CN109161292A - Self-stabilizing P (VDF-HFP) slurry, preparation method thereof and lithium ion battery separator - Google Patents
Self-stabilizing P (VDF-HFP) slurry, preparation method thereof and lithium ion battery separator Download PDFInfo
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- 239000002002 slurry Substances 0.000 title claims abstract description 41
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000011248 coating agent Substances 0.000 claims abstract description 26
- 238000000576 coating method Methods 0.000 claims abstract description 26
- 239000008367 deionised water Substances 0.000 claims abstract description 19
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 239000006185 dispersion Substances 0.000 claims abstract description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- 239000003112 inhibitor Substances 0.000 claims abstract description 10
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 10
- 238000004090 dissolution Methods 0.000 claims abstract description 9
- 230000005251 gamma ray Effects 0.000 claims abstract description 9
- 239000011261 inert gas Substances 0.000 claims abstract description 7
- 238000011105 stabilization Methods 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 10
- 238000005119 centrifugation Methods 0.000 claims description 9
- 230000005855 radiation Effects 0.000 claims description 9
- 231100000987 absorbed dose Toxicity 0.000 claims description 8
- 230000007717 exclusion Effects 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical group O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 7
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 7
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 3
- 238000007639 printing Methods 0.000 claims description 3
- 238000007650 screen-printing Methods 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 2
- -1 dip coated Substances 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 claims 1
- 239000000853 adhesive Substances 0.000 abstract description 13
- 230000001070 adhesive effect Effects 0.000 abstract description 13
- 239000004094 surface-active agent Substances 0.000 abstract description 7
- 239000003792 electrolyte Substances 0.000 abstract description 4
- 238000007789 sealing Methods 0.000 abstract 1
- 229920000098 polyolefin Polymers 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 229920002125 Sokalan® Polymers 0.000 description 9
- 239000004584 polyacrylic acid Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000919 ceramic Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000007761 roller coating Methods 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 4
- 238000005213 imbibition Methods 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 210000002469 basement membrane Anatomy 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 210000004379 membrane Anatomy 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 238000007613 slurry method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F259/00—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00
- C08F259/08—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing fluorine
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
-
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Cell Separators (AREA)
Abstract
The invention discloses a preparation method of self-stabilizing P (VDF-HFP) slurry, which comprises the steps of adding acrylic monomer and polymerization inhibitor into deionized water for mixing and dissolvingDissolving, and then adding P (VDF-HFP) powder to obtain a mixed system; introducing inert gas into the mixed system to remove air in the mixed system, and then sealing and storing; putting the mixed system hermetically stored in the step b into60Irradiating in a Co gamma-ray irradiation chamber to obtain a dispersion liquid; and centrifugally washing the dispersion liquid, and dispersing the dispersion liquid into deionized water again to prepare self-stabilizing P (VDF-HFP) slurry. The slurry prepared by the invention does not need to add any surfactant and adhesive, and is used for coating the lithium ion battery diaphragm without worrying about performance reduction and potential safety hazard caused by the dissolution of the surfactant and the adhesive in the electrolyte, thereby fundamentally improving the performance and the safety performance of the lithium ion battery.
Description
Technical field
The present invention relates to lithium ion battery separator fields, and in particular to a kind of self-stabilization P (VDF-HFP) slurry and its preparation
Method further relates to a kind of lithium ion battery separator.
Background technique
In recent years, with the emergence of this emerging strategic type industry of new-energy automobile, energy density is high, safety is excellent
The power lithium ion battery different, course continuation mileage is outstanding is paid close attention to by more and more people.Diaphragm as lithium ion battery four
One of big key main material (anode, cathode, diaphragm, electrolyte) primarily serves isolation positive and negative anodes and lithium ion is allowed to pass freely through
Effect.Diaphragm although and be not involved in the electrochemical reaction in battery, directly affect the capacity, cycle performance and peace of battery
Full performance.With being widely used for the raising of battery energy density, especially tertiary cathode material, to battery with two side terminals and peace
The requirement of full performance is also higher and higher.Wherein, carrying out surface coating to polyalkene diaphragm is to improve battery with two side terminals and safety
The effective means of performance coats vinylidene fluoride and hexafluoropropylene copolymer [P on conventional membrane surface by certain technique
(VDF-HFP)] coating is a kind of means being widely used.
P (VDF-HFP) coating common at present is to disperse P (VDF-HFP) under the action of dispersing agent and/or wetting agent
Yu Shuizhong is carried out coating again and is sticked to polyalkene diaphragm surface by adhesive.Although this mode has certain excellent
Gesture, but be on the one hand that the hydrogen bond of formation in P (VDF-HFP) strand is very strong, the oxygen electricity in water is negative there is also many flaws
Property be insufficient to allow its hydrogen bond separate, cause P (VDF-HFP) not disperse substantially in water, so needing that surfactant is added
It reduces the surface tension of water and improves the surface free energy of P (VDF-HFP)；On the other hand, it also needs that adhesive is added in slurry
To realize that cohering between P (VDF-HFP) and polyalkene diaphragm prevents from losing powder.And the introducing of surfactant and adhesive may be
It is dissolved under the long-term infiltration of electrolyte, potential security risk is generated to battery with two side terminals especially safety in this way.
Summary of the invention
In view of the above-mentioned problems, the present invention provides a kind of safety more preferably self-stabilization P (VDF-HFP) slurry and its preparations
Method, slurry obtained do not need that any surfactant and adhesive is added, and are used for coating lithium ion battery separator,
There is no concern that surfactant and adhesive dissolve brought performance decline and security risk in the electrolytic solution, fundamentally mention
The high performance and security performance of lithium ion battery.
The present invention to achieve the goals above, using following technical scheme:
A kind of preparation method of self-stabilization P (VDF-HFP) slurry, comprising the following steps:
A, mixed dissolution in deionized water is added in acrylic monomers, polymerization inhibitor, P (VDF-HFP) powder is then added, obtains
To mixed system；
B, the air being passed through in mixed system in inert gas exclusion mixed system, is then sealed；
C, the mixed system being sealed in step b is put into60It is irradiated, is dispersed in Co γ-ray irradiation devices
Liquid；
D, it will be scattered in again in deionized water after dispersion liquid centrifugation washing, self-stabilization P (VDF-HFP) slurry be made.
Preferably, the weight ratio of each component is acrylic monomers in the step a: polymerization inhibitor: P (VDF-HFP) powder: being gone
Ionized water=(10~300): (1~20): (5~100): 1000.
Preferably, the polymerization inhibitor is one in green vitriol, ferrous sulfate, copper sulphate or Salzburg vitriol
Kind.
Further, inert gas is passed through the time as 20min or more in the step b.
Preferably, its radiation dose rate of irradiation process is 2~50Gy/min in the step c, and irradiation time is 2~72h,
The total absorbed dose of irradiation is 5~50kGy.
Further, it is at least once that washing times are centrifuged in the step d.
Preferably, the solid content of self-stabilization P (VDF-HFP) slurry is 1~30%.
It is another object of the present invention to provide one kind self-stabilization P as made from preparation method described in any of the above embodiments
(VDF-HFP) slurry.
Third object of the present invention is to provide a kind of lithium ion battery separator, surface be coated with it is described above from
Stablize P (VDF-HFP) slurry.
Further, the application pattern be silk-screen printing, micro- rotogravure application, spraying, spot printing, blade coating, in dip coated
One kind, coating thickness be 0.5~5 μm, coating surface density be 0.2~2g/m2。
Compared with prior art, the invention has the following advantages:
The present invention is grafted PAA (polyacrylic acid) in P (VDF-HFP) microsphere surface using radiation grafted method, then will
Grafting PAA modified P (VDF-HFP) microballoon, which is coated to polyalkene diaphragm or has been coated with ceramic polyalkene diaphragm surface, obtains lithium
Ion battery diaphragm.P (VDF-HFP) slurry of the PAA modification obtained by this method does not need that any surface work is added
Property agent and adhesive.On the one hand, the surface free energy of P (VDF-HFP) can be improved in the extremely strong hydrophilic interaction of PAA chain, to promote
Into P (VDF-HFP) dispersion well in water；On the other hand, PAA is that good aqueous adhesive can be by the jail P (VDF-HFP)
Polyalkene diaphragm is sticked to firmly or has been coated with the polyalkene diaphragm surface of ceramics.By obtained high security lithium ion battery every
Film is in lithium ion battery, it is not necessary to worry surfactant and adhesive dissolve in the electrolytic solution brought by performance decline with
Security risk fundamentally improves the performance and security performance of lithium ion battery.
Specific embodiment
The invention discloses a kind of preparation methods of self-stabilization P (VDF-HFP) slurry, comprising the following steps:
A, mixed dissolution in deionized water is added in acrylic monomers, polymerization inhibitor, P (VDF-HFP) powder is then added, obtains
To mixed system；
B, the air being passed through in mixed system in inert gas exclusion mixed system, is then sealed；
C, the mixed system being sealed in step b is put into60It is irradiated, is dispersed in Co γ-ray irradiation devices
Liquid；
D, it will be scattered in again in deionized water after dispersion liquid centrifugation washing, self-stabilization P (VDF-HFP) slurry be made.
Self-stabilization P (VDF-HFP) slurry is made in preparation method in through the invention, on the one hand since its surface grafting has
PAA, therefore dispersing agent can be served as, promote P (VDF-HFP) microballoon to disperse well in water；On the other hand, the PAA of grafting
Adhesive can be served as, makes to bond well between the P (VDF-HFP) and diaphragm of coating.And the self-stabilization P (VDF- in the present invention
HFP) slurry does not contain the dispersing agent and adhesive that can be dissolved by the electrolyte, and avoids due to introducing surface-active in coating procedure
Potential risk brought by the auxiliary agents such as agent and adhesive coats diaphragm using self-stabilization P (VDF-HFP) slurry to improve
Battery electrical property, safety and stability.
Preferably, the weight ratio of each component is acrylic monomers in the step a: polymerization inhibitor: P (VDF-HFP) powder: being gone
Ionized water=(10~300): (1~20): (5~100): 1000.Wherein, the polymerization inhibitor is green vitriol, sulfuric acid
One of ferrous, copper sulphate or Salzburg vitriol.
In the step b inert gas in an embodiment of the present invention be most preferably nitrogen, be passed through the time be 20min with
On, most preferably 30min, it can guarantee excludes the air in mixed system completely, while not causing to waste.
Its radiation dose rate of irradiation process in the step c is 2~50Gy/min, and irradiation time is 2~72h, irradiation
Total absorbed dose be 5~50kGy.
It is that at least once, centrifugation washing times here are to guarantee to remove unreacted that washing times are centrifuged in the step d
Acrylic monomers and non-grafted polyacrylic acid be limited.
Preferably, the solid content of self-stabilization P (VDF-HFP) slurry is 1~30%, most preferably 5~20%.
Simultaneously the invention discloses a kind of self-stabilization P (VDF-HFP) slurry, it is prepared by any of the above-described kind of preparation method
It arrives.
Furthermore also disclose a kind of lithium ion battery for being coated with self-stabilization P (VDF-HFP) slurry of the present invention every
Film.
Preferably, the application pattern be silk-screen printing, micro- rotogravure application, spraying, spot printing, blade coating, in dip coated
One kind, coating thickness are 0.5~5 μm, and coating surface density is 0.2~2g/m2。
Further clear and complete explanation is done to technical solution of the present invention below with reference to specific embodiment.
Embodiment 1
A, mixed dissolution in 50ml deionized water is added in 5g acrylic monomers, 0.25g green vitriol, then added
Enter 1.5gP (VDF-HFP) powder, obtains mixed system；
B, the air being passed through in mixed system in nitrogen 30min exclusion mixed system, is then sealed；
C, the mixed system being sealed in step b is put into60It is in radiation dose rate in Co γ-ray irradiation devices
9Gy/min is irradiated for 24 hours, and irradiation total absorbed dose is 13kGy, obtains dispersion liquid；
D, it will be scattered in again in 30ml deionized water after dispersion liquid centrifugation washing 6 times, it is 1% self-stabilization that solid content, which is made,
P (VDF-HFP) slurry；
F, by self-stabilization P (VDF-HFP) slurry using dimple roller coating be distributed in polyolefin or have been coated with ceramics polyolefin every
Lithium ion battery separator is made in the surface of film, and applied thickness is 0.5 μm, and coating surface density is 0.2g/m2。
Embodiment 2
A, mixed dissolution in 100ml deionized water is added in 15g acrylic monomers, 0.5g copper sulphate, 4g P is then added
(VDF-HFP) powder obtains mixed system；
B, the air being passed through in mixed system in nitrogen 25min exclusion mixed system, is then sealed；
C, the mixed system being sealed in step b is put into60It is in radiation dose rate in Co γ-ray irradiation devices
6Gy/min irradiates 40h, and irradiation total absorbed dose is 50kGy, obtains dispersion liquid；
D, it will be scattered in again in 40ml deionized water after dispersion liquid centrifugation washing 5 times, it is 5% self-stabilization that solid content, which is made,
P (VDF-HFP) slurry；
F, by self-stabilization P (VDF-HFP) slurry using dimple roller coating be distributed in polyolefin or have been coated with ceramics polyolefin every
Lithium ion battery separator is made in the surface of film, and applied thickness is 1 μm, and coating surface density is 0.2g/m2。
Embodiment 3
A, mixed dissolution in 50ml deionized water is added in 0.5g acrylic monomers, 0.05g green vitriol, then
0.25g P (VDF-HFP) powder is added, obtains mixed system；
B, the air being passed through in mixed system in nitrogen 30min exclusion mixed system, is then sealed；
C, the mixed system being sealed in step b is put into60It is in radiation dose rate in Co γ-ray irradiation devices
2Gy/min irradiates 72h, and irradiation total absorbed dose is 8.6kGy, obtains dispersion liquid；
D, it will be scattered in again in 25ml deionized water after dispersion liquid centrifugation washing 6 times, it is 15% from surely that solid content, which is made,
Determine P (VDF-HFP) slurry；
F, by self-stabilization P (VDF-HFP) slurry using dimple roller coating be distributed in polyolefin or have been coated with ceramics polyolefin every
Lithium ion battery separator is made in the surface of film, and applied thickness is 2 μm, and coating surface density is 0.5g/m2。
Embodiment 4
A, mixed dissolution in 100ml deionized water is added in 30g acrylic monomers, 2g copper sulphate, 10gP is then added
(VDF-HFP) powder obtains mixed system；
B, the air being passed through in mixed system in nitrogen 30min exclusion mixed system, is then sealed；
C, the mixed system being sealed in step b is put into60It is in radiation dose rate in Co γ-ray irradiation devices
50Gy/min irradiates 2h, and irradiation total absorbed dose is 5kGy, obtains dispersion liquid；
D, it will be scattered in again in 20ml deionized water after dispersion liquid centrifugation washing 6 times, it is 20% from surely that solid content, which is made,
Determine P (VDF-HFP) slurry；
F, by self-stabilization P (VDF-HFP) slurry using dimple roller coating be distributed in polyolefin or have been coated with ceramics polyolefin every
Lithium ion battery separator is made in the surface of film, and applied thickness is 5 μm, and coating surface density is 2g/m2。
Embodiment 5
A, mixed dissolution in 100ml deionized water is added in 10g acrylic monomers, 0.75g green vitriol, then
3gP (VDF-HFP) powder is added, obtains mixed system；
B, the air being passed through in mixed system in nitrogen 30min exclusion mixed system, is then sealed；
C, the mixed system being sealed in step b is put into60It is in radiation dose rate in Co γ-ray irradiation devices
15Gy/min irradiates 18h, and irradiation total absorbed dose is 16.2kGy, obtains dispersion liquid；
D, it will be scattered in again in 20ml deionized water after dispersion liquid centrifugation washing 6 times, it is 30% from surely that solid content, which is made,
Determine P (VDF-HFP) slurry；
F, by self-stabilization P (VDF-HFP) slurry using dimple roller coating be distributed in polyolefin or have been coated with ceramics polyolefin every
Lithium ion battery separator is made in the surface of film, and applied thickness is 2 μm, and coating surface density is 0.8g/m2。
Comparative example
The gluing diaphragm for P (VDF-HFP) the slurry preparation for taking conventional dispersant to disperse, applied thickness are 2 μm, and applicator surface is close
Degree is 0.8g/m2, basement membrane is consistent with embodiment.
Embodiment 5 and comparative example are subjected to partial materialization measured performance parameter, measurement result is shown in Table 1.
1 embodiment 5 of table and comparative example physical and chemical performance parameter
As shown in Table 1, using in the present invention self-stabilization P (VDF-HFP) slurry coat made of diaphragm ventilative increment,
Contact angle and imbibition rate are superior to comparative example.Using identical basement membrane, increment of breathing freely is small, illustrates coating to the hole plug of diaphragm
Degree is small.Contact angle and imbibition rate height illustrate that the imbibition water retainability of diaphragm of the present invention is more excellent.
Example 5 prepare coating diaphragm and comparative example apply diaphragm, respectively with the iron phosphate lithium positive pole of preparation and stone
Black cathode uses lamination process, is made soft bag lithium ionic cell, the performance comparisons examination such as carries out battery capacity, internal resistance, fills, puts again again
It tests, acquired results are shown in Table 2:
2 embodiment 5 of table and comparative example soft bag lithium ionic cell the performance test results
| Capacity/Ah | Internal resistance/m Ω | 2C discharge capacity ratio/% | |
| Embodiment 5 | 6.72 | 2.96 | 95.95 |
| Comparative example | 6.55 | 3.03 | 97.11 |
As shown in Table 2, comparative example is compared using the battery of slurry of the present invention coating diaphragm preparation, there is higher capacity,
Lower internal resistance, and outstanding discharge-rate performance.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent alternative, be included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of self-stabilization P (VDF-HFP) slurry, it is characterised in that: the following steps are included:
A, mixed dissolution in deionized water is added in acrylic monomers, polymerization inhibitor, P (VDF-HFP) powder is then added, is mixed
Zoarium system；
B, the air being passed through in mixed system in inert gas exclusion mixed system, is then sealed；
C, the mixed system being sealed in step b is put into60It is irradiated in Co γ-ray irradiation devices, obtains dispersion liquid；
D, it will be scattered in again in deionized water after dispersion liquid centrifugation washing, self-stabilization P (VDF-HFP) slurry be made.
2. preparation method as described in claim 1, it is characterised in that: the weight ratio of each component is acrylic acid in the step a
Monomer: polymerization inhibitor: P (VDF-HFP) powder: deionized water=(10 ~ 300): (1 ~ 20): (5 ~ 100): 1000.
3. preparation method as described in claim 1, it is characterised in that: the polymerization inhibitor is green vitriol, sulfuric acid Asia
One of iron, copper sulphate or Salzburg vitriol.
4. preparation method as described in claim 1, it is characterised in that: inert gas is passed through the time as 20min in the step b
More than.
5. preparation method as described in claim 1, it is characterised in that: its radiation dose rate of irradiation process is 2 in the step c
~ 50Gy/min, irradiation time are 2 ~ 72h, and the total absorbed dose of irradiation is 5 ~ 50kGy.
6. preparation method as described in claim 1, it is characterised in that: being centrifuged washing times in the step d is at least once.
7. preparation method as described in claim 1, it is characterised in that: the solid content of self-stabilization P (VDF-HFP) slurry is
1~30%。
8. a kind of self-stabilization P (VDF-HFP) slurry prepared using preparation method as claimed in any one of claims 1 to 7.
9. the lithium ion battery separator that a kind of surface is coated with self-stabilization P (VDF-HFP) slurry as claimed in claim 8.
10. lithium ion battery separator as claimed in claim 8, it is characterised in that: the application pattern is silk-screen printing, dimple
One of version coating, spraying, spot printing, blade coating, dip coated, coating thickness are 0.5 ~ 5 μm, and coating surface density is 0.2 ~ 2g/
m2。
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110452336A (en) * | 2019-08-15 | 2019-11-15 | 宁德卓高新材料科技有限公司 | The method for preparing modified partial fluorine ethylene polymer powder |
| CN115074059A (en) * | 2022-07-07 | 2022-09-20 | 合肥国轩高科动力能源有限公司 | Preparation method of high-adhesion water system P (VDF-HFP) gluing membrane and lithium ion battery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102977276A (en) * | 2012-09-20 | 2013-03-20 | 中国科学院上海应用物理研究所 | Aqueous polytetrafluoroethylene material, preparation method and uses thereof |
| CN104868081A (en) * | 2014-12-22 | 2015-08-26 | 上海恩捷新材料科技股份有限公司 | Water-based multi-layer membrane for lithium ion battery |
-
2018
- 2018-08-22 CN CN201810961375.2A patent/CN109161292B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102977276A (en) * | 2012-09-20 | 2013-03-20 | 中国科学院上海应用物理研究所 | Aqueous polytetrafluoroethylene material, preparation method and uses thereof |
| CN104868081A (en) * | 2014-12-22 | 2015-08-26 | 上海恩捷新材料科技股份有限公司 | Water-based multi-layer membrane for lithium ion battery |
Non-Patent Citations (1)
| Title |
|---|
| 李晓 等: "射线辐照接枝丙烯酸改性 PVDF 超滤膜", 《膜科学与技术》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110452336A (en) * | 2019-08-15 | 2019-11-15 | 宁德卓高新材料科技有限公司 | The method for preparing modified partial fluorine ethylene polymer powder |
| CN110452336B (en) * | 2019-08-15 | 2021-10-01 | 宁德卓高新材料科技有限公司 | Method for preparing modified vinylidene fluoride polymer powder |
| CN115074059A (en) * | 2022-07-07 | 2022-09-20 | 合肥国轩高科动力能源有限公司 | Preparation method of high-adhesion water system P (VDF-HFP) gluing membrane and lithium ion battery |
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