CN109065811A - Aqueous PVDF coating diaphragm and its preparation method and application - Google Patents
Aqueous PVDF coating diaphragm and its preparation method and application Download PDFInfo
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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
- H01M10/058—Construction or manufacture
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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
- H01M50/411—Organic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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Abstract
The present invention provides a kind of aqueous PVDF coating diaphragm and its preparation method and application, and the preparation process is as follows: preparing modified water-soluble PVDF powder first, further prepares PVDF coating slurry, further prepares aqueous PVDF coating diaphragm.So that obtained aqueous PVDF coating slurry is obviously improved the dispersibility and stability of PVDF particle in aqueous solution by the modification to PVDF, and then is obviously improved the comprehensive performance of lithium ion battery separator.
Description
Technical field
The present invention relates to battery diaphragm material technical field, it particularly relates to a kind of aqueous PVDF coating diaphragm and its
Preparation method and application.
Background technique
Due to booming, more and more cokes of the energy and environment problem and electronics and information industry that get worse
Point is gathered in high-energy-density, safe and non-toxic energy and material.Lithium ion secondary battery have high-energy density, have extended cycle life,
The characteristic of memory-less effect, and have many advantages, such as safe, environmentally friendly, reliable and energy fast charging and discharging.Thus become in recent years
The hot spot for carrying out energy storage technology research, is widely used in mobile phone, laptop, the portable electronic products such as digital camera also must
The preferred energy storing devices of hybrid vehicle and electric car will be become.
Currently, diaphragm used in power battery is ceramics or polymer-coated diaphragm.Use PVDF as coating, it is main
The adhesive layer that functions as pole piece is bonded together with diaphragm, the benefit of bonding is that battery can be harder, solid, production fortune
There is very big advantage in defeated, another advantage of adhesive layer is can to ensure that the safety of battery with imbibition.Therefore,
Present PVDF coating is inside smart phone using most.
PVDF coating processes mainly have oiliness coating and aqueous coating.Being used using oiliness coating processes needs is largely had
Solvent, causes serious pollution to the environment and cost is very high.A kind of coating processes of the aqueous coating mainly using water as solvent, the work
Skill environmental pollution is small, is the developing direction for producing PVDF coating diaphragm in enormous quantities.However, PVDF is as hydrophobic polymer,
Bad dispersibility in water, particle are easy to reunite, settle, and cause PVDF coating granule sense after coating very strong, are hardly formed PVDF
The coating that grain is evenly distributed.
Summary of the invention
For above-mentioned technical problem in the related technology, the present invention provides a kind of aqueous PVDF coating diaphragm and its preparations
Methods and applications are obviously improved the dispersibility and stability of PVDF particle in aqueous solution, and then are obviously improved lithium ion battery
The comprehensive performance of diaphragm.
To realize the above-mentioned technical purpose, the technical scheme of the present invention is realized as follows:
On the one hand, the present invention provides a kind of preparation method of modified water-soluble PVDF powder, includes the following steps:
1) latex A is prepared: by PVDF powder, the first fluorine ion surfactant, perfluoroalkyl acrylate, metering system
PVDF mixed emulsion is obtained after sour methyl esters, Long carbon chain benzene alkene and the mixing of the first deionized water, PVDF mixed emulsion is ground to obtain
Latex A；
2) solution B is prepared: in a nitrogen atmosphere, by initiator, the second fluorine ion surfactant and the second deionized water
Heating stirring is configured to solution B after mixing；
3) it prepares modified water-soluble PVDF powder: in a nitrogen atmosphere, latex A being slowly added in solution B, heating stirring,
It filters, washing, drying, obtains modified water-soluble PVDF powder.
Further, the PVDF powder, the first fluorine ion surfactant, perfluoroalkyl acrylate, metering system
Sour methyl esters, Long carbon chain benzene alkene and the first deionized water, according to the mass fraction, ratio are 8~20: 0.11~0.75: 0.1~0.5:
0.3~0.9: 1~2: 70~90.
Further, the grinding carries out 0.5~3h in grinder.
Further, the initiator, the second fluorine ion surfactant and the second deionized water, according to the mass fraction,
Ratio is 0.1~1: 0.1~0.5: 80~100.
Further, in step 2), the heating stirring refers to 0.5~8h of stirring at 50~80 DEG C.
Further, in step 3), the latex A and solution B, according to the mass fraction, ratio are 20~50: 50~80.
Further, in step 3), the heating stirring refers to 0.5~8h of stirring at 50~80 DEG C.
On the one hand, the present invention provides a kind of preparation method of aqueous PVDF coating diaphragm, includes the following steps:
Modified water-soluble PVDF powder, bonding agent prepared by the present invention, thickener, wetting agent and deionized water are mixed and stirred
It mixes to obtain aqueous PVDF coating slurry；
After the aqueous PVDF coating slurry of gained is coated in polyalkene diaphragm, drying obtains aqueous PVDF coating diaphragm.
Further, the modified water-soluble PVDF powder, bonding agent, thickener, wetting agent and deionized water, by mass parts
Number meter, ratio are 10~20: 0.05~0.7: 0.01~0.6: 0.01~0.7: 78~89.93.
Further, the mixing time is 2~8h.
Further, the drying temperature is 40~70 DEG C.
Fluorine ion surfactant of the present invention includes perfluorooctanoic acid, perfluoro-heptanoic acid, perfluorododecyl sodium sulfonate
One of or it is a variety of.
The perfluoroalkyl acrylate includes perfluor alkyl ethyl acrylate, perfluorooctanol acrylate, 2- (perfluor
Hexyl) ethylmethyl acrylate, one of perluorooctyl acrylate or a variety of.
The Long carbon chain benzene alkene includes one of 4- phenyl -1- butylene, 1- phenyl amylene, propenyl benzene or a variety of.
The grinder is ground using the zirconium oxide microballon that particle size is 0.1-0.5mm, when grinding, the oxidation
The mass ratio of zirconium microballon and PVDF mixed emulsion is 1: 3~5, and grinder rotating speed is 10-50 revs/min.
The initiator includes: azodiisobutyronitrile, ammonium persulfate or two t-amyl peroxy compounds.
The binder include butadiene-styrene latex, styrene-acrylic latex, polyvinyl alcohol, ethylene-vinyl acetate copolymer, in polyurethane
It is one or more；
The thickener includes hydroxyethyl cellulose, methyl hydroxyethylcellulose, sodium carboxymethylcellulose, polyacrylamide
One of amine, sodium alginate are a variety of；
The wetting agent include fluoro-alkyl methoxyl group ether alcohol, fluoro-alkyl ethyoxyl ether alcohol, alkyl phenol polyoxyethylene ether,
One of fatty alcohol polyoxyethylene ether, aliphatic acid polyethenoxy ether are a variety of.
On the other hand, the present invention provides a kind of aqueous PVDF coating diaphragm, and the method is prepared into through the invention
It arrives.
On the other hand, the present invention provides a kind of lithium ion battery, including positive electrode and negative electrode material, in positive electrode and
There is above-mentioned aqueous PVDF to coat diaphragm between negative electrode material.
The present invention is amphipathic with fluorine ion surfactant, and PVDF particle can be modified monomer cladding completely, makes
Obtaining PVDF can effectively and uniformly be dispersed in water, and improve the cementability of modified PVDF powder.
The present invention can be improved the spy of the glass transition temperature of material using phenyl ring segment by addition Long carbon chain benzene alkene
Property, improve the thermal stability of material.
The present invention uses the crosslinked action of perfluoroalkyl acrylate, methyl methacrylate, Long carbon chain benzene alkene, improves
The crystallinity of PVDF is realized the storage stability and dilution stability of the PVDF coating slurry of modified PVDF powder preparation, is conducive to
Subsequent film forming increases the application performance of modified PVDF powder especially PVDF coating slurry.
Beneficial effects of the present invention:
The present invention provides a kind of aqueous PVDF coating diaphragm and its preparation method and application, has the advantage that
1) present invention solvent modified as PVDF using water first, obtains modified PVDF powder；In modifying process, adopt
Fluorochemical monomer to the surface PVDF have better compatibility, enable PVDF particle be modified completely monomer cladding, improve
The dispersibility of modified PVDF particle in water, so that the modification PVDF powder of preparation is more evenly, stability and distribution are more preferable；It adopts
PVDF is modified with the monomer of super low concentration, PVDF stable structure after making before modified.
2) PVDF coating slurry is further prepared in the present invention in water, using PVDF powder modified, so that
The coating slurry stable storing of preparation avoids PVDF particle from the case where plug-hole occur in subsequent coated diaphragm；The coating of preparation
Neat close, the good permeability of particle arrangement on diaphragm, imbibition rate and ionic conductivity are high, and coating stripping intensity is high.
3) coating slurry prepared by the present invention, after being coated on diaphragm, the particle in modified PVDF coating can mutually glue
Knot, greatly reduces the usage amount of binder；The coating slurry stability of preparation is good.
4) preparation method simple process of the invention, environmental pollution is few, adaptable to existing equipment, is suitable for industrialization
Production.
Detailed description of the invention
It in order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, below will be to institute in embodiment
Attached drawing to be used is needed to be briefly described, it should be apparent that, the accompanying drawings in the following description is only some implementations of the invention
Example, for those of ordinary skill in the art, without creative efforts, can also obtain according to these attached drawings
Obtain other attached drawings.
Fig. 1 is that the aqueous PVDF of preferred embodiment of the present invention preparation coats the SEM figure of diaphragm.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's every other embodiment obtained, shall fall within the protection scope of the present invention.
Unless otherwise defined, all technical terms used hereinafter and the normally understood meaning of those skilled in the art
It is identical.Technical term used herein is intended merely to the purpose of description specific embodiment, is not intended to the limitation present invention
Protection scope.
Except there is a special instruction, the various reagents used in the present invention, raw material be can commodity commercially or
Person can the product as made from well known method.
Embodiment 1
By 8g PVDF powder, 0.5g perfluoro-heptanoic acid, 0.1g perfluor alkyl ethyl acrylate, ten trifluoro of 0.4g acrylic acid
Monooctyl ester, 0.3g methyl methacrylate, 1g 4- phenyl -1- butylene and the mixing of 85.3g deionized water, obtain PVDF mixed emulsion.
The zirconium oxide microballon that grinder is 0.1mm using particle size, the quality of zirconium oxide microballon and PVDF mixed emulsion
Than being 1: 3, grinder rotating speed is 50 revs/min, obtains latex A after PVDF mixed emulsion is ground 3h in grinder.
In N20.6g azodiisobutyronitrile, 0.1g perfluoro-heptanoic acid and 99.3g deionized water are mixed under gas shield, 50
8h is stirred at DEG C, is configured to solution B.
In N2Under gas shield, 50g latex A is slowly added in 80g solution B, stirs 6h at 50 DEG C.Reaction is completed
Afterwards, modified PVDF mixed liquor is obtained.Modified PVDF mixed liquor is filtered with vacuum filtration machine, is washed with deionized 5 times, dries
Afterwards, modified PVDF powder is obtained.
By 12g modified PVDF particle, 0.3g butadiene-styrene latex, 0.4g ethylene-vinyl acetate copolymer, 0.01g ethoxy
8h is mixed in cellulose, 0.7g fatty alcohol polyoxyethylene ether, obtains modified PVDF coating slurry.
Modified PVDF coating slurry is coated on polyalkene diaphragm, obtained after being dried at 70 DEG C aqueous PVDF coating every
Film.
Aqueous PVDF coating slurry manufactured in the present embodiment does not settle after standing 7 days at room temperature.
Coating diaphragm coating layer thickness manufactured in the present embodiment is 2 μm, and air permeability increases 10s (100cc/in after coating2), point
Solution voltage is 4.9V, is heat-shrinked respectively 0.43% (direction MD), 0.12% (direction TD) after 2h is toasted under the conditions of 105 DEG C,
Imbibition rate is 263.7%, and broken film temperature is 159 DEG C, and lithium ion conductivity is 1.26 × 10-3S/cm, lithium ion transference number are
0.61, coating stripping intensity is 305N/m.
Cobalt acid lithium, lithium piece, electrolyte and aqueous PVDF coating diaphragm are assembled into button cell and test its performance, in 3C
Charge-discharge magnification under circulation 500 circle after capacity retention ratio be 86.9%.
Embodiment 2
By 20g PVDF powder, 0.45g perfluorooctanoic acid, 0.3g perfluorododecyl sodium sulfonate, 0.1g perfluorooctanol third
Olefin(e) acid ester, 0.61g methyl methacrylate, 0.9g 1- phenyl amylene, 0.8 propenyl benzene and the mixing of 70g deionized water, obtain
PVDF mixed emulsion.
The zirconium oxide microballon that grinder is 0.5mm using particle size, the quality of zirconium oxide microballon and PVDF mixed emulsion
Than being 1: 4, grinder rotating speed is 30 revs/min, obtains latex A after PVDF mixed emulsion is ground 0.5h in grinder.
In N2Bis- t-amyl peroxy compound of 0.6g, 0.1g perfluorooctanoic acid and 99.3g deionized water are mixed under gas shield
It closes, stirs 0.5h at 80 DEG C, be configured to solution B.
In N2Under gas shield, 20g latex A is slowly added in 65g solution B, stirs 0.5h at 80 DEG C.Reaction is completed
Afterwards, modified PVDF mixed liquor is obtained.Modified PVDF mixed liquor is filtered with vacuum filtration machine, is washed with deionized 3 times, dries
Afterwards, modified PVDF powder is obtained.
By 10g modified PVDF particle, 0.05g polyvinyl alcohol, 0.6g methyl hydroxyethylcellulose, 0.38g fluoro-alkyl
3h is mixed in the pure and mild 88.97g deionized water of methoxy-ether, obtains modified PVDF coating slurry.It will modified PVDF coating slurry
Diaphragm is coated coated in aqueous PVDF on polyalkene diaphragm, is obtained after drying at 40 DEG C.
Aqueous PVDF coating slurry manufactured in the present embodiment does not settle after standing 7 days at room temperature.
Aqueous PVDF coating diaphragm coating layer thickness manufactured in the present embodiment is 2 μm, and air permeability increases 8s (100cc/ after coating
in2), decomposition voltage 4.7V is heat-shrinked respectively 0.58% (direction MD), 0.21% (TD after toasting 2h under the conditions of 105 DEG C
Direction), imbibition rate 257.9%, broken film temperature is 167 DEG C, and lithium ion conductivity is 1.31 × 10-3S/cm, lithium ion mobility
Number is 0.69, and coating stripping intensity is 327N/m.
Cobalt acid lithium, lithium piece, electrolyte and aqueous PVDF coating diaphragm are assembled into button cell and test its performance, in 3C
Charge-discharge magnification under circulation 500 circle after capacity retention ratio be 88.4%.
Embodiment 3
By 15g PVDF powder, 0.11g perfluorododecyl sodium sulfonate, 0.3g 2- (perfluoro hexyl) ethyl-methyl propylene
Acid esters, 0.9g methyl methacrylate, 2g 1- phenyl amylene and the mixing of 90g deionized water, obtain PVDF mixed emulsion.
The zirconium oxide microballon that grinder is 0.3mm using particle size, the quality of zirconium oxide microballon and PVDF mixed emulsion
Than being 1: 5, grinder rotating speed is 10 revs/min, obtains latex A after PVDF mixed emulsion is ground 1.5h in grinder.
In N20.6g ammonium persulfate, 0.1g perfluorododecyl sodium sulfonate and 99.3g deionized water are mixed under gas shield
It closes, stirs 5h at 75 DEG C, be configured to solution B.
In N2Under gas shield, 30g latex A is slowly added in 50g solution B, stirs 8h at 60 DEG C.Reaction is completed
Afterwards, modified PVDF mixed liquor is obtained.Modified PVDF mixed liquor is filtered with vacuum filtration machine, is washed with deionized 4 times, dries
Afterwards, modified PVDF powder is obtained.
By 20g modified PVDF particle, 0.3g polyurethane, 0.37g sodium carboxymethylcellulose, 0.2g sodium alginate, 0.01g
2h is mixed in aliphatic acid polyethenoxy ether and 79.12g deionized water, obtains modified PVDF coating slurry.Modified PVDF is applied
Slurry is covered coated on polyalkene diaphragm, obtains aqueous PVDF coating diaphragm after drying at 55 DEG C.
Aqueous PVDF coating slurry manufactured in the present embodiment does not settle after standing 7 days at room temperature.
Aqueous PVDF coating diaphragm coating layer thickness manufactured in the present embodiment is 2 μm, and air permeability increases 11s after coating
(100cc/in2), decomposition voltage 4.9V, under the conditions of 105 DEG C toast 2h after be heat-shrinked be respectively 0.57% (direction MD),
0.18% (direction TD), imbibition rate 235.7%, broken film temperature are 173 DEG C, and lithium ion conductivity is 1.79 × 10-3S/cm, lithium
Transference number of ions is 0.63, and coating stripping intensity is 294N/m.
Cobalt acid lithium, lithium piece, electrolyte and aqueous PVDF coating diaphragm are assembled into button cell and test its performance, in 3C
Charge-discharge magnification under circulation 500 circle after capacity retention ratio be 91.3%.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of modified water-soluble PVDF powder, which comprises the steps of:
1) latex A is prepared: by PVDF powder, the first fluorine ion surfactant, perfluoroalkyl acrylate, methyl methacrylate
PVDF mixed emulsion is obtained after ester, Long carbon chain benzene alkene and the mixing of the first deionized water, grinds PVDF mixed emulsion to obtain lotion
A；
2) it prepares solution B: in a nitrogen atmosphere, initiator, the second fluorine ion surfactant and the second deionized water being mixed
Heating stirring is configured to solution B afterwards；
3) it prepares modified water-soluble PVDF powder: in a nitrogen atmosphere, latex A being slowly added in solution B, heating stirring, filter,
Washing, drying, obtain modified water-soluble PVDF powder.
2. the preparation method of modified water-soluble PVDF powder according to claim 1, which is characterized in that the PVDF powder,
First fluorine ion surfactant, perfluoroalkyl acrylate, methyl methacrylate, Long carbon chain benzene alkene and the first deionization
Water, according to the mass fraction, ratio are 8 ~ 20:0.11 ~ 0.75:0.1 ~ 0.5:0.3 ~ 0.9:1 ~ 2:70 ~ 90；
The grinding carries out 0.5 ~ 3h in grinder.
3. the preparation method of modified water-soluble PVDF powder according to claim 1, which is characterized in that the initiator,
Difluoro ionic surface active agent and the second deionized water, according to the mass fraction, ratio are 0.1 ~ 1:0.1 ~ 0.5:80 ~ 100；
In step 2, the heating stirring refers to 0.5 ~ 8h of stirring at 50 ~ 80 DEG C.
4. the preparation method of modified water-soluble PVDF powder according to claim 1, which is characterized in that described in step 3)
Latex A and solution B, according to the mass fraction, ratio are 20 ~ 50:50 ~ 80；
The heating stirring refers to 0.5 ~ 8h of stirring at 50 ~ 80 DEG C.
5. the preparation method of modified water-soluble PVDF powder according to claim 1, which is characterized in that the fluorine ion surface
Activating agent includes one of perfluorooctanoic acid, perfluoro-heptanoic acid, perfluorododecyl sodium sulfonate or a variety of；
The perfluoroalkyl acrylate include perfluor alkyl ethyl acrylate, perfluorooctanol acrylate, 2- (perfluor oneself
Base) ethylmethyl acrylate, one of perluorooctyl acrylate or a variety of；
The Long carbon chain benzene alkene includes one of 4- phenyl -1- butylene, 1- phenyl amylene, propenyl benzene or a variety of；
The initiator includes azodiisobutyronitrile, ammonium persulfate or two t-amyl peroxy compounds.
6. a kind of preparation method of aqueous PVDF coating diaphragm, which comprises the steps of:
By modified water-soluble PVDF powder, bonding agent, thickener, wetting agent and deionization prepared by any one of claim 1 ~ 5
Water is mixed to obtain aqueous PVDF coating slurry；
After the aqueous PVDF coating slurry of gained is coated in polyalkene diaphragm, drying obtains aqueous PVDF coating diaphragm.
7. the preparation method of aqueous PVDF coating diaphragm according to claim 6, which is characterized in that the modified water-soluble
PVDF powder, bonding agent, thickener, wetting agent and deionized water, according to the mass fraction, ratio are 10 ~ 20:0.05 ~ 0.7:
0.01~0.6:0.01~0.7:78~89.93；
The mixing time is 2 ~ 8h；
The drying temperature is 40 ~ 70 DEG C.
8. the preparation method of aqueous PVDF coating diaphragm according to claim 6, which is characterized in that the binder includes
One of butadiene-styrene latex, styrene-acrylic latex, polyvinyl alcohol, ethylene-vinyl acetate copolymer, polyurethane are a variety of；
The thickener includes hydroxyethyl cellulose, methyl hydroxyethylcellulose, sodium carboxymethylcellulose, polyacrylamide, sea
One of mosanom is a variety of；
The wetting agent includes fluoro-alkyl methoxyl group ether alcohol, fluoro-alkyl ethyoxyl ether alcohol, alkyl phenol polyoxyethylene ether, fat
One of alcohol polyoxyethylene ether, aliphatic acid polyethenoxy ether are a variety of.
9. a kind of aqueous PVDF coats diaphragm, which is characterized in that be prepared by the described in any item methods of claim 6 ~ 8
It arrives.
10. a kind of lithium ion battery, which is characterized in that including positive electrode and negative electrode material, in positive electrode and negative electrode material
Between there is aqueous PVDF as claimed in claim 9 to coat diaphragm.
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| CN201810947509.5A CN109065811B (en) | 2018-08-20 | 2018-08-20 | Water-based PVDF (polyvinylidene fluoride) coated diaphragm and preparation method and application thereof |
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| CN201810947509.5A CN109065811B (en) | 2018-08-20 | 2018-08-20 | Water-based PVDF (polyvinylidene fluoride) coated diaphragm and preparation method and application thereof |
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| CN110707266A (en) * | 2019-09-23 | 2020-01-17 | 河北金力新能源科技股份有限公司 | PVDF (polyvinylidene fluoride) mixed coating slurry, preparation method thereof and diaphragm |
| CN111180638A (en) * | 2020-01-17 | 2020-05-19 | 江苏厚生新能源科技有限公司 | PVDF (polyvinylidene fluoride) modified diaphragm and preparation method thereof |
| CN111341974A (en) * | 2020-03-13 | 2020-06-26 | 江苏厚生新能源科技有限公司 | PVDF (polyvinylidene fluoride) coated diaphragm and preparation method thereof, PVDF coated layer and lithium battery |
| CN111816826A (en) * | 2020-07-24 | 2020-10-23 | 佛山市金辉高科光电材料股份有限公司 | Aqueous polymer functional slurry and preparation method and application thereof |
| CN112795247A (en) * | 2021-01-08 | 2021-05-14 | 厦门大学 | High-viscosity PVDF (polyvinylidene fluoride) coated diaphragm and preparation method thereof |
| CN114292554A (en) * | 2022-01-27 | 2022-04-08 | 上海水立方新材料有限公司 | Modified nano-silica reinforced aqueous PVDF coating and preparation method thereof |
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| CN114716775B (en) * | 2022-03-21 | 2023-09-12 | 惠州市豪鹏科技有限公司 | Material for electrolyte separator, preparation method and battery |
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