CN109830630A - Coating diaphragm with hierarchical porous structure and its preparation method and application - Google Patents
Coating diaphragm with hierarchical porous structure and its preparation method and application Download PDFInfo
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- CN109830630A CN109830630A CN201811637390.8A CN201811637390A CN109830630A CN 109830630 A CN109830630 A CN 109830630A CN 201811637390 A CN201811637390 A CN 201811637390A CN 109830630 A CN109830630 A CN 109830630A
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- 238000000576 coating method Methods 0.000 title claims abstract description 88
- 239000011248 coating agent Substances 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 229920000642 polymer Polymers 0.000 claims abstract description 78
- 239000012528 membrane Substances 0.000 claims abstract description 55
- 239000000758 substrate Substances 0.000 claims abstract description 35
- 239000007788 liquid Substances 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims description 101
- 239000012530 fluid Substances 0.000 claims description 30
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 239000011230 binding agent Substances 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 24
- 239000004094 surface-active agent Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 14
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 10
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 10
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 9
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 9
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 9
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 9
- 239000004952 Polyamide Substances 0.000 claims description 8
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 8
- 229920002647 polyamide Polymers 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 7
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000003618 dip coating Methods 0.000 claims description 7
- 229920000193 polymethacrylate Polymers 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 claims description 6
- LGCNDZIFJKHQHB-UHFFFAOYSA-N 1,3-dioxacycloundecan-2-one Chemical compound O=C1OCCCCCCCCO1 LGCNDZIFJKHQHB-UHFFFAOYSA-N 0.000 claims description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 229930188620 butyrolactone Natural products 0.000 claims description 6
- 239000003822 epoxy resin Substances 0.000 claims description 6
- 229920002313 fluoropolymer Polymers 0.000 claims description 6
- 239000004811 fluoropolymer Substances 0.000 claims description 6
- 229920001519 homopolymer Polymers 0.000 claims description 6
- -1 phthalic acid ester Chemical class 0.000 claims description 6
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 6
- 229920000647 polyepoxide Polymers 0.000 claims description 6
- 229920000728 polyester Polymers 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 229920000098 polyolefin Polymers 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 5
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 5
- 239000011118 polyvinyl acetate Substances 0.000 claims description 5
- 239000008096 xylene Substances 0.000 claims description 5
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 claims description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- 229910001416 lithium ion Inorganic materials 0.000 claims description 4
- 229920000058 polyacrylate Polymers 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 238000007761 roller coating Methods 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims 2
- 229920001721 polyimide Polymers 0.000 claims 2
- 238000004026 adhesive bonding Methods 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- 238000007334 copolymerization reaction Methods 0.000 claims 1
- 238000010422 painting Methods 0.000 claims 1
- 229920006316 polyvinylpyrrolidine Polymers 0.000 claims 1
- 238000005213 imbibition Methods 0.000 abstract description 8
- 239000010410 layer Substances 0.000 description 26
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 230000003213 activating effect Effects 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- 229960000583 acetic acid Drugs 0.000 description 3
- 125000005909 ethyl alcohol group Chemical group 0.000 description 3
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229940113088 dimethylacetamide Drugs 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical class OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 210000004709 eyebrow Anatomy 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000013047 polymeric layer Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Cell Separators (AREA)
- Laminated Bodies (AREA)
Abstract
A kind of coating diaphragm and its preparation method and application with hierarchical porous structure, the coating diaphragm includes porous membrane substrate and the polymer-coated layer coated at least one surface of porous membrane substrate, and the hierarchical porous structure at least two apertures is distributed on polymer-coated layer.Liquid measure is protected in coating diaphragm porosity with higher of the invention and imbibition, is conducive to the raising of diaphragm ionic conductivity and battery.
Description
Technical field
The present invention relates to battery diaphragm technical fields, and in particular to a kind of coating diaphragm and its system with hierarchical porous structure
Preparation Method and purposes.
Background technique
As the important component of lithium ion battery, safety and service life of the composition and performance of diaphragm to battery
Etc. performances have an important influence.For the service life for improving battery, the most commonly used is coat one layer on the surface of diaphragm to be formed
Diaphragm can be improved in the coating diaphragm that the polymeric layer of porous structure is formed, the coating diaphragm with porous structure polymer layer
Porosity, and then increase diaphragm liquid absorption amount, improve the cycle life of respective battery.
For general porous structure polymer layer due to type of polymer and preparation method, the porous structure of formation is poly-
The aperture size for closing nitride layer is relatively uniform, and it is little that the corresponding porosity for coating diaphragm and liquid absorption amount improve degree, to diaphragm from
The raising of electron conductivity and battery has little significance.
Summary of the invention
The present invention provides a kind of coating diaphragm and its preparation method and application with hierarchical porous structure, coating diaphragm tool
There are higher porosity and imbibition to protect liquid measure, is conducive to the raising of diaphragm ionic conductivity and battery.
According in a first aspect, providing a kind of coating diaphragm with hierarchical porous structure, including perforated membrane in a kind of embodiment
Substrate and polymer-coated layer coated on above-mentioned at least one surface of porous membrane substrate are distributed on above-mentioned polymer-coated layer
The hierarchical porous structure at least two apertures.
In a preferred embodiment, above-mentioned porous membrane substrate is selected from polyolefin single or multilayer porous film, polyester perforated membrane, gathers
One of acid imide perforated membrane and polyamide perforated membrane are a variety of.
In a preferred embodiment, above-mentioned porous membrane substrate with a thickness of 5-30 μm, porosity ranges 30%-90%, hole
Diameter range is 0.005-0.20 μm.
In a preferred embodiment, polymer is selected from copolymer and/or homopolymer in above-mentioned polymer-coated layer.
In a preferred embodiment, polymer is selected from polyacrylonitrile, polymethacrylates, gathers in above-mentioned polymer-coated layer
One of vinylpyrrolidone, Kynoar, Kynoar-hexafluoropropene, polyvinyl acetate and polyethylene glycol oxide
Or it is a variety of.
In a preferred embodiment, above-mentioned polymer-coated layer by containing polymer, binder, surfactant, solvent and
The coating liquid of at least two non-solvents is at least one surface of above-mentioned porous membrane substrate and dry formation, wherein above-mentioned solvent
For the solvent that can dissolve above-mentioned polymer；Above-mentioned non-solvent is the solvent for being lean solvent relative to above-mentioned polymer.
In a preferred embodiment, above-mentioned non-solvent is selected from methanol, ethyl alcohol, normal propyl alcohol, isopropanol, butanol, propylene glycol, 3 third
Glycol, water, benzene,toluene,xylene, n-hexane, hexamethylene, ethylene carbonate, propene carbonate and phthalic acid ester.
In a preferred embodiment, above-mentioned solvent is selected from n,N-Dimethylformamide, n,N-dimethylacetamide, tetrahydro furan
It mutters, acetone, methyl ethyl ketone, N-Methyl pyrrolidone, N, N, N ', N '-tetramethylurea, dimethyl sulfoxide, triethyl phosphate, acetic acid are just
Butyl ester, cyclohexanone, diacetone alcohol and butyrolactone.
In a preferred embodiment, solid content is 1-25wt% in above-mentioned coating fluid.
In a preferred embodiment, the ratio of above-mentioned solvent and non-solvent is 50-99.9wt%.
In a preferred embodiment, above-mentioned binder is selected from carboxymethyl cellulose, butadiene-styrene rubber, epoxy resin, polyacrylic acid
One of ester and their derivative are a variety of.
In a preferred embodiment, above-mentioned surfactant is in ethylene oxide polymer, polyethers and fluoropolymer
It is one or more.
In a preferred embodiment, the content of above-mentioned binder is 0.5-10wt%, above-mentioned table in above-mentioned polymer-coated layer
The content of face activating agent is 0.05-5wt%.
According to second aspect, a kind of method of coating diaphragm prepared with hierarchical porous structure is provided in a kind of embodiment,
Include:
(a) provide containing polymer, binder, surfactant, solvent and at least two non-solvents coating fluid, wherein
Above-mentioned solvent is the solvent that can dissolve above-mentioned polymer；Above-mentioned non-solvent is the solvent for being lean solvent relative to above-mentioned polymer；
(b) by above-mentioned coating liquid at least one surface of porous membrane substrate；With
(c) drying at least one surface of above-mentioned porous membrane substrate of above-mentioned coating fluid is made to form polymer-coated layer, on
State the hierarchical porous structure that at least two apertures are distributed on polymer-coated layer.
In a preferred embodiment, above-mentioned porous membrane substrate is selected from polyolefin single or multilayer porous film, polyester perforated membrane, gathers
One of acid imide perforated membrane and polyamide perforated membrane are a variety of.
In a preferred embodiment, above-mentioned porous membrane substrate with a thickness of 5-30 μm, porosity ranges 30%-90%, hole
Diameter range is 0.005-0.20 μm.
In a preferred embodiment, above-mentioned polymer is selected from copolymer and/or homopolymer.
In a preferred embodiment, above-mentioned polymer be selected from polyacrylonitrile, polymethacrylates, polyvinylpyrrolidone,
One of Kynoar, Kynoar-hexafluoropropene, polyvinyl acetate and polyethylene glycol oxide are a variety of.
In a preferred embodiment, above-mentioned non-solvent is selected from methanol, ethyl alcohol, normal propyl alcohol, isopropanol, butanol, propylene glycol, 3 third
Glycol, water, benzene,toluene,xylene, n-hexane, hexamethylene, ethylene carbonate, propene carbonate and phthalic acid ester.
In a preferred embodiment, above-mentioned solvent is selected from n,N-Dimethylformamide, n,N-dimethylacetamide, tetrahydro furan
It mutters, acetone, methyl ethyl ketone, N-Methyl pyrrolidone, N, N, N ', N '-tetramethylurea, dimethyl sulfoxide, triethyl phosphate, acetic acid are just
Butyl ester, cyclohexanone, diacetone alcohol and butyrolactone.
It should be noted that the difference (Δ) of the solubility parameter between two or more different non-solvents and solvent is in ladder
Degree distribution.
In a preferred embodiment, solid content is 1-25wt% in above-mentioned coating fluid.
In a preferred embodiment, the ratio of above-mentioned solvent and non-solvent is 50-99.9wt%.
In a preferred embodiment, above-mentioned binder is selected from carboxymethyl cellulose, butadiene-styrene rubber, epoxy resin, polyacrylic acid
One of ester and their derivative are a variety of.
In a preferred embodiment, above-mentioned surfactant is in ethylene oxide polymer, polyethers and fluoropolymer
It is one or more.
In a preferred embodiment, the content of above-mentioned binder is 0.5-10wt%, above-mentioned table in above-mentioned polymer-coated layer
The content of face activating agent is 0.05-5wt%.
The coating method of coating fluid in above-mentioned steps (b) is not particularly limited, as long as coating fluid can be made to be uniformly coated on
Any coating method on porous membrane substrate surface is all suitable for.In a preferred embodiment, in above-mentioned steps (b), above-mentioned coating fluid
Coating method is selected from one of scraper for coating method, Meyer stick rubbing method, intaglio plate roller coating method and dip-coating or a variety of.
In a preferred embodiment, in above-mentioned steps (c), above-mentioned drying is to spontaneously dry or dry.
In a preferred embodiment, drying need to carry out in the environment of certain temperature and humidity, so that non-solvent is volatilized step by step, obtain
To the coating diaphragm with hierarchical porous structure.
In a preferred embodiment, the temperature of above-mentioned natural drying is 15 DEG C -35 DEG C；The temperature of above-mentioned drying is 50 DEG C -90
DEG C, preferably 70 DEG C.
In a preferred embodiment, the envionmental humidity of above-mentioned drying is 20-95%.
According to the third aspect, prepared by the coating diaphragm with hierarchical porous structure that first aspect is provided in a kind of embodiment
Purposes in the diaphragm of lithium ion battery.
The hierarchical porous structure at least two apertures is distributed on the polymer-coated layer of coating diaphragm of the invention.It is prepared
In method, after non-solvent is added in coating fluid, since polymer does not dissolve in non-solvent, in the perforated membrane for being coated with coating fluid
In substrate drying process, non-solvent can volatilize together with solvent, and solvent position to be formed as solvent volatilizees in coating fluid
Polymer supports, non-solvent position form pore structure with volatilization, eventually form porous coating diaphragm；Non-solvent with it is molten
The difference (Δ) of solubility parameter between agent is different, and the pore size of the porous coating diaphragm of formation is not also identical.The present invention
Porous coating diaphragm during the preparation process, non-solvent has at least two, and the solubility parameter between non-solvent and solvent
Difference (Δ) distribution gradient, in the drying process, different non-solvents will form various sizes of hole, to obtain with more
The coating diaphragm of grade pore structure.This hierarchical porous structure porosity with higher is conducive to diaphragm imbibition and protects liquid rate and ion
The raising of conductivity.
Specific embodiment
Below by specific embodiment, invention is further described in detail.Below in an example, many details
Description is in order to enable the application can be better understood.However, those skilled in the art can recognize without lifting an eyebrow,
Middle Partial Feature is dispensed in varied situations, or can be substituted by other materials, method.
It is formed respectively in addition, feature described in this description, operation or feature can combine in any suitable way
Kind embodiment.Meanwhile each step in method description or movement can also can be aobvious and easy according to those skilled in the art institute
The mode carry out sequence exchange or adjustment seen.Therefore, the various sequences in specification are intended merely to clearly describe some implementation
Example, is not meant to be necessary sequence, wherein some sequentially must comply with unless otherwise indicated.
Firstly, providing a kind of coating diaphragm with hierarchical porous structure, including perforated membrane in a kind of embodiment of the invention
Substrate and polymer-coated layer coated on above-mentioned at least one surface of porous membrane substrate are distributed on above-mentioned polymer-coated layer
The hierarchical porous structure at least two apertures.
Preferably, porous membrane substrate is selected from polyolefin single or multilayer porous film, polyester perforated membrane, polyamides
One of imines perforated membrane and polyamide perforated membrane are a variety of.The thickness of porous membrane substrate can be 5-30 μm, such as 6 μm, 8
μm, 10 μm, 15 μm, 20 μm, 22 μm, 25 μm, 20 μm or 30 μm, porosity ranges can be 30%-90%, for example, 35%,
40%, 50%, 60%, 70%, 80%, 85% or 88%, pore diameter range can be 0.005-0.20 μm, such as 0.006 μm,
0.01 μm, 0.02 μm, 0.05 μm, 0.1 μm, 0.12 μm, 0.15 μm, 0.18 μm or 0.19 μm.Polymer in polymer-coated layer
Can be selected from copolymer or homopolymer, such as polyacrylonitrile, polymethacrylates, polyvinylpyrrolidone, Kynoar,
One of Kynoar-hexafluoropropene, polyvinyl acetate and polyethylene glycol oxide are a variety of.
Preferably, polymer-coated layer is by containing polymer, binder, surfactant, solvent and extremely
The coating liquid of few two kinds of non-solvents is at least one surface of porous membrane substrate and dry formation, and wherein solvent is solvable depolymerization
Close the solvent of object；Non-solvent be the solvent of lean solvent, such as methanol, ethyl alcohol, normal propyl alcohol, isopropanol, fourth relative to polymer
Alcohol, propylene glycol, tripropylene glycol, water, benzene,toluene,xylene, n-hexane, hexamethylene, ethylene carbonate, propene carbonate or neighbour
Phthalic acid ester etc..Solvent can be selected from N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, tetrahydrofuran, acetone, first and second
Ketone, N-Methyl pyrrolidone, N, N, N ', N '-tetramethylurea, dimethyl sulfoxide, triethyl phosphate, n-butyl acetate, cyclohexanone,
Diacetone alcohol and butyrolactone.In coating fluid solid content be 1-25wt%, such as 2wt%, 4wt%, 6wt%, 8wt%, 10wt%,
12wt%, 15wt%, 18wt%, 20wt%, 22wt% or 25wt% etc..The ratio of solvent and non-solvent can be 50-
99.9wt%, for example, 52%, 55%, 56%, 58%, 60%, 70%, 80%, 85%, 88%, 90%, 92%, 95%,
98%, 99% or 99.5% etc..Binder can selected from carboxymethyl cellulose, butadiene-styrene rubber, epoxy resin, polyacrylate and
One of their derivative is a variety of.Surfactant can be selected from ethylene oxide polymer, polyethers and fluoropolymer
One of object is a variety of.The content of above-mentioned binder can be 0.5-10wt% in polymer-coated layer, such as 0.6wt%,
1wt%, 2wt%, 4wt%, 5wt%, 6wt%, 8wt%, 9wt%, 9.5wt% or 9.8wt%.The content of surfactant can
To be 0.05-5wt%, 0.05wt%, 0.06wt%, 0.1wt%, 0.2wt%, 0.4wt%, 0.8wt%, 1wt%, 2wt%,
3wt%, 3.5wt%, 4wt%, 4.5wt% or 4.8wt% etc..
Secondly, providing a kind of side of coating diaphragm prepared with hierarchical porous structure in another embodiment of the invention
Method, comprising:
(a) provide containing polymer, binder, surfactant, solvent and at least two non-solvents coating fluid, wherein
Above-mentioned solvent is the solvent that can dissolve above-mentioned polymer；Above-mentioned non-solvent is the solvent for being lean solvent relative to above-mentioned polymer；
(b) by above-mentioned coating liquid at least one surface of porous membrane substrate；With
(c) drying at least one surface of above-mentioned porous membrane substrate of above-mentioned coating fluid is made to form polymer-coated layer, on
State the hierarchical porous structure that at least two apertures are distributed on polymer-coated layer.
Preferably, porous membrane substrate is selected from polyolefin single or multilayer porous film, polyester perforated membrane, polyamides
One of imines perforated membrane and polyamide perforated membrane are a variety of.The thickness of porous membrane substrate can be 5-30 μm, porosity model
It encloses and can be 30%-90%, pore diameter range can be 0.005-0.20 μm.Polymer is selected from copolymer and/or homopolymer, such as
Polyacrylonitrile, polymethacrylates, polyvinylpyrrolidone, Kynoar, Kynoar-hexafluoropropene, poly-vinegar acid
One of vinyl acetate and polyethylene glycol oxide are a variety of.Non-solvent can selected from methanol, ethyl alcohol, normal propyl alcohol, isopropanol, butanol,
Propylene glycol, tripropylene glycol, water, benzene,toluene,xylene, n-hexane, hexamethylene, ethylene carbonate, propene carbonate and adjacent benzene two
Formic acid esters.Solvent can be selected from N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, tetrahydrofuran, acetone, methyl ethyl ketone, N-
Methyl pyrrolidone, N, N, N ', N '-tetramethylurea, dimethyl sulfoxide, triethyl phosphate, n-butyl acetate, cyclohexanone, dipropyl
Keto-alcohol and butyrolactone.It should be noted that the difference of the solubility parameter between two or more different non-solvents and solvent
(Δ) distribution gradient.Solid content can be 1-25wt% in coating fluid.The ratio of solvent and non-solvent can be 50-
99.9wt%.Binder can be selected from carboxymethyl cellulose, butadiene-styrene rubber, epoxy resin, polyacrylate and their derivative
One of object is a variety of.Surfactant can be selected from one of ethylene oxide polymer, polyethers and fluoropolymer
Or it is a variety of.The content of above-mentioned binder can be 0.5-10wt% in polymer-coated layer, and the content of surfactant can be
0.05-5wt%.
The coating method of coating fluid in step (b) is not particularly limited, as long as it is porous that coating fluid can be made to be uniformly coated on
Any coating method on film base material surface is all suitable for.Preferably, in step (b), the coating side of above-mentioned coating fluid
Formula is selected from one of scraper for coating method, Meyer stick rubbing method, intaglio plate roller coating method and dip-coating or a variety of.Drying need to be in certain temperature
It is carried out in degree and the environment of humidity, so that non-solvent is volatilized step by step, obtain the coating diaphragm with hierarchical porous structure.In step (c),
Drying can be natural drying or drying.The temperature of natural drying can be 15 DEG C -35 DEG C, the temperature of drying can be 50 DEG C -
90 DEG C, preferably 70 DEG C.Dry envionmental humidity can be 20-95%.
In addition, prepared by the coating diaphragm with hierarchical porous structure for providing first aspect in a kind of embodiment of the invention
Purposes in the diaphragm of lithium ion battery.
Below by way of specific embodiment and the comparative example technical solution that the present invention will be described in detail, it is to be appreciated that these are implemented
Example and comparative example are merely exemplary, and should not be understood as limiting the scope of the invention.
Embodiment 1
The polymer of the polymer-coated layer of the present embodiment is Kynoar, and binder is carboxymethyl cellulose, surface
Activating agent is polyethylene oxide, and solvent is acetone, and non-solvent is ethyl alcohol and toluene.By polymer, binder, surfactant,
Solvent, non-solvent carry out being mixed with coating fluid according to weight ratio 9:0.9:0.1:82:8.
The porous membrane substrate that the present embodiment uses for Shenzhen Zhong Xing innovative material Technology Co., Ltd. prepare with a thickness of 16 μ
The single layer PP film of m, after preparing coating fluid, using the method for dip-coating by coating liquid on two surfaces of PP film.It applies
Covering speed is 20m/min, and drying temperature is 70 DEG C, and environment temperature is 22 DEG C, humidity 50%RH.
Using the conventional test manner of this field, the coating diaphragm manufactured in the present embodiment with hierarchical porous structure is carried out
Porosity, imbibition protect the detection such as liquid rate, ionic conductivity.
Embodiment 2
The polymer of the polymer-coated layer of the present embodiment is Kynoar, and binder is butadiene-styrene rubber, surface-active
Agent is polyethylene oxide, and solvent is acetone, and non-solvent is water and toluene.By polymer, binder, surfactant, solvent, non-
Solvent carries out being mixed with coating fluid according to weight ratio 12:0.8:0.2:79:8.
The porous membrane substrate that the present embodiment uses for Shenzhen Zhong Xing innovative material Technology Co., Ltd. prepare with a thickness of 16 μ
The single layer PP film of m, after preparing coating fluid, using the method for dip-coating by coating liquid on two surfaces of PP film.It applies
Covering speed is 20m/min, and drying temperature is 70 DEG C, and environment temperature is 22 DEG C, humidity 50%RH.
Using the conventional test manner of this field, the coating diaphragm manufactured in the present embodiment with hierarchical porous structure is carried out
Porosity, imbibition protect the detection such as liquid rate, ionic conductivity.
Embodiment 3
The polymer of the polymer-coated layer of the present embodiment is polymethacrylates, and binder is carboxymethyl cellulose,
Surfactant is polyethylene oxide, and solvent is N-Methyl pyrrolidone, and non-solvent is ethyl alcohol and n-hexane.By polymer, glue
Knot agent, surfactant, solvent, non-solvent carry out being mixed with coating fluid according to weight ratio 15:0.9:0.1:77:7.
The porous membrane substrate that the present embodiment uses for Shenzhen Zhong Xing innovative material Technology Co., Ltd. prepare with a thickness of 14 μ
The single layer PP film of m, after preparing coating fluid, using the method for dip-coating by coating liquid on two surfaces of PP film.It applies
Covering speed is 20m/min, and drying temperature is 70 DEG C, and environment temperature is 20 DEG C, humidity 48%RH.
Using the conventional test manner of this field, the coating diaphragm manufactured in the present embodiment with hierarchical porous structure is carried out
Porosity, imbibition protect the detection such as liquid rate, ionic conductivity.
Comparative example 1
The polymer of the polymer-coated layer of this comparative example is Kynoar, and binder is carboxymethyl cellulose, surface
Activating agent is polyethylene oxide, and solvent is acetone, and non-solvent is ethyl alcohol.By polymer, binder, surfactant, solvent, non-
Solvent carries out being mixed with coating fluid according to weight ratio 9:0.9:0.1:82:8.
The porous membrane substrate that this comparative example uses for Shenzhen Zhong Xing innovative material Technology Co., Ltd. prepare with a thickness of 16 μ
The single layer PP film of m, after preparing coating fluid, using the method for dip-coating by coating liquid on two surfaces of PP film.It applies
Covering speed is 20m/min, and drying temperature is 70 DEG C, and environment temperature is 22 DEG C, humidity 50%RH.
Same as Example 1 to the detection project and detection method of the coating diaphragm of this comparative example preparation, test result is such as
Shown in table 1.
The test result of the diaphragm of 1 embodiment and comparative example of table preparation
By above-mentioned testing result it is found that the hole of the coating diaphragm with hierarchical porous structure with two kinds of non-solvent preparations
Rate, imbibition rate protect liquid rate and ionic conductivity obviously higher than the coating diaphragm prepared with a kind of non-solvent, and liquid is protected in diaphragm imbibition
The raising of rate and ionic conductivity facilitates the promotion of battery cycle life.
Use above specific case is illustrated the present invention, is merely used to help understand the present invention, not to limit
The system present invention.For those skilled in the art, according to the thought of the present invention, can also make several simple
It deduces, deform or replaces.
Claims (10)
1. a kind of coating diaphragm with hierarchical porous structure, which is characterized in that the coating diaphragm includes porous membrane substrate and painting
It is overlying on the polymer-coated layer at least one surface of porous membrane substrate, is distributed at least two on the polymer-coated layer
The hierarchical porous structure in aperture.
2. coating diaphragm according to claim 1, which is characterized in that the porous membrane substrate is selected from polyolefin single or more
One of layer perforated membrane, polyester perforated membrane, polyimide porous membrane and polyamide perforated membrane are a variety of；
Preferably, the porous membrane substrate with a thickness of 5-30 μm, porosity ranges 30%-90%, pore diameter range 0.005-
0.20μm。
3. coating diaphragm according to claim 1, which is characterized in that polymer is selected from copolymerization in the polymer-coated layer
Object and/or homopolymer；
Preferably, polymer is selected from polyacrylonitrile, polymethacrylates, polyvinylpyrrolidine in the polymer-coated layer
One of ketone, Kynoar, Kynoar-hexafluoropropene, polyvinyl acetate and polyethylene glycol oxide are a variety of.
4. coating diaphragm according to claim 1, which is characterized in that the polymer-coated layer is by containing polymer, gluing
The coating liquid of agent, surfactant, solvent and at least two non-solvents is tied at least one surface of the porous membrane substrate
And dry formation, wherein the solvent is the solvent that can dissolve the polymer；The non-solvent is relative to the polymer
For the solvent of lean solvent.
5. coating diaphragm according to claim 4, which is characterized in that the non-solvent be selected from methanol, ethyl alcohol, normal propyl alcohol,
Isopropanol, butanol, propylene glycol, tripropylene glycol, water, benzene,toluene,xylene, n-hexane, hexamethylene, ethylene carbonate, carbonic acid third
Enester and phthalic acid ester；
Preferably, the solvent is selected from n,N-Dimethylformamide, n,N-dimethylacetamide, tetrahydrofuran, acetone, first and second
Ketone, N-Methyl pyrrolidone, N, N, N ', N '-tetramethylurea, dimethyl sulfoxide, triethyl phosphate, n-butyl acetate, cyclohexanone,
Diacetone alcohol and butyrolactone；
Preferably, solid content is 1-25wt% in the coating fluid；
Preferably, the ratio of the solvent and non-solvent is 50-99.9wt%；
Preferably, the binder be selected from carboxymethyl cellulose, butadiene-styrene rubber, epoxy resin, polyacrylate and they spread out
One of biology is a variety of；
Preferably, the surfactant is selected from one of ethylene oxide polymer, polyethers and fluoropolymer or a variety of；
Preferably, the content of binder described in the polymer-coated layer is 0.5-10wt%, the content of the surfactant
For 0.05-5wt%.
6. a kind of method of the coating diaphragm prepared with hierarchical porous structure, which is characterized in that the described method includes:
(a) provide containing polymer, binder, surfactant, solvent and at least two non-solvents coating fluid, wherein described
Solvent is the solvent that can dissolve the polymer；The non-solvent is the solvent for being lean solvent relative to the polymer；
(b) by the coating liquid at least one surface of porous membrane substrate；With
(c) coating fluid drying at least one surface of the porous membrane substrate is made to form polymer-coated layer, it is described poly-
Close the hierarchical porous structure that at least two apertures are distributed on object coat.
7. according to the method described in claim 6, it is characterized in that, the porous membrane substrate is selected from polyolefin single or multilayer is more
One of pore membrane, polyester perforated membrane, polyimide porous membrane and polyamide perforated membrane are a variety of；
Preferably, the porous membrane substrate with a thickness of 5-30 μm, porosity ranges 30%-90%, pore diameter range 0.005-
0.20μm；
Preferably, the polymer is selected from copolymer and/or homopolymer；
Preferably, the polymer is selected from polyacrylonitrile, polymethacrylates, polyvinylpyrrolidone, Kynoar, gathers
One of biasfluoroethylene-hexafluoropropylene, polyvinyl acetate and polyethylene glycol oxide are a variety of；
Preferably, the non-solvent be selected from methanol, ethyl alcohol, normal propyl alcohol, isopropanol, butanol, propylene glycol, tripropylene glycol, water, benzene,
Toluene, dimethylbenzene, n-hexane, hexamethylene, ethylene carbonate, propene carbonate and phthalic acid ester；
Preferably, the solvent is selected from n,N-Dimethylformamide, n,N-dimethylacetamide, tetrahydrofuran, acetone, first and second
Ketone, N-Methyl pyrrolidone, N, N, N ', N '-tetramethylurea, dimethyl sulfoxide, triethyl phosphate, n-butyl acetate, cyclohexanone,
Diacetone alcohol and butyrolactone；
Preferably, solid content is 1-25wt% in the coating fluid；
Preferably, the ratio of the solvent and non-solvent is 50-99.9wt%；
Preferably, the binder be selected from carboxymethyl cellulose, butadiene-styrene rubber, epoxy resin, polyacrylate and they spread out
One of biology is a variety of；
Preferably, the surfactant is selected from one of ethylene oxide polymer, polyethers and fluoropolymer or a variety of；
Preferably, the content of binder described in the polymer-coated layer is 0.5-10wt%, the content of the surfactant
For 0.05-5wt%.
8. according to the method described in claim 6, it is characterized in that, the coating method of the coating fluid selects in the step (b)
From one of scraper for coating method, Meyer stick rubbing method, intaglio plate roller coating method and dip-coating or a variety of.
9. according to the method described in claim 6, it is characterized in that, the drying is to spontaneously dry or dry in the step (c)
It is dry；
Preferably, the temperature of the natural drying is 15 DEG C -35 DEG C；The temperature of the drying is 50 DEG C -90 DEG C, preferably 70 DEG C；
Preferably, the envionmental humidity of the drying is 20-95%.
10. use of the coating diaphragm described in claim 1 to 5 with hierarchical porous structure in the diaphragm for preparing lithium ion battery
On the way.
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| CN110344127A (en) * | 2019-06-23 | 2019-10-18 | 浙江理工大学 | A kind of centrifugal spinning preparation method of porous Kynoar/polyethylene glycol oxide micro/nano-fibre |
| CN111341975A (en) * | 2020-03-16 | 2020-06-26 | 四川优源新能源有限公司 | Diaphragm for high-efficiency lithium ion secondary battery and preparation method thereof |
| CN111732754A (en) * | 2020-07-02 | 2020-10-02 | 四川大学 | Three-dimensional scaffold with multi-level holes, three-dimensional functional scaffold and preparation method thereof |
| CN111842072A (en) * | 2020-07-31 | 2020-10-30 | 中国人民解放军国防科技大学 | Application of hydrophobic heat-insulating and cooling film |
| CN112259927A (en) * | 2020-10-23 | 2021-01-22 | 青岛大学 | Lithium-sulfur battery diaphragm compounded with redox graphene and preparation method thereof |
| CN117954781A (en) * | 2023-12-29 | 2024-04-30 | 安徽壹石通材料科学研究院有限公司 | Lithium ion battery diaphragm, preparation method thereof and lithium ion battery |
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| CN111341975A (en) * | 2020-03-16 | 2020-06-26 | 四川优源新能源有限公司 | Diaphragm for high-efficiency lithium ion secondary battery and preparation method thereof |
| CN111341975B (en) * | 2020-03-16 | 2022-11-15 | 四川优源新能源有限公司 | Diaphragm for high-efficiency lithium ion secondary battery and preparation method thereof |
| CN111732754A (en) * | 2020-07-02 | 2020-10-02 | 四川大学 | Three-dimensional scaffold with multi-level holes, three-dimensional functional scaffold and preparation method thereof |
| CN111732754B (en) * | 2020-07-02 | 2021-04-23 | 四川大学 | Three-dimensional scaffold with multi-level holes, three-dimensional functional scaffold and preparation method thereof |
| CN111842072A (en) * | 2020-07-31 | 2020-10-30 | 中国人民解放军国防科技大学 | Application of hydrophobic heat-insulating and cooling film |
| CN112259927A (en) * | 2020-10-23 | 2021-01-22 | 青岛大学 | Lithium-sulfur battery diaphragm compounded with redox graphene and preparation method thereof |
| CN117954781A (en) * | 2023-12-29 | 2024-04-30 | 安徽壹石通材料科学研究院有限公司 | Lithium ion battery diaphragm, preparation method thereof and lithium ion battery |
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