CN110379979A - Organic composite diaphragm and its preparation method and application - Google Patents
Organic composite diaphragm and its preparation method and application Download PDFInfo
- Publication number
- CN110379979A CN110379979A CN201810330871.8A CN201810330871A CN110379979A CN 110379979 A CN110379979 A CN 110379979A CN 201810330871 A CN201810330871 A CN 201810330871A CN 110379979 A CN110379979 A CN 110379979A
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- CN
- China
- Prior art keywords
- fibrous layer
- organic composite
- composite diaphragm
- polymer
- ceramic nanoparticle
- Prior art date
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- Pending
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- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 238000000576 coating method Methods 0.000 claims abstract description 45
- 239000000919 ceramic Substances 0.000 claims abstract description 44
- 229920000642 polymer Polymers 0.000 claims abstract description 44
- 239000011248 coating agent Substances 0.000 claims abstract description 41
- 239000002105 nanoparticle Substances 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 24
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- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 17
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- 239000002002 slurry Substances 0.000 claims abstract description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 11
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- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 4
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—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
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
-
- 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
- H01M50/463—Separators, membranes or diaphragms characterised by their shape
-
- 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
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Abstract
The present invention relates to field of batteries, a kind of organic composite diaphragm and its preparation method and application is disclosed.The organic composite diaphragm includes: fibrous layer and the hydrophilic coating coated on the fibrous layer unilateral or bilateral, and the fibrous layer is formed by the mixture of ceramic nanoparticle and polymer through electrostatic spinning, the hydrophilic coating with a thickness of 0.3-4 μm.The invention also discloses a kind of methods for preparing organic composite diaphragm and organic composite diaphragm obtained by this method, comprising: the polymer solution for being suspended with ceramic nanoparticle is carried out electrostatic spinning, obtains the fibrous layer that load has ceramic nanoparticle；Aqueous slurry containing hydroaropic substance is coated on to the unilateral or bilateral of fibrous layer, to form hydrophilic coating.The invention also discloses the application of above-mentioned organic composite diaphragm in a lithium ion secondary battery.Organic composite diaphragm of the invention has high porosity, high-liquid absorbing rate and good heat resistance, and can fall off to avoid ceramic nanoparticle.
Description
Technical field
The present invention relates to field of batteries, and in particular, to a kind of organic composite diaphragm and its preparation method and application.
Background technique
Lithium ion battery under conditions of high current, easily leads to a large amount of Li dendrites, punctures battery diaphragm, causes inside battery short
Pass sends out security risk.The lithium ion battery separator of commercial applications is polypropylene (PP) and polyethylene (PE) diaphragm at present, this
Kind of diaphragm have now there are two outstanding problem, one is melting point polymer is generally lower, PE fusing point is 135 DEG C, and PP fusing point is 165
℃；The second is since polyalkene diaphragm itself has hydrophobicity, and often contain a high proportion of polar solvent in electrolyte, diaphragm
Wellability and liquid retention it is weaker.The diaphragm can not fully meet the requirement in increasingly developed power battery market.
The security performance of lithium ion battery separator is that diaphragm is required to have good thermal dimensional stability, in certain high temperature ring
Without obvious deformation under border；With preferable hot closed pore performance, hot closed pore occurs before battery short circuit and without obvious mechanical strength
Loss, thermally safe temperature with higher.Since power battery has higher operating temperature, more complex dynamic row environment can
Explosion, burning etc. can occur under unconventional state, i.e., abnormal charge and discharge state, the abnormal heated abuse with mechanical condition, therefore dynamic
The thermal safety of power lithium ion battery is particularly important.
In order to solve this problem, following several method is mainly taken at present: first is that coating one layer of ceramics in membrane surface
Film, as CN102516585A discloses a kind of fibrination pore membrane that can be used for lithium ion secondary battery membrane, feature packet
It includes in the both side surface coating sodium alginate of cellulose electrostatic spinning non-woven membrane, fluoropolymer, poly(aryl ether ketone), polyamides Asia
Amine, poly- norborneol be dilute and/or inorganic nano-particle.However, the ceramic particle for being coated in membrane surface is easy to fall off, especially exist
In electric core winding technique, ceramic powder, which falls off, will lead to a series of problems, such as: the ceramic particle to fall off causes membrane properties uneven
One, influence battery performance consistency；The ceramic particle to fall off is that lithium ion mobility increases resistance in electrolyte, and it is fast to be unfavorable for fast charge
It puts；The ceramic particle to fall off can potentially migrate into positive and negative pole surface, influence lithium ion insertion and abjection.Second is that using PP, PE or
The non-woven membrane of its composite membrane and high-fire resistance carries out hot-pressing processing, as disclosed a kind of lithium battery nanometer in CN103085442A
The preparation method of fibre diaphragm specifically includes polyethylene terephthalate (PET) electrospinning film and PP non-woven fabrics carrying out roll-in
It is compound；Such method preparation process is cumbersome, and non-woven fabrics porosity can not control well, and the uniformity of diaphragm cannot be guaranteed,
It is at high cost.
Summary of the invention
The purpose of the invention is to overcome the problems, such as that the existing membrane properties of the prior art are poor, provide a kind of organic
Composite diaphragm and its preparation method and application.
To achieve the goals above, one aspect of the present invention provides a kind of organic composite diaphragm, the organic composite diaphragm packet
Include: fibrous layer and the hydrophilic coating coated on the fibrous layer unilateral or bilateral, the fibrous layer by ceramic nanoparticle with
The mixture of polymer is formed through electrostatic spinning, the hydrophilic coating with a thickness of 0.3-4 μm.
Second aspect, the present invention provides a kind of methods for preparing organic composite diaphragm, this method comprises:
(1) polymer solution for being suspended with ceramic nanoparticle is subjected to electrostatic spinning, obtaining load has ceramic nano grain
The fibrous layer of son；
(2) aqueous slurry containing hydroaropic substance is coated on to the unilateral or bilateral of fibrous layer, to form hydrophily
Coating, the hydrophilic coating that the thickness of coating makes with a thickness of 0.3-4 μm.
The third aspect, the present invention provides organic composite diaphragms prepared by the above method.
Fourth aspect, the present invention provides the application of above-mentioned organic composite diaphragm in a lithium ion secondary battery.
Through the above technical solutions, organic composite diaphragm of the invention has high porosity, high-liquid absorbing rate and good resistance to
It is hot；In addition, hydrophilic coating coats ceramic nanoparticle wherein it is possible to which ceramic nanoparticle is avoided to fall off a system of generation
Column problem.Moreover, the formation of hydrophilic coating is without acetone (a kind of toxogen material processed), N-Methyl pyrrolidone (NMP) etc.
Oiliness coats solvent, reduces the insecurity of production.In addition, hydrophilic coating is not easy to plug fiber compared to hydrophobic coating
The pore structure of layer especially increases the effective use space of battery plus-negative plate material, changes to be conducive to the maintenance of battery performance
Kind battery capacity and performance.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
Organic composite diaphragm provided by the invention includes: fibrous layer and coated on the hydrophilic of the fibrous layer unilateral or bilateral
Property coating, the fibrous layer formed by the mixture of ceramic nanoparticle and polymer through electrostatic spinning, and the hydrophily applies
Layer with a thickness of 0.3-4 μm, preferably 0.5-2 μm.Wherein, hydrophilic when the bilateral of fibrous layer is coated with hydrophilic coating
The thickness of property coating refers to the thickness of one-sided coatings.
In the present invention, as long as fibrous layer is formed together using ceramic nanoparticle and polymer, to the thickness of fibrous layer
Degree etc. does not require particularly, and the thickness of the fibrous layer is preferably 5-40 μm, and preferably 20-35 μm.
Preferably, the weight ratio in fibrous layer between ceramic nanoparticle and polymer is 1:5-20, more preferably 1:10-
20.It was found by the inventors of the present invention that institute can further be improved by loading upper specific quantity ceramic nanoparticle when forming fibrous layer
Obtain the performance of diaphragm.
In the present invention, the ceramic nanoparticle can be the conventional selection of this field, for example, the oxidation of Group IIA metal
The oxidation of object, the sulfate of Group IIA metal, the hydroxide of Group IIA metal, the oxide of Group IVB metal, Group IIIA metal
At least one of object, hydrated alumina and silica.The partial size of the ceramic nanoparticle is preferably 50-500nm.It is more excellent
Selection of land, the ceramic nanoparticle be selected from aluminum oxide, magnesia, silica, zirconium dioxide, titanium dioxide, boehmite,
At least one of barium sulfate and magnesium hydroxide.In the present invention, " partial size " is the equal average grain diameter of index.
In the present invention, the specific type for the polymer for forming fibrous layer is not required particularly, as long as institute can be supported
State polymer coating.But under preferable case, the polymer for forming fibrous layer is selected from substitution or unsubstituted C2-6Alkene
At least one of polymer, polyester, polyimides and polyamide, wherein replace C2-6The group of alkene is selected from halogen (especially
It is fluorine) and/or cyano.C2-6Alkene is further preferably selected from ethylene or propylene.It is highly preferred that forming the polymer choosing of fibrous layer
From polypropylene, polyester (such as polyethylene terephthalate or polymethyl methacrylate), polyimides, polyamide, polyethylene,
At least one of polyacrylonitrile, Kynoar, vinylidene and hexafluoropropylene copolymer.
In the present invention, the hydrophilic coating can be only present in the side of the fibrous layer, can also exist on fiber
The two sides of layer, and can be formed by the common hydroaropic substance in this field, when the polymer for forming the fibrous layer is hydrophily
When substance, the hydroaropic substance for forming hydrophilic coating can be identical or different with the polymer of formation fibrous layer.In the present invention,
Hydroaropic substance refers to the molecule with polar group, has affinity to water, can attract hydrone (and be not dissolved in water,
Solubility at 20 DEG C in water is less than 0.01g/100g water) substance.
Under preferable case, the hydrophilic coating is by hydrophilic in aqueous binder, surfactant and thickener
Property substance is formed.Aqueous binder, surfactant and thickener weight ratio are preferably (10-65): (1-5): 1.
The aqueous binder is the bonding agent referred to using water as solvent, preferably polysaccharide and its derivative, height
At least one of molecule lotion, natural gum and its derivative and aqueous chain macromolecule.More carbohydrates and their derivatives are preferred
For at least one of carboxymethyl cellulose, chitosan, lignin, cyclodextrin and sodium alginate.The macromolecule emulsion is preferred
For in styrene-butadiene latex, styrene-acrylic latex, polymethyl methacrylate, polyethyl acrylate, acrylonitrile multiple copolymer and polyurethane
At least one.The natural gum and its derivative are preferably at least one in gelatin, xanthan gum, Arabic gum and guar gum
Kind.The water solubility chain macromolecule is preferably that polyvinyl alcohol, polyacrylate, polyamide and ethylene and vinyl acetate are total
At least one of polymers.
The surfactant can be various common surfactants, preferably nonionic surfactant, more excellent
It is selected as polyethylene glycol, perfluoroalkyl ethyoxyl ether alcohol, aliphatic amine polyoxyethylene ether, aliphatic acid polyethenoxy ether, polyoxyethylene alkane
At least one of base amide and fatty alcohol polyoxyethylene ether.
The thickener is the substance for referring to improve and increase bonding agent viscosity, preferably polyacrylic acid, poly- methyl
At least one of acrylic acid, sodium carboxymethylcellulose and poly- ethylacrylic acid.
According to a kind of particularly preferred embodiment, the hydrophilic coating is by aqueous binder, surfactant and increasing
Thick dosage form at, and the weight ratio of three be (10-65): (1-5): 1, the aqueous binder be selected from styrene-butadiene latex, polyvinyl alcohol,
At least one of acrylonitrile multiple copolymer, polyurethane and polyethyl acrylate, the surfactant are selected from perfluoroalkyl
Ethyoxyl ether alcohol and/or polyethylene glycol, the thickener are selected from sodium carboxymethylcellulose and/or polyacrylic acid.
The method provided by the invention for preparing organic composite diaphragm includes:
(1) polymer solution for being suspended with ceramic nanoparticle is subjected to electrostatic spinning, obtaining load has ceramic nano grain
The fibrous layer of son；
(2) aqueous slurry containing hydroaropic substance is coated on to the unilateral or bilateral of fibrous layer, to form hydrophily
Coating, the hydrophilic coating that the thickness of coating makes with a thickness of 0.3-4 μm, preferably 0.5-2 μm.It should be noted that
Thickness herein refers to the thickness of hydrophilic coating in final products (after removing solvent).When the bilateral of fibrous layer is coated with parent
When aqueous coating, the thickness of hydrophilic coating refers to the thickness of one-sided coatings.
According to the present invention it is possible to carry out electrostatic spinning according to conventional condition, but preferably, the condition of electrostatic spinning makes
The fibrous layer with a thickness of 5-40 μm (more preferably 20-35 μm), porosity is 30-90% (more preferably 55-75%).
It is further preferred that it is 12-30kV (more preferably 20-30kV) that the condition of electrostatic spinning, which includes: voltage, flow velocity is
3-10ml/h (more preferably 3-5ml/h), rotating receiver distance are 10-40cm (more preferably 20-30cm).
According to the present invention, in step (1), the weight ratio between polymer in ceramic nanoparticle and polymer solution is excellent
It is selected as 1:5-20, more preferably 1:10-20.
According to the present invention, the ceramic nanoparticle can be the conventional selection of this field, for example, the oxygen of Group IIA metal
The oxidation of compound, the sulfate of Group IIA metal, the hydroxide of Group IIA metal, the oxide of Group IVB metal, Group IIIA metal
At least one of object, hydrated alumina and silica.The partial size of the ceramic nanoparticle is preferably 50-500nm, more excellent
Selection of land, the ceramic nanoparticle be selected from aluminum oxide, magnesia, silica, zirconium dioxide, titanium dioxide, boehmite,
At least one of barium sulfate and magnesium hydroxide.
According to the present invention, the concentration of polymer in the polymer solution of step (1) is not particularly limited, for example, can
Think 5-30 weight %.In the present invention, in the absence of explanation to the contrary, the concentration of polymer solution refers to solution system
In, the weight of polymer accounts for the percentage of the total weight of polymer and solvent.
According to the preferred embodiment of the present invention, the polymer in the polymer solution of step (1) be selected from replace or not by
Substituted C2-6At least one of polymer, polyester, polyimides and polyamide of alkene, wherein replace C2-6The base of alkene
Group is selected from halogen (especially fluorine) and/or cyano.C2-6Alkene is further preferably selected from ethylene or propylene.It is highly preferred that step
(1) the polymer in polymer solution is selected from polypropylene, polyester (such as polyethylene terephthalate or poly-methyl methacrylate
Ester), polyimides, polyamide, polyethylene, polyacrylonitrile, Kynoar, in vinylidene and hexafluoropropylene copolymer extremely
Few one kind.
According to the present invention, in step (1), solvent used in the polymer solution can be commonly used in the art
Various organic solvents, it is sub- to be preferably selected from dimethylformamide (DMF), acetone, tetrahydrofuran, chloroform, methylene chloride, dimethyl
At least one of sulfone, N-Methyl pyrrolidone (NMP), trifluoroethanol and hexafluoroisopropanol.
According to the present invention, the content of hydroaropic substance in the aqueous slurry of step (2) is not particularly limited, for example,
It can be 1-10 weight %.
According to the present invention, the aqueous slurry can obtain as follows: hydroaropic substance is mixed to (mixing with water
The content of hydroaropic substance can be 1-10 weight % in object), it is heated to 40-80 DEG C and stirs evenly.
According to the present invention, when the polymer for forming the fibrous layer is hydroaropic substance, hydrophily is formed in step (2)
The hydroaropic substance of coating can be identical or different with the polymer of formation fibrous layer in step (1).It is according to the present invention preferred
Embodiment, hydroaropic substance used in step (2) are selected from aqueous binder, surfactant and thickener.Aqueous binder
The specific type and dosage of agent, surfactant and thickener are referred to foregoing teachings, and details are not described herein.
According to the present invention, in step (2), solvent used in the aqueous slurry is water, preferably deionized water.
According to the present invention, in step (2), the mode of the coating is not required particularly, it can be normal using this field
The various coating methods seen, such as spraying, blade coating, dip-coating or roller coating.
According to the present invention, it in order to obtain organic composite separator product, after step (2), can also be dried, it is dry
Mode or condition can be conventional selection, as long as removing residual solvent as far as possible, this will not be detailed here.
The present invention also provides organic composite diaphragms made from foregoing method.
In addition, the application the present invention also provides foregoing organic composite diaphragm in a lithium ion secondary battery.
The present invention will be described in detail by way of examples below.In following embodiment, slurry viscosity is viscous by Ubbelohde
Degree measures；Room temperature refers to about 25 DEG C of temperature；The thickness addressed in embodiment is the coating layer thickness for removing and measuring after solvent；
The weight average molecular weight of Kynoar is 60-100W, and producer A Kema, the trade mark is Kynar HSV9000；
The weight average molecular weight of Kynoar-hexafluoropropene (vinylidene and hexafluoropropylene copolymer) is 60-70W；Factory
Family is A Kema, trade mark SL-023；
The weight average molecular weight of polyacrylonitrile is 15W, and producer is lark prestige, product number 226749；
PET；Density is about 1.68g/ml, producer Sigma, product number 429252；
Styrene-butadiene latex: SBR1500,23 weight % of solid content, Lanzhou Petrochemical Company；
Acrylonitrile multiple copolymer: LA132,15 weight % of solid content, Chengdu Yindile Power Source Science and Technology Co., Ltd；
The weight average molecular weight of polyvinyl alcohol is 8.5-12.4W, degree of hydrolysis 87-89%；Producer is Sigma, product number
It is 363081；
Perfluoroalkyl ethyoxyl ether alcohol, pH 6-8, producer are Harbin Xue Jiafu chemistry of silicones Co., Ltd, trade mark S-
201；
Viscosity < 200mPas of polyurethane, producer are Wanhua Chemical Group Co., Ltd., trade mark Adwel
1650；
The viscosity of sodium carboxymethylcellulose is 800 centipoises, and producer is lark prestige, product number 241297；
The weight average molecular weight of polyethyl acrylate is 9.5W, producer Sigma, product number 181889；
The weight average molecular weight of polyethylene glycol is 20000, producer Sigma, product number 95172；
The weight average molecular weight of polyacrylic acid is 45W, producer Aldrich, product number 181285.
Embodiment 1
(1) Kynoar-hexafluoropropene 28g, aluminum oxide (partial size 150nm) 2.8g, DMF 132g are weighed,
NMP 47g is mixed, and is stirred at room temperature 12 hours and is obtained mixture one to homogeneous transparent；By mixture one voltage be 20kV,
Solution flow velocity is 5ml/h, and rotating receiver distance carries out electrostatic spinning under conditions of being 20cm, obtains comprising ceramic nanoparticle
Electrospun fibers film (i.e. fibrous layer)；The electrospun fibers film comprising ceramic nanoparticle with a thickness of 30 μm,
Porosity is 70%.
(2) styrene-butadiene latex 10g, sodium carboxymethylcellulose 0.2g, polyvinyl alcohol 1g, perfluoroalkyl ethyoxyl ether alcohol are weighed
0.2g, deionized water 100g mixing, are heated to 50 DEG C and stir evenly；Aqueous slurry is coated on by packet using plate gravure coating method
Electrospun fibers film two sides containing ceramic nanoparticle, application rate 20m/min form hydrophilic coating (bilateral thickness
Be 1 μm), in 60 DEG C of baking ovens dry 24 hours to remove residual solvent, obtain organic composite diaphragm.
Embodiment 2
(1) polyacrylonitrile 40g is weighed, titanium dioxide (partial size 100nm) 4g, DMF 150g, acetone 50g are mixed,
It is stirred at room temperature 12 hours and obtains mixture one to homogeneous transparent；By mixture one voltage be 25kV, solution flow velocity be 3ml/h,
Rotating receiver distance carries out electrostatic spinning under conditions of being 25cm, obtains the electrospun fibers comprising ceramic nanoparticle
Film；The electrospun fibers film comprising ceramic nanoparticle with a thickness of 20 μm, porosity 75%.
(2) acrylonitrile multiple copolymer 10g, polyurethane 0.5g, sodium carboxymethylcellulose 0.2g, perfluoroalkyl ethoxy are weighed
Base ether alcohol 0.3g, deionized water 90g mixing, is heated to 40 DEG C and stirs evenly；Using dip-coating formula coating method by aqueous slurry
The electrospun fibers film two sides comprising ceramic nanoparticle are coated on, (bilateral thickness is 2 μ to form hydrophilic coating
M), (60 DEG C, for 24 hours) are dried using baking oven, obtain organic composite diaphragm.
Embodiment 3
(1) polyacrylonitrile 20g, Kynoar-hexafluoropropene 20g, zirconium oxide (partial size 50nm) 2g, DMF are weighed
120g, tetrahydrofuran 50g are mixed, and are stirred at room temperature 12 hours and are obtained mixture one to homogeneous transparent；By mixture one in electricity
Pressure is 30kV, and solution flow velocity is 5ml/h, and rotating receiver distance carries out electrostatic spinning under conditions of being 30cm, obtains comprising pottery
The electrospun fibers film (i.e. fibrous layer) of porcelain nanoparticle；The thickness of the electrospun fibers film comprising ceramic nanoparticle
Degree is 35 μm, porosity 55%.
(2) polyethyl acrylate 5g, polyurethane 1g, polyvinyl alcohol 0.5g, polyethylene glycol 0.2g, polyacrylic acid are weighed
0.1g, perfluoroalkyl ethyoxyl ether alcohol 0.25g, deionized water 100g mixing, is heated to 60 DEG C and stirs evenly；It is applied using intaglio plate
Aqueous slurry is coated on the electrospun fibers film two sides comprising ceramic nanoparticle by mode for cloth, application rate 20m/min,
It is formed hydrophilic coating (bilateral thickness is 0.5 μm), has been obtained with removing residual solvent within drying 24 hours in 60 DEG C of baking ovens
Machine composite diaphragm,
Embodiment 4
Organic composite diaphragm is prepared according to the method for embodiment 1, unlike, the styrene-butadiene latex in step (2) is replaced
For etc. weight PET.
Embodiment 5
Organic composite diaphragm is prepared according to the method for embodiment 1, unlike, Kynoar-hexafluoro third in step (1)
The dosage of alkene is 20.8g, and the dosage of aluminum oxide is 10g.
Comparative example 1
Organic composite diaphragm is prepared according to the method for embodiment 1, unlike, aluminum oxide such as is replaced at the weight
Kynoar.
Comparative example 2
Organic composite diaphragm is prepared according to the method for embodiment 1, unlike, in step (2), when coating, bilateral thickness
It is 10 μm.
Comparative example 3
Organic composite diaphragm is prepared according to the method that embodiment 1 in CN103545472A is recorded.
Test case 1
The performance parameter of testing example and comparative example diaphragm obtained, it is shown that the specific test method is as follows, test knot
Fruit is as shown in table 1.
Thickness: thickness is tested using micrometer (0.01 millimeter of precision), arbitrarily takes 5 points on sample, and be averaged；
Porosity: diaphragm is immersed in n-butanol 2 hours, porosity (p) is then calculated according to formula:
Wherein, ρ1And ρ2It is the density of n-butanol and the dry density of diaphragm, m1And m2It is the quality of the n-butanol of diaphragm sucking
With the quality of diaphragm itself；
Imbibition rate: diaphragm is immersed in n-butanol 12 hours, imbibition rate (P) is then calculated according to formula:
Wherein, W2And W1It is the quality of the n-butanol of diaphragm sucking and the quality of diaphragm itself；
Percent thermal shrinkage: size percent thermal shrinkage is measured using baking oven, 150 DEG C of sample are heat-treated 2 hours, then according to formula
It calculates percent thermal shrinkage (δ):
Wherein, S1And S2It is the area of diaphragm heat treatment front and back；
Tensile strength: the tensile strength of diaphragm is tested using the plastic tensile experimental method of GB1040-79；
Conductivity: using electrochemical workstation measure diaphragm conductivity, the frequency range 0.001Hz-105Hz of test, so
Conductivity (σ) is calculated according to formula afterwards:
Wherein, σ is the conductivity (S/cm) of diaphragm, and d is the thickness (cm) of diaphragm, RbFor the bulk resistance (Ω) of diaphragm, A
Effective area (the cm contacted for diaphragm with electrode2)。
Table 1
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (11)
1. a kind of organic composite diaphragm, which is characterized in that the organic composite diaphragm include: fibrous layer and be coated on the fibrous layer
The hydrophilic coating of unilateral or bilateral, the fibrous layer by the mixture of ceramic nanoparticle and polymer through electrostatic spinning shape
At, the hydrophilic coating with a thickness of 0.3-4 μm.
2. organic composite diaphragm according to claim 1, wherein the fibrous layer with a thickness of 5-40 μm.
3. organic composite diaphragm according to claim 1 or 2, wherein in fibrous layer ceramic nanoparticle and polymer it
Between weight ratio be 1:5-20.
4. organic composite diaphragm according to claim 3, wherein the partial size of the ceramic nanoparticle is 50-500nm,
The ceramic nanoparticle be selected from the oxide of Group IIA metal, the sulfate of Group IIA metal, Group IIA metal hydroxide,
At least one of the oxide of Group IVB metal, the oxide of Group IIIA metal, hydrated alumina and silica, preferably
In aluminum oxide, magnesia, silica, zirconium dioxide, titanium dioxide, boehmite, barium sulfate and magnesium hydroxide at least
It is a kind of；
And/or the polymer of fibrous layer is formed selected from substitution or unsubstituted C2-6Polymer, polyester, the polyimides of alkene
At least one of with polyamide, replace C2-6The group of alkene is selected from halogen and/or cyano, preferably polypropylene, poly- to benzene two
Formic acid second diester, polyimides, polyamide, polyethylene, polyacrylonitrile, Kynoar, vinylidene and hexafluoropropene are copolymerized
At least one of object and polymethyl methacrylate；
And/or the hydrophilic coating is by the hydroaropic substance shape in aqueous binder, surfactant and thickener
At aqueous binder, surfactant and thickener weight ratio are preferably 10-65:1-5:1；The aqueous binder is preferably
At least one of more carbohydrates and their derivatives, macromolecule emulsion, natural gum and its derivative and aqueous chain macromolecule；It is described more
Carbohydrates and their derivative is preferably at least one of carboxymethyl cellulose, chitosan, lignin, cyclodextrin and sodium alginate；Institute
Stating macromolecule emulsion is preferably that styrene-butadiene latex, styrene-acrylic latex, polymethyl methacrylate, polyethyl acrylate, acrylonitrile are polynary
At least one of copolymer and polyurethane；The natural gum and its derivative are preferably gelatin, xanthan gum, Arabic gum and melon
At least one of your glue；The water solubility chain macromolecule is preferably polyvinyl alcohol, polyacrylate, polyamide, Yi Jiyi
At least one of alkene and acetate ethylene copolymer；The surfactant is preferably nonionic surfactant, more preferably
Polyethylene glycol, perfluoroalkyl ethyoxyl ether alcohol, aliphatic amine polyoxyethylene ether, aliphatic acid polyethenoxy ether, polyxyethylated acyl
At least one of amine and fatty alcohol polyoxyethylene ether；The thickener is polyacrylic acid, polymethylacrylic acid, carboxymethyl cellulose
At least one of plain sodium and poly- ethylacrylic acid.
5. a kind of method for preparing organic composite diaphragm, which is characterized in that this method comprises:
(1) polymer solution for being suspended with ceramic nanoparticle is subjected to electrostatic spinning, obtaining load has ceramic nanoparticle
Fibrous layer；
(2) aqueous slurry containing hydroaropic substance is coated on to the unilateral or bilateral of fibrous layer, so that hydrophilic coating is formed,
The hydrophilic coating that the thickness of coating makes with a thickness of 0.3-4 μm.
6. according to the method described in claim 5, wherein, the condition of electrostatic spinning make the fibrous layer with a thickness of 5-40 μ
M, porosity 30-90%；
The condition of electrostatic spinning includes: that voltage is 12-30kV, and flow velocity 3-10ml/h, rotating receiver distance is 10-40cm.
7. method according to claim 5 or 6, wherein in step (1), in ceramic nanoparticle and polymer solution
Weight ratio between polymer is 1:5-20.
8. according to the method described in claim 5, wherein, the concentration of polymer is 5-30 weight in the polymer solution of step (1)
Measure %；
And/or the content of hydroaropic substance is 1-10 weight % in the aqueous slurry of step (2).
9. the method according to claim 5 or 8, wherein the partial size of the ceramic nanoparticle is 50-500nm, the pottery
Porcelain nanoparticle is selected from the oxide of Group IIA metal, the sulfate of Group IIA metal, the hydroxide of Group IIA metal, Group IVB gold
At least one of the oxide of category, the oxide of Group IIIA metal, hydrated alumina and silica, preferably three oxidations two
At least one of aluminium, magnesia, silica, zirconium dioxide, titanium dioxide, boehmite, barium sulfate and magnesium hydroxide；
And/or the polymer in the polymer solution of step (1) is selected from substitution or unsubstituted C2-6The polymer of alkene gathers
At least one of ester, polyimides and polyamide replace C2-6The group of alkene be selected from halogen and/or cyano, preferably poly- third
Alkene, polyethylene terephthalate, polyimides, polyamide, polyethylene, polyacrylonitrile, Kynoar, vinylidene and six
At least one of fluoropropene copolymer and polymethyl methacrylate；
And/or in step (1), solvent used in the polymer solution is selected from dimethylformamide, acetone, tetrahydro furan
It mutters, at least one of chloroform, methylene chloride, dimethyl sulfoxide, N-Methyl pyrrolidone, trifluoroethanol and hexafluoroisopropanol；
And/or hydroaropic substance used in step (2) is selected from aqueous binder, surfactant and thickener；Aqueous binder
Agent, surfactant and thickener weight ratio are preferably 10-65:1-5:1；The aqueous binder is preferably polysaccharide and its derivative
At least one of object, macromolecule emulsion, natural gum and its derivative and aqueous chain macromolecule；More carbohydrates and their derivatives
Preferably at least one of carboxymethyl cellulose, chitosan, lignin, cyclodextrin and sodium alginate；The macromolecule emulsion
Preferably styrene-butadiene latex, styrene-acrylic latex, polymethyl methacrylate, polyethyl acrylate, acrylonitrile multiple copolymer and poly- ammonia
At least one of ester；The natural gum and its derivative be preferably in gelatin, xanthan gum, Arabic gum and guar gum at least
It is a kind of；The water solubility chain macromolecule is preferably polyvinyl alcohol, polyacrylate, polyamide and ethylene and vinyl acetate
At least one of copolymer；The surfactant is preferably nonionic surfactant, more preferably polyethylene glycol, perfluor
Alkyl ethoxy ether alcohol, aliphatic amine polyoxyethylene ether, aliphatic acid polyethenoxy ether, polyoxyethylene alkylamide and fatty alcohol polyoxy
At least one of vinethene；The thickener is polyacrylic acid, polymethylacrylic acid, sodium carboxymethylcellulose and poly- ethyl third
At least one of olefin(e) acid；
And/or in step (2), solvent used in the aqueous slurry is deionized water.
10. organic composite diaphragm made from method described in any one of claim 5-9.
11. the application of organic composite diaphragm in a lithium ion secondary battery described in any one of claim 1-4 and 10.
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| CN113300004A (en) * | 2020-02-21 | 2021-08-24 | 香港中文大学 | Molecular-crowding electrolyte, battery comprising same, and method for manufacturing same |
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