Although core-shell particles have certain reunion on film, population distribution is uniform, and the loose structure of Modified Membrane is obvious.
The thickness of the PET non-woven fabric type power lithium battery diaphragms that the present embodiment is obtained is 29 μm, 160 DEG C of percent thermal shrinkages two
All it is 0 on direction；Film surface is white without dust, and ionic conductivity is 0.863mScm-1；And the index of common PP barrier films
It is as follows：22 μm of thickness, porosity 44.43%, 160 DEG C of percent thermal shrinkages 100%, conductivity at room temperature is 0.085mScm-1；
The membrane properties of the present embodiment have obtained great lifting.
Embodiment 2
(1) silicon dioxide is modified：1g silicon dioxide is weighed in round-bottomed flask, 25ml methanol is added, is accounted for silicon dioxide
The γ of mass fraction 12%-(methacryloxypropyl) propyl trimethoxy silicane (KH570), ultrasonic disperse is uniform, in 1000r/
Under the mechanical agitation of min, 0.8ml ammonia is added dropwise over, rotating speed is adjusted to into 60r/min after stirring 1h, in the bar of condensing tube backflow
Under part, 70 DEG C of reaction 5h are warming up to, by the product with methylalcohol centrifuge washing that obtains three times, 50 DEG C of vacuum drying 12h obtain white
Powder double bond improved silica；
(2) preparation of core-shell particles：The double bond improved silica that 1g steps (1) are obtained and 0.12g PVP-K30 are super
Sound is dispersed in 90ml deionized waters, and above-mentioned solution is transferred in round-bottomed flask the methacrylic acid for adding 3g vacuum distillations
Methyl ester, plugs condensing tube and opening magnetic stirrer 15min makes solution stirring be formed uniformly milky emulsion, will
Potassium peroxydisulfate after 0.05g recrystallization is dissolved in 15ml deionized waters and is added in round-bottomed flask, and nitrogen is led to while stirring
Gas 30min, is warmed up to 80 DEG C and reacts 6h under nitrogen atmosphere, and by the product deionized water centrifuge washing that obtains 3 times, 50 DEG C true
Sky is dried 12h, obtains core-shell particles；
(3) preparation of modification liquid：The above-mentioned core-shell particles ultrasound 30min of 0.5g are well dispersed in 6ml deionized waters, will
0.015g polyethylene glycol dimethacrylates are dissolved in 0.6ml ethanol and are added in above-mentioned dispersion liquid, and use high speed homogenization
Agitator stirs, and the corase particleses in solution are fallen with filtered through gauze, obtains milky modification liquid；
(4) preparation of non-woven fabric type power lithium battery diaphragm：PET non-woven fabrics are immersed in above-mentioned modification liquid and are taken after 3min
Go out drying, obtain uniform core-shell particles Modified Membrane；Then Modified Membrane is immersed in the acetone soln of the PVDF-HFP of 6wt%
In, barrier film is taken out from solution and by slit control thickness, film is placed in 130 DEG C of baking oven after the dry solvent that volatilizees is dried
14min, is placed in 60 DEG C of vacuum drying ovens after taking-up and is dried 12h, obtains PET non-woven fabric type power lithium battery diaphragms.
The scanning electron microscope (SEM) photograph of gained core-shell particles Modified Membrane by Fig. 2 as shown in Fig. 2 can be seen in the present embodiment step (4)
Go out：Although core-shell particles have certain reunion on film, population distribution is uniform, and the loose structure of Modified Membrane is obvious.
The thickness of the PET non-woven fabric type power lithium battery diaphragms that the present embodiment is obtained is 31 μm, 160 DEG C of percent thermal shrinkages two
All it is 0 on direction；Film surface is white without dust, and ionic conductivity is 0.179mScm-1；And the index of common PP barrier films
It is as follows：22 μm of thickness, porosity 44.43%, 160 DEG C of percent thermal shrinkages 100%, conductivity at room temperature is 0.085mScm-1；
The membrane properties of the present embodiment have obtained great lifting.
Embodiment 3
(1) silicon dioxide is modified：1g silicon dioxide is weighed in round-bottomed flask, 20ml methanol is added, is accounted for silicon dioxide
The γ of mass fraction 8%-(methacryloxypropyl) propyl trimethoxy silicane (KH570), ultrasonic disperse is uniform, in 1100r/
Under the mechanical agitation of min, 0.6ml ammonia is added dropwise over, rotating speed is adjusted to into 60r/min after stirring 1h, in the bar of condensing tube backflow
Under part, 75 DEG C of reaction 5h are warming up to, by the product with methylalcohol centrifuge washing that obtains three times, 50 DEG C of vacuum drying 12h obtain white
Powder double bond improved silica；
(2) preparation of core-shell particles：The double bond improved silica that 1g steps (1) are obtained and 0.16g PVP-K30 are super
Sound is dispersed in 120ml deionized waters, and above-mentioned solution is transferred in round-bottomed flask the metering system for adding 4g vacuum distillations
Sour methyl ester, plugs condensing tube and opening magnetic stirrer 15min makes solution stirring be formed uniformly milky emulsion, will
Potassium peroxydisulfate after 0.068g recrystallization is dissolved in 20ml deionized waters and is added in round-bottomed flask, and nitrogen is led to while stirring
Gas 30min, is warmed up to 80 DEG C and reacts 6h under nitrogen atmosphere, and by the product deionized water centrifuge washing that obtains 3 times, 50 DEG C true
Sky is dried 12h, obtains core-shell particles；
(3) preparation of modification liquid：The above-mentioned core-shell particles ultrasound 30min of 0.5g are well dispersed in 6ml deionized waters, will
0.01g polyethylene glycol dimethacrylates are dissolved in 0.8ml ethanol and are added in above-mentioned dispersion liquid, and are stirred with high speed homogenization
Mix device to stir, the corase particleses in solution are fallen with filtered through gauze, obtain milky modification liquid；
(4) preparation of non-woven fabric type power lithium battery diaphragm：PET non-woven fabrics are immersed in above-mentioned modification liquid and are taken after 3min
Go out drying, obtain uniform core-shell particles Modified Membrane；Then Modified Membrane is immersed in the acetone soln of the PVDF-HFP of 7wt%
In, barrier film is taken out from solution and by slit control thickness, film is placed in 130 DEG C of baking oven after the dry solvent that volatilizees is dried
14min, is placed in 60 DEG C of vacuum drying ovens after taking-up and is dried 12h, obtains PET non-woven fabric type power lithium battery diaphragms.
The scanning electron microscope (SEM) photograph of gained core-shell particles Modified Membrane by Fig. 3 as shown in figure 3, can be seen in the present embodiment step (4)
Go out：Core-shell particles have been filled between the hole of PET, due to the content of PMMA it is more, so defining part compact texture.
The thickness of the PET non-woven fabric type power lithium battery diaphragms that the present embodiment is obtained is 23 μm, 160 DEG C of percent thermal shrinkages two
All it is 0 on direction；Film surface is white without dust, and ionic conductivity is 0.522mScm-1；And the index of common PP barrier films
It is as follows：22 μm of thickness, porosity 44.43%, 160 DEG C of percent thermal shrinkages 100%, conductivity at room temperature is 0.085mScm-1；
The membrane properties of the present embodiment have obtained great lifting.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention not by above-described embodiment
Limit, other any spirit and the changes, modification, replacement made under principle without departing from the present invention, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (8)
1. a kind of preparation method of non-woven fabric type power lithium battery diaphragm, it is characterised in that：Including following preparation process：
(1) silicon dioxide is modified：Silicon dioxide, solvent and silane coupler containing vinyl are added in reactor, are surpassed
Sound is uniformly dispersed, then in stirring condition Deca ammonia, mix homogeneously, be warming up to 65～75 DEG C reaction 4～6h, product separate,
It is dried, obtains double bond improved silica；
(2) preparation of core-shell particles：Double bond improved silica, polyvinylpyrrolidone and deionization prepared by step (1)
Water is added in reactor, and ultrasonic disperse is uniform, adds methyl methacrylate monomer, is uniformly mixing to obtain white emulsion, so
After add persulfate aqueous solution, the logical nitrogen deoxygenation of stirring is warming up to 65～80 DEG C and is reacted, after the completion of reaction, by product
Separate, be dried, obtain core-shell particles；
(3) preparation of modification liquid：The core-shell particles of step (2) are added in deionized water, it is dense that ultrasonic disperse is prepared into quality
Spend the milk-white coloured suspension for 4.5%～9%；It is added to after polyethylene glycol dimethacrylate ethanol is dissolved above-mentioned outstanding
In supernatant liquid, milky modification liquid is obtained after homogenizing；
(4) preparation of non-woven fabric type power lithium battery diaphragm：Non-woven fabrics are immersed in the modification liquid prepared by step (3), 3～
Drying is taken out after 5min, uniform core-shell particles Modified Membrane is obtained；Then Modified Membrane is immersed in into the poly- inclined of 4wt%～8wt%
In the solution of viton copolymers, solvent is volatilized after taking-up, be subsequently placed in 125～140 DEG C of baking oven and bake
10～20min, vacuum drying, obtains non-woven fabric type power lithium battery diaphragm；
Silicon dioxide described in step (1) refers to the silicon dioxide that particle diameter is 10～100nm；Described solvent refers to methanol,
The addition of solvent is 20～30ml/g with the volume mass ratio of silicon dioxide；
The solvent that the solution of the Kynoar-hexafluoropropylene copolymer described in step (4) is used includes acetone, N, N- bis-
Methylformamide, tetrahydrofuran or dimethyl acetylamide.
2. the preparation method of a kind of non-woven fabric type power lithium battery diaphragm according to claim 1, it is characterised in that：It is described
The silane coupler containing vinyl refer to γ-(methacryloxypropyl) propyl trimethoxy silicane, the silane idol containing vinyl
The addition of connection agent is the 5%～12% of silicon dioxide quality.
3. the preparation method of a kind of non-woven fabric type power lithium battery diaphragm according to claim 1, it is characterised in that：Step
(2) the K values of polyvinylpyrrolidone described in are 30～40；The addition of polyvinylpyrrolidone is double bond improved silica
The 4%～28% of quality；The addition of the methyl methacrylate monomer is 1～7 times of double bond improved silica quality；
The addition of the potassium peroxydisulfate is the 1%～3% of methyl methacrylate monomer quality.
4. the preparation method of a kind of non-woven fabric type power lithium battery diaphragm according to claim 1, it is characterised in that：Step
(1) drying and described in step (2) to be referred to and be vacuum dried 12h at 50 DEG C.
5. the preparation method of a kind of non-woven fabric type power lithium battery diaphragm according to claim 1, it is characterised in that：Step
(3) number-average molecular weight of polyethylene glycol dimethacrylate described in is 300～750, polyethylene glycol dimethacrylate
Addition for core-shell particles quality 2%～6%.
6. the preparation method of a kind of non-woven fabric type power lithium battery diaphragm according to claim 1, it is characterised in that：It is described
Homogenizing refer to using homogenizer 3～5min of homogenizing.
7. the preparation method of a kind of non-woven fabric type power lithium battery diaphragm according to claim 1, it is characterised in that：Step
(4) non-woven fabrics described in include polypropylene non-woven fabric, cellulose fibre non-woven fabrics or polyethylene terephthalate nonwoven
Cloth；The thickness of non-woven fabrics is 10～30 μm, mean porosities are 50%～80%.
8. a kind of non-woven fabric type power lithium battery diaphragm, it is characterised in that：By the method described in any one of claim 1～7
Prepare.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105895844A (en) * | 2016-04-15 | 2016-08-24 | 合肥国轩高科动力能源有限公司 | Sticky ceramic diaphragm and preparation method thereof |
| CN106571438B (en) * | 2016-09-18 | 2019-12-13 | 中山大学 | Preparation method of polypropylene battery diaphragm filled with high-content glass fibers |
| CN107611323A (en) * | 2017-08-29 | 2018-01-19 | 苏州市苏真床垫有限公司 | A kind of composite lithium ion cell barrier film of nano-silicon dioxide modified polypropylene non-woven fabric and preparation method thereof |
| CN110504441B (en) * | 2018-05-17 | 2021-06-01 | 华为技术有限公司 | Modified silicon-based negative electrode material, preparation method thereof and lithium ion battery |
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| CN104157812A (en) * | 2014-04-23 | 2014-11-19 | 华南理工大学 | Lithium ion battery diaphragm, preparation method of lithium ion battery diaphragm and lithium ion battery |
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