CN110453372A - A kind of composite diaphragm and its preparation method and application - Google Patents
A kind of composite diaphragm and its preparation method and application Download PDFInfo
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- CN110453372A CN110453372A CN201910708924.XA CN201910708924A CN110453372A CN 110453372 A CN110453372 A CN 110453372A CN 201910708924 A CN201910708924 A CN 201910708924A CN 110453372 A CN110453372 A CN 110453372A
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0069—Electro-spinning characterised by the electro-spinning apparatus characterised by the spinning section, e.g. capillary tube, protrusion or pin
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0092—Electro-spinning characterised by the electro-spinning apparatus characterised by the electrical field, e.g. combined with a magnetic fields, using biased or alternating fields
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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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
-
- 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
-
- 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
Abstract
The invention discloses a kind of composite diaphragm and its preparation method and application, preparation method includes: that PMMA is added in PMIA solution to mix, and obtains uniform PMMA/PMIA mixed solution;Nano-oxide solution is added in the PMMA/PMIA mixed solution, mixing obtains spinning solution;By the spinning solution electrostatic spinning, the composite diaphragm is made.Composite diaphragm obtained not only has the stronger electrolyte affinity of PMMA material, imbibition and liquid-keeping property, simultaneously also in relation with the high-fire resistance of PMIA material, anti-flammability, chemical stability and mechanical stability, and diaphragm is modified using nano-oxide, further improve conductivity, thermal stability and mechanical performance.
Description
Technical field
The invention belongs to field of lithium ion battery, and in particular to a kind of composite diaphragm and its preparation method and application.
Background technique
Lithium ion battery has energy density high, and self-discharge rate is low, and good rate capability has extended cycle life, memory-less effect,
The a series of advantage such as environmentally friendly, is not only widely used in mobile phone, digital camera, laptop, and electric vehicle,
The fields such as electric car and energy-storage system are also used widely.
Diaphragm as one of layer assembly in key in lithium ion battery, function be for lithium ion in liquid electrolyte
Transmission provides channel, and yin-yang the two poles of the earth that battery is isolated directly contact to avoid two electrodes and cause short circuit.In lithium ion battery
In, interfacial structure, internal resistance of the superiority and inferiority of diaphragm and battery etc. are closely related, and then to the capacity, cycle performance, safety of battery
The generations such as energy influence accordingly.
Currently, the polyethylene (PE) of commercialization, polypropylene (PP) and polypropylene, polyethylene/polypropylene (PP/PE/PP) etc.
The porosity and fusing point of polyolefin film are lower, and wetability and thermal stability are bad, lead to battery short circuit, cause thermal runaway, cause
The a series of safety problem such as battery explosion.Therefore, exploitation heat resistance is good, porosity is high and has excellent mechanical properties
Lithium ion battery separator become current research work hot spot.
The polyimide fiber film of method of electrostatic spinning preparation not only has polyimides heat resistance outstanding and chemical stabilization
Property, while having the characteristic of nano fibrous membrane high porosity and specific area, it is concerned in lithium electric separator field.But at present to lithium from
The power requirement of sub- battery is higher and higher, and the heat resistance of existing polyimide nanofiber membrane, mechanical property and wellability are equal
It is unable to satisfy the requirement of high-power lithium ion battery;Although thering is preferable imbibition to protect in addition, PMMA is strong to the affinity of electrolyte
Liquid ability, but its mechanical performance is poor.
Summary of the invention
Based on this, the present invention provides a kind of preparation method of lithium ion battery separator, comprehensive PMIA's and PMMA is respective
A little, using method of electrostatic spinning, and nano-oxide is introduced inside PMIA/PMMA diaphragm, solves prior art septation
Porosity and fusing point are low, wetability and thermal stability are bad, the unsafe problem of battery, and the present invention is organic by carrying out three
Inorganic compounding prepares high-performance composite diaphragm.
To achieve the goals above, the invention adopts the following technical scheme:
A kind of preparation method of composite diaphragm, comprising the following steps:
S1, it will be mixed in PMMA addition PMIA solution, obtain uniform PMMA/PMIA mixed solution;
S2, nano-oxide solution is added in the PMMA/PMIA mixed solution, mixing obtains spinning solution;
S3, by the spinning solution electrostatic spinning, the lithium ion battery composite separation membrane is made.
Further, in step S1, the PMIA solution the preparation method comprises the following steps: by PMIA be added DMAc/LiCl mix it is molten
5~8h is stirred in 50~80 DEG C of sealings in agent, wherein the DMAc/LiCl mixed solvent is that anhydrous LiCl is added in DMAc
It is completely dissolved to obtain;
In the PMIA solution, the mass fraction that the mass fraction of PMIA is 6~15%, LiCl is 1~3%.
Preferably, for the PMIA by being dried, the temperature of the drying is 100~130 DEG C, and the time is 0.5~2h.
Further, in step S1, for the PMMA by being dried, the temperature of the drying is 70~90 DEG C, the time
For 0.5~2h.
Further, in step S1, in the PMMA/PMIA mixed solution, the mass ratio of PMMA and PMIA be 1:(3~
5)。
Further, in step S2, the nano-oxide solution the preparation method comprises the following steps: alcohols is added in nano-oxide
It is fully dispersed in solvent that the nano-oxide solution is made, wherein the alcohols solvent be methanol, ethyl alcohol, in propyl alcohol extremely
Few one kind;According to the concentration of the nano-oxide solution of addition and PMMA/PMIA mixed solution, heretofore described spinning solution
Concentration no longer does specific restriction between 15~25wt% here.
Preferably, in step S2,0.0075~0.25g nano-oxide is added in alcohols solvent described in every 10mL, it is described
Nano-oxide is at least one of silica, titanium dioxide, aluminum oxide.
Further, in step S3, the parameter setting of the electrostatic spinning are as follows: injection promote rate be 0.1mL/h~
0.3mL/h, spinning voltage 15kV~30kV, receiver board is 15cm~25cm at a distance from syringe needle, in syringe needle
Diameter is 0.15mm~0.4mm.
It is another object of the present invention to provide a kind of composite diaphragms, are made using above-mentioned preparation method.
Third object of the present invention is to provide above-mentioned composite diaphragm in the application being used to prepare in lithium ion battery.
Compared with prior art, the invention has the following advantages:
Polymethacrylates (PMMA) has good electrical insulation capability, and good with compatibility of electrolyte, interface impedance is low
The advantages that, and the strong effect of hydrogen bond makes PMIA with good resistance in poly (PMIA) crystal structure
Hot, anti-flammability, chemical stability, while nano-oxide has the mechanical property of reinforcing fiber film and the spy of high-temperature stability
Property, therefore, the present invention combines the respective advantage of PMIA and PMMA, is prepared for composite diaphragm using the method for Static Spinning, described
Composite diaphragm not only has the stronger electrolyte affinity of PMMA material, imbibition and liquid-keeping property, while also in relation with PMIA material
High-fire resistance, anti-flammability, chemical stability and mechanical stability, and diaphragm is modified using nano-oxide, into one
Step improves conductivity, thermal stability and mechanical performance.
The experimental results showed that the lithium ion battery composite separation membrane conductivity height in the present invention, thermodynamic stability are good, diaphragm
150 DEG C at a temperature of almost without contraction, have excellent performance.
In addition, the present invention uses electrostatic spinning to prepare diaphragm, not only preparation process is simple, and productivity is high, and can satisfy height
The requirement of capacity lithium ion battery high-performance, high security.
Specific embodiment
To facilitate the understanding of the present invention, below in conjunction with specific embodiments to invention is more fully described.But
It is that the invention can be realized in many different forms, however it is not limited to embodiments described herein.On the contrary, providing
The purpose of these embodiments is to make to make the present disclosure more fully understandable.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.
Embodiment 1
By PMIA under the conditions of 120 DEG C dry 2h, then weighing 4.8g PMIA, to be added to 54g DMAc/LiCl mixing molten
In agent, wherein the mass fraction of LiCl is 2%, equal to solution mixing in 60 DEG C of at a temperature of sealing stirring 4h with magnetic stirring apparatus
It is even;
By nanometer PMMA, dry 2h, the PMMA particle after then weighing 1.2g drying are added to middle PMIA under the conditions of 80 DEG C
In solution, stirring 4h under confined conditions dissolves it sufficiently, obtains uniform PMMA/PMIA mixed liquor;
The mixing of 10mL methanol/ethanol/propyl alcohol is taken as solvent, is added the silica of 0.03g, after ultrasonic oscillation 2h,
Obtain uniform silicon dioxde solution;
By scattered Nano-meter SiO_22Solution is added in PMMA/PMIA mixed solution, obtains spinning solution after mixing evenly;
Spinning solution is put into syringe, under the following conditions spinning: the propulsion rate of syringe pump is 0.15mL/h, spinning
It is 0.2mm that voltage 15kV, receiver board, which are 20cm, syringe needle internal diameter at a distance from syringe needle,.
Comparative example 1
PMIA is dried into 2h under the conditions of 120 DEG C, 3.84g PMIA is then weighed and is added to 55.2g DMAc/LiCl mixing
In solvent, wherein the mass fraction of LiCl is 2%, stirs 4h to solution mixing in 60 DEG C of at a temperature of sealing with magnetic stirring apparatus
Uniformly, PMIA solution is obtained;
By nanometer PMMA, dry 2h, the PMMA particle after then weighing 0.96g drying are added to PMIA under the conditions of 80 DEG C
In solution, stirring 4h under confined conditions dissolves it sufficiently, obtains uniform PMMA/PMIA mixed liquor;
PMMA/PMIA mixed liquor is put into syringe, under the following conditions spinning: the propulsion rate of syringe pump is
It is 0.2mm that 0.15mL/h, spinning voltage 15kV, receiver board, which are 20cm, syringe needle internal diameter at a distance from syringe needle,.
Comparative example 2
By PMIA under the conditions of 120 DEG C dry 2h, then weighing 4.8g PMIA, to be added to 54g DMAc/LiCl mixing molten
In agent, wherein the mass fraction of LiCl is 2%, equal to solution mixing in 60 DEG C of at a temperature of sealing stirring 4h with magnetic stirring apparatus
It is even, obtain PMIA solution;
Nanometer PMMA is dried into 2h under the conditions of 80 DEG C, it is molten that the PMMA particle after then weighing 1.2g drying is added to PMIA
In liquid, stirring 4h under confined conditions dissolves it sufficiently, obtains uniform PMMA/PMIA mixed liquor;
PMMA/PMIA mixed liquor is put into syringe, under the following conditions spinning: the propulsion rate of syringe pump is
It is 0.2mm that 0.15mL/h, spinning voltage 15kV, receiver board, which are 20cm, syringe needle internal diameter at a distance from syringe needle,.
Comparative example 3
By PMIA under the conditions of 120 DEG C dry 2h, then weighing 7.2g PMIA, to be added to 51g DMAc/LiCl mixing molten
In agent, wherein the mass fraction of LiCl is 2%, equal to solution mixing in 60 DEG C of at a temperature of sealing stirring 4h with magnetic stirring apparatus
It is even, obtain PMIA solution;
Nanometer PMMA is dried into 2h under the conditions of 80 DEG C, it is molten that the PMMA particle after then weighing 1.8g drying is added to PMIA
In liquid, stirring 4h under confined conditions dissolves it sufficiently, obtains uniform PMMA/PMIA mixed liquor;
PMMA/PMIA mixed liquor is put into syringe, under the following conditions spinning: the propulsion rate of syringe pump is
It is 0.2mm that 0.15mL/h, spinning voltage 15kV, receiver board, which are 20cm, syringe needle internal diameter at a distance from syringe needle,.
Embodiment 2
By PMIA under the conditions of 120 DEG C dry 2h, then weighing 4.8g PMIA, to be added to 54g DMAc/LiCl mixing molten
In agent, wherein the mass fraction of LiCl is 2%, equal to solution mixing in 60 DEG C of at a temperature of sealing stirring 3h with magnetic stirring apparatus
It is even;
By nanometer PMMA, dry 2h, the PMMA particle after then weighing 1.2g drying are added to middle PMIA under the conditions of 80 DEG C
In solution, stirring 4h under confined conditions dissolves it sufficiently, obtains uniform PMMA/PMIA mixed liquor;
It takes 10mL methanol/ethanol/propyl alcohol mixing as solvent, the Nano-meter SiO_2 of 0.06g is added2, after ultrasonic oscillation 2h,
Obtain uniform inorganic nano SiO2Solution;
By scattered Nano-meter SiO_22Solution is added in PMMA/PMIA mixed solution, obtains spinning solution after mixing evenly;
Spinning solution is put into syringe, under the following conditions spinning: the propulsion rate of syringe pump is 0.15mL/h, spinning
It is 0.2mm that voltage 15kV, receiver board, which are 20cm, syringe needle internal diameter at a distance from syringe needle,.
Embodiment 3
By PMIA under the conditions of 120 DEG C dry 2h, then weighing 4.8g PMIA, to be added to 54g DMAc/LiCl mixing molten
In agent, wherein the mass fraction of LiCl is 2%, equal to solution mixing in 60 DEG C of at a temperature of sealing stirring 4h with magnetic stirring apparatus
It is even;
By nanometer PMMA, dry 2h, the PMMA particle after then weighing 1.2g drying are added to middle PMIA under the conditions of 80 DEG C
In solution, stirring 4h under confined conditions dissolves it sufficiently, obtains uniform PMMA/PMIA mixed liquor;
It takes 10mL methanol/ethanol/propyl alcohol mixing as solvent, the Nano-meter SiO_2 of 0.12g is added2, after ultrasonic oscillation 2h,
Obtain uniform Nano-meter SiO_22Solution;
By scattered Nano-meter SiO_22Solution is added in PMMA/PMIA mixed solution, obtains spinning solution after mixing evenly;
Spinning solution is put into syringe, under the following conditions spinning: the propulsion rate of syringe pump is 0.15mL/h, spinning
It is 0.2mm that voltage 15kV, receiver board, which are 20cm, syringe needle internal diameter at a distance from syringe needle,.
Embodiment 4
By PMIA under the conditions of 100 DEG C dry 2h, then weighing 3.45g PMIA, to be added to 54g DMAc/LiCl mixing molten
In agent, wherein the mass fraction of LiCl is 1%, equal to solution mixing in 50 DEG C of at a temperature of sealing stirring 8h with magnetic stirring apparatus
It is even;
By nanometer PMMA under the conditions of 70 DEG C dry 2h, during the PMMA particle after then weighing 1.15g drying is added to
In PMIA solution, stirring 4h under confined conditions dissolves it sufficiently, obtains uniform PMMA/PMIA mixed liquor;
It takes 10mL methanol/ethanol/propyl alcohol mixing as solvent, the nano-TiO of 0.25g is added2, after ultrasonic oscillation 2h,
Obtain uniform inorganic nano TiO2Solution;
By scattered nano-TiO2Solution is added in PMMA/PMIA mixed solution, obtains spinning solution after mixing evenly;
Spinning solution is put into syringe, under the following conditions spinning: the propulsion rate of syringe pump is 0.15mL/h, spinning
It is 0.2mm that voltage 15kV, receiver board, which are 20cm, syringe needle internal diameter at a distance from syringe needle,.
Embodiment 5
PMIA is dried into 0.5h under the conditions of 130 DEG C, 9.5g PMIA is then weighed and is added to 54g DMAc/LiCl mixing
In solvent, wherein the mass fraction of LiCl is 3%, stirs 5h to solution mixing in 80 DEG C of at a temperature of sealing with magnetic stirring apparatus
Uniformly;
By nanometer PMMA under the conditions of 90 DEG C dry 0.5h, during the PMMA particle after then weighing 1.9g drying is added to
In PMIA solution, stirring 4h under confined conditions dissolves it sufficiently, obtains uniform PMMA/PMIA mixed liquor;
It takes 10mL methanol/ethanol/propyl alcohol mixing as solvent, the nanometer Al of 0.0075g is added2O3, ultrasonic oscillation 2h
Afterwards, uniform inorganic nano nanometer Al is obtained2O3;
By scattered nanometer Al2O3Solution is added in PMMA/PMIA mixed solution, obtains spinning solution after mixing evenly;
Spinning solution is put into syringe, under the following conditions spinning: the propulsion rate of syringe pump is 0.15mL/h, spinning
It is 0.2mm that voltage 15kV, receiver board, which are 20cm, syringe needle internal diameter at a distance from syringe needle,.
Composite diaphragm progress contact angle, porosity, imbibition rate, ion-conductance obtained in comparative example 1~3 and Examples 1 to 3
The measurement of conductance and percent thermal shrinkage, test method are as follows:
1, the test of mechanical property: the specimen size cut is 20 × 50mm, and setting tensile speed is 10mm/min.It stretches
Breaking strength calculation formula are as follows: δ=F/ (L*d), wherein δ is tensile strength, and F is sample tensile load, and L is specimen width, d
For specimen width.
2, the test of porosity: impregnating 2h for film in n-butanol, and the n-butanol of film surface absorption is blotted in taking-up with filter paper,
Impregnated with electronic balance weighing film it is of poor quality before and after n-butanol, then with the stereometer of the density divided by n-butanol and film of poor quality
Calculate porosity.
3, the test of ionic conductivity: cutting the diaphragm to match with resistance test mold, be put into electrolyte, sealing leaching
2h is steeped, obtains and calculates conductivity with formula σ=d/ (R*S) after resistance value, wherein σ is the ionic conductivity of diaphragm, and R is diaphragm
Resistance value, d is the thickness of diaphragm, and S be the diaphragm area that cuts when testing.
4, the test method of percent thermal shrinkage: cutting 100mm × 100mm sample 5 and open, at a temperature of 150 DEG C in vacuum drying oven
0.5h is handled, its longitudinal size is then surveyed.Percent thermal shrinkage: Δ L=(L-L0)/L × 100%, L are longitudinal length before heating, L0
To heat preceding longitudinal length, unit mm.
Above-mentioned test result is referring to table 1.
The dependence test result of composite diaphragm in 1 comparative example 1~3 of table and Examples 1 to 3
The membrane properties of the lithium ion battery separator of Examples 1 to 3 preparation are substantially better than comparative example as can be seen from Table 1
Diaphragm in 1~3, and diaphragm 150 DEG C at a temperature of almost without contraction, lithium ion battery separator prepared by the present invention
It can be excellent.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of preparation method of composite diaphragm, which comprises the following steps:
S1, it will be mixed in PMMA addition PMIA solution, obtain uniform PMMA/PMIA mixed solution;
S2, nano-oxide solution is added in the PMMA/PMIA mixed solution, mixing obtains spinning solution;
S3, by the spinning solution electrostatic spinning, the composite diaphragm is made.
2. preparation method as described in claim 1, which is characterized in that in step S1, the PMIA solution the preparation method comprises the following steps:
DMAc/LiCl in the mixed solvent is added in PMIA and stirs 5 ~ 8h in 50 ~ 80 DEG C of sealings, wherein the DMAc/LiCl mixed solvent
It is completely dissolved to obtain for anhydrous LiCl to be added in DMAc;
In the PMIA solution, the mass fraction that the mass fraction of PMIA is 6 ~ 15%, LiCl is 1 ~ 3%.
3. preparation method as described in claim 1, which is characterized in that PMIA described in step S1 is described by being dried
Dry temperature is 100 ~ 130 DEG C, and the time is 0.5 ~ 2h.
4. preparation method as described in claim 1, which is characterized in that in step S1, the PMMA is described by being dried
Dry temperature is 70 ~ 90 DEG C, and the time is 0.5 ~ 2h.
5. preparation method as described in claim 1, which is characterized in that in step S1, in the PMMA/PMIA mixed solution,
The mass ratio of PMMA and PMIA is 1:(3 ~ 5).
6. preparation method as described in claim 1, which is characterized in that in step S2, the preparation of the nano-oxide solution
Method are as follows: the nano-oxide solution is made by fully dispersed in nano-oxide addition alcohols solvent, wherein the alcohols
Solvent is at least one of methanol, ethyl alcohol, propyl alcohol.
7. preparation method as claimed in claim 6, which is characterized in that in step S2, be added in alcohols solvent described in every 10mL
0.0075 ~ 0.25g nano-oxide, the nano-oxide are silica, titanium dioxide, at least one in aluminum oxide
Kind.
8. preparation method as described in claim 1, which is characterized in that in step S3, the parameter setting of the electrostatic spinning are as follows:
Injection promotes rate for 0.1mL/h ~ 0.3mL/h, spinning voltage 15kV~30kV, and receiver board is at a distance from syringe needle
15cm ~ 25cm, syringe needle internal diameter are 0.15mm ~ 0.4mm.
9. a kind of composite diaphragm, which is characterized in that be made using the preparation method as described in claim 1 ~ 8.
10. composite diaphragm as claimed in claim 9 is in the application being used to prepare in lithium ion battery.
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Citations (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102242464A (en) * | 2010-05-10 | 2011-11-16 | 中国科学院理化技术研究所 | Polymer-ceramic compound nanometer fibrous membrane as well as preparation method and application thereof |
CN102931370A (en) * | 2012-10-24 | 2013-02-13 | 江苏大学 | Organic/inorganic composite nanofiber membrane of lithium ion power battery and preparation method of organic/inorganic composite nanofiber membrane |
CN103824988A (en) * | 2014-02-24 | 2014-05-28 | 东华大学 | Composite nanofiber lithium battery diaphragm and making method thereof |
CN103898771A (en) * | 2014-03-05 | 2014-07-02 | 符思敏 | Method for preparing nano fiber composite material containing PMMA (Polymethyl Methacrylate) |
CN104157817A (en) * | 2014-09-01 | 2014-11-19 | 中国工程物理研究院化工材料研究所 | Lithium ion battery diaphragm for overcharge protection and preparation method thereof |
CN104681764A (en) * | 2015-02-10 | 2015-06-03 | 龙岩紫荆创新研究院 | Composite lithium ion battery ceramic diaphragm and preparation method thereof |
CN104766938A (en) * | 2015-02-10 | 2015-07-08 | 龙岩紫荆创新研究院 | Composite lithium ion battery diaphragm and preparation method thereof |
CN105428572A (en) * | 2015-11-27 | 2016-03-23 | 厦门大学 | Preparation method of electrospun composite membrane for lithium ion battery |
CN107706340A (en) * | 2017-08-31 | 2018-02-16 | 东莞市沃泰通新能源有限公司 | A kind of nano electrostatic spinning for ferric phosphate lithium cell strengthens barrier film and preparation method thereof |
CN107785519A (en) * | 2016-08-29 | 2018-03-09 | 比亚迪股份有限公司 | A kind of composite membrane of polymer and preparation method thereof and the lithium ion battery for including it |
CN108172736A (en) * | 2016-12-07 | 2018-06-15 | 中南大学 | A kind of preparation method of lithium ion battery hydridization diaphragm |
CN109004155A (en) * | 2018-07-26 | 2018-12-14 | 江西省通瑞新能源科技发展有限公司 | A kind of preparation method of aramid fiber composite diaphragm for lithium battery |
CN109244331A (en) * | 2018-09-28 | 2019-01-18 | 青岛大学 | A kind of preparation method of lithium ion battery separator |
CN109713203A (en) * | 2018-12-11 | 2019-05-03 | 天津工业大学 | A kind of lithium ion battery separator and preparation method thereof |
-
2019
- 2019-08-01 CN CN201910708924.XA patent/CN110453372A/en active Pending
Patent Citations (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102242464A (en) * | 2010-05-10 | 2011-11-16 | 中国科学院理化技术研究所 | Polymer-ceramic compound nanometer fibrous membrane as well as preparation method and application thereof |
CN102931370A (en) * | 2012-10-24 | 2013-02-13 | 江苏大学 | Organic/inorganic composite nanofiber membrane of lithium ion power battery and preparation method of organic/inorganic composite nanofiber membrane |
CN103824988A (en) * | 2014-02-24 | 2014-05-28 | 东华大学 | Composite nanofiber lithium battery diaphragm and making method thereof |
CN103898771A (en) * | 2014-03-05 | 2014-07-02 | 符思敏 | Method for preparing nano fiber composite material containing PMMA (Polymethyl Methacrylate) |
CN104157817A (en) * | 2014-09-01 | 2014-11-19 | 中国工程物理研究院化工材料研究所 | Lithium ion battery diaphragm for overcharge protection and preparation method thereof |
CN104766938A (en) * | 2015-02-10 | 2015-07-08 | 龙岩紫荆创新研究院 | Composite lithium ion battery diaphragm and preparation method thereof |
CN104681764A (en) * | 2015-02-10 | 2015-06-03 | 龙岩紫荆创新研究院 | Composite lithium ion battery ceramic diaphragm and preparation method thereof |
CN105428572A (en) * | 2015-11-27 | 2016-03-23 | 厦门大学 | Preparation method of electrospun composite membrane for lithium ion battery |
CN107785519A (en) * | 2016-08-29 | 2018-03-09 | 比亚迪股份有限公司 | A kind of composite membrane of polymer and preparation method thereof and the lithium ion battery for including it |
CN108172736A (en) * | 2016-12-07 | 2018-06-15 | 中南大学 | A kind of preparation method of lithium ion battery hydridization diaphragm |
CN107706340A (en) * | 2017-08-31 | 2018-02-16 | 东莞市沃泰通新能源有限公司 | A kind of nano electrostatic spinning for ferric phosphate lithium cell strengthens barrier film and preparation method thereof |
CN109004155A (en) * | 2018-07-26 | 2018-12-14 | 江西省通瑞新能源科技发展有限公司 | A kind of preparation method of aramid fiber composite diaphragm for lithium battery |
CN109244331A (en) * | 2018-09-28 | 2019-01-18 | 青岛大学 | A kind of preparation method of lithium ion battery separator |
CN109713203A (en) * | 2018-12-11 | 2019-05-03 | 天津工业大学 | A kind of lithium ion battery separator and preparation method thereof |
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