CN110048058A - A kind of compound lithium ion battery separator and preparation method thereof - Google Patents
A kind of compound lithium ion battery separator and preparation method thereof Download PDFInfo
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- CN110048058A CN110048058A CN201910284657.8A CN201910284657A CN110048058A CN 110048058 A CN110048058 A CN 110048058A CN 201910284657 A CN201910284657 A CN 201910284657A CN 110048058 A CN110048058 A CN 110048058A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
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- 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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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The present invention relates to a kind of compound lithium ion battery separators and preparation method thereof.Compound lithium ion battery separator is made of substrate layer with the inorganic/organic composite porous film layer that substrate layer surface is arranged in, and substrate layer is polyolefin porous membrane；Inorganic/organic composite porous film layer is the composite layer containing inorganic nano-particle and aqueous binders.Being uniformly mixed the preparation method comprises the following steps: inorganic aqueous dispersion liquid, organic water borne dispersion liquid and surfactant are added in deionized water for compound lithium ion battery separator, is made coating；By substrate layer infiltration into configured coating, after carrying out lifting coating, vacuum drying is dry after drying at room temperature, and compound lithium ion battery separator is made.The present invention problem unstable for diaphragm safety energy, forms the porous membrane of the uniform hydridization of organic-inorganic in its surface cure, realizes the safety of the thermal stability, lithium ion battery of diaphragm and the raising of chemical corrosion resistance.
Description
Technical field
The invention belongs to lithium ion battery separator fields, and in particular to a kind of compound lithium ion battery separator and its system
Preparation Method.
Background technique
Lithium ion battery is considered as the choosing of the ideal of high capacity, high power battery.In order to meet ever-increasing application
Demand, it is good that lithium ion battery should be provided simultaneously with stable circulation performance, and reversible capacity is high, the chemical properties such as fast charging and discharging,
With the large-scale application of lithium ion battery, safety problem is also increasingly prominent.
Diaphragm is the key component in lithium ion battery, between the positive electrode and negative electrode of battery, avoids the object of two electrodes
Reason contact, while keeping the transmission of free ion.Diaphragm is mainly made of polymer film or non-woven membrane, and is had abundant
Cellular structure.Diaphragm needs to have enough porositys, wetability, holds fluidity, mechanical strength, thermal stability, and is forming
Have excellent ionic conductivity, lithium ion transference number, electrochemical stability, multiplying power and charge-discharge performance after battery.So
And the presence of battery septation occupies the originally few confined space of inside battery, this properties to lithium ion battery
It will have adverse effect on.In view of this, suitable diaphragm the comprehensive performance of lithium ion battery is played it is vital
Effect.
For the battery of high-energy density, it is desirable that the thickness of diaphragm is sufficiently thin and cellular structure had not only been enriched but also uniform, simultaneously
Also need to keep certain mechanical strength, the Li dendrite for preventing cathode from generating pierces through diaphragm, and contacting with anode leads to short circuit.Also
It is required that diaphragm has certain thermal stability, cellular structure can be closed when lithium ion battery overheats, and size receipts do not occur
Deformation occurs for contracting, prevents short circuit to separate positive and negative anodes.Therefore, it is related to that a thermal stability is good, the high lithium-ion electric of security performance
The current technical issues that need to address of pond diaphragm type.
Summary of the invention
That the purpose of the present invention is to provide a kind of coating thickness uniformities is good, is avoided that diaphragm thermal deformation, can improve diaphragm
To the aqueous coating lithium ion battery separator material of electrolyte solution wetability.The present invention safely can not for polyalkene diaphragm
Stable problem forms the porous membrane of the uniform hydridization of organic-inorganic in its surface cure, realizes thermal stability, the lithium of diaphragm
The safety of ion battery and the raising of chemical corrosion resistance.Meanwhile preparation method of the invention is all made of aqueous solvent, takes
For traditional organic solvent, has the characteristics that safety and environmental friendliness；The present invention is to the safety for improving lithium ion battery and makes
With the service life, the development of China's green power energy is pushed, is had great importance.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of compound lithium ion battery separator is more by substrate layer and inorganic/organic composite that substrate layer surface is arranged in
Hole film layer is constituted, and the substrate layer is polyolefin porous membrane；The inorganic/organic composite porous film layer is containing organic/inorganic nano
The composite layer of particle and aqueous binders, the inorganic/organic composite porous film layer is in substrate layer unilateral side with a thickness of 1-4um.
As the further improvement of above-described embodiment, the polyolefin porous membrane is polyethylene porous film, polypropylene is more
One of hole film or polypropylene, polyethylene/polypropylene composite materials porous membrane, the polyolefin porous membrane with a thickness of 7-
16μm。
As the further improvement of above-described embodiment, the inorganic nano-particle is silicon dioxide granule, aluminum oxide
One of particle or Si-Al molecular sieve；The aqueous binders are point of aqueous polyvinylidene vinyl fluoride, acrylate or polyurethane
One of dispersion liquid；Preferably silicon dioxide granule.The synthetic method of Si-Al molecular sieve of the invention is by tetraethyl orthosilicate
And NaAlO2It is hydrolyzed in the aqueous solution of tetrapropylammonium hydroxide first.At a temperature of 80-90 DEG C, after evaporating ethanol, obtain
It is SiO to molar ratio2:Al2O3: tetrapropylammonium hydroxide: H2The clear solution of O=20:1:0.25:15.Finally, after being concentrated
Solution pour into the autoclave of teflon liner, and be heat-treated 24 hours at 170 DEG C, after heat treatment, use distilled water
The product being obtained by filtration is washed, the molecular sieve solution of 10% solid content is obtained；The molecular sieve solution of remaining solid content passes through dense
Contracting or dilution can be realized.Remaining inorganic nano-particle and aqueous binders used in the present invention are that direct purchase is got,
Specially water-and acrylate (AE) technical grade is bought from Yiwu City Rui Long adhesive Co., Ltd；Aqueous polyurethane (PU),
Technical grade is bought from Jining Hua Kai resin Co., Ltd；Kynoar (PVDF, RC-10-206), analyze it is pure, purchase from Ah
Kerma (unit of kinetic energy) (China) Investment Co., Ltd；Aqueous silica dispersion liquid (SiO2), technical grade, Guangdong Well-Silicasol Co., Ltd..
The present invention also provides a kind of preparation methods of compound lithium ion battery separator, comprising the following steps:
Coating preparation: inorganic aqueous dispersion liquid, organic water borne dispersion liquid and surfactant are added in deionized water
It is uniformly mixed, coating is made；
The preparation of compound lithium ion battery separator: by substrate layer infiltration into configured coating, lifting coating is carried out
Afterwards, drying at room temperature certain time in air, then in vacuum drying oven under certain temperature it is dry after a certain period of time, be made multiple
Mould assembly lithium ion battery separator.
Each component and its weight percentage as the further improvement of above-described embodiment, in the coating are as follows:
As the further improvement of above-described embodiment, the inorganic aqueous dispersion liquid be inorganic nano-particle in water
Dispersion liquid, wherein the solid content of inorganic nano-particle is 30%-70% in inorganic aqueous dispersion liquid；Described inorganic aqueous point
The partial size of inorganic particulate in dispersion liquid is 10-150nm.
As the further improvement of above-described embodiment, the organic water borne dispersion liquid is point of aqueous binders in water
Dispersion liquid, wherein the solid content of aqueous binders is 5%-20% in organic water borne dispersion liquid；The organic water borne dispersion liquid
The partial size of middle organic filler is 100-500nm.
As the further improvement of above-described embodiment, the surfactant is nonionic surfactant and fluorine carbon
One of surfactant；The nonionic surfactant specifically: non-ionic polyacrylamide, alkyl phenol polyoxy second
Alkene ether or polyoxyethylene carboxylate etc., the fluorocarbon surfactant specifically: alcohol amine salt type anion fluoro-carbon surface active
Agent INTECHEM-01, carboxylic acid potassium type anion fluorocarbon surfactant (FC-5) or amine oxide type cation fluorine carbon surface active
Agent (FC-08) etc..
As the further improvement of above-described embodiment, the condition of the lifting coating are as follows: the decrease speed 100mm/ of lifting
Min, rate of climb 60mm/min；Coating process is lifted without stop.
As the further improvement of above-described embodiment, the time of drying at room temperature is 15-30min in air；It is dried in vacuum
Drying condition in case: vacuum drying temperature is 60-100 DEG C, vacuum drying time are as follows: 0.5-1.5h.
Inventive principle: in composite lithium battery membrane of the invention, the thermal stability of inorganic particle, so that entire THIN COMPOSITE
The thermal contraction of film is suppressed, and organic component can also improve the thermal stability of diaphragm, while coat inorganic component as binder
In membrane surface；Organic inorganic hybridization coating also assigns MIcroporous polyolefin film higher mechanical strength simultaneously；In addition diaphragm reaches
After ultimate tensile strength fracture, the binder on surface can also properly increase its tensile strength；The pure thorn of diaphragm one can be broken
It splits, then its surface coats one layer of slurry, when puncture first punctures the slurry on surface, could pierce through diaphragm, therefore puncture strength obtains very
Big to be promoted, this also can be avoided the Li dendrite in battery from puncturing diaphragm and cause short circuit, to improve the security performance of battery.
Beneficial effect
In terms of thermal stability, the diaphragm after coating is not shunk lithium battery diaphragm of the invention to 170 DEG C；Power
Aspect of performance is learned, the diaphragm puncture intensity after coating reaches 700gF mm-2Left and right；In terms of wetability, the diaphragm after covering can be accomplished
The complete spreading wetting on surface, contact angle are 14.9 °；In terms of ionic conductivity, the ionic conductivity of the diaphragm after coating reaches
0.42mS cm-1Left and right.
Cloth diaphragm is applied after directly mixing present invention employs inorganic component with inorganic component, step is simple.
The present invention uses the binder of aqueous solvent to accomplish under the premise of suitably increasing cost to zero environmental.
In inorganic particulate of the present invention and organic binder proportion, inorganic particulate accounts for major part, plays most important thermostabilization and makees
With organic binder accounts for small part, and the coating formed in this way can make inorganic particulate is well-proportioned to be very well coated in diaphragm table
Face.For lithium battery diaphragm thickness control of the invention in 1-4um or so, diaphragm cannot be too thick, it is too thick if positive and negative pole material will
Bao Liao influences the performance of battery, can not be very little, it is very little can mechanical performance it is bad.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of lithium ion battery separator of the invention；
Fig. 2 is the Electronic Speculum test chart of lithium ion battery separator of the invention；Wherein (a) is composite lithium ion cell diaphragm
Surface topography test chart；It (b) is the thickness test chart of composite lithium ion cell diaphragm.
Specific embodiment
The invention will be further elucidated with reference to specific embodiments.
Embodiment 1
(1) deionization coating preparation: is added in inorganic aqueous dispersion liquid, organic water borne dispersion liquid and surfactant
It stirs 3 hours and is uniformly mixed in water, coating is made；Wherein, inorganic aqueous dispersion liquid is the water nano SiO of 50% solid content2
Dispersion liquid；Organic water borne dispersion liquid is Kynoar (PVDF) dispersion liquid of 50% solid content；Surfactant is nonionic
Polyacrylamide；Wherein, the additional amount of inorganic aqueous dispersion liquid is 56wt%, and the additional amount of organic water borne dispersion liquid is
1wt%, the additional amount of surfactant are 0.7wt%, and the additional amount of deionized water is 42.3wt%.Inorganic aqueous dispersion liquid
The partial size of middle inorganic particulate is 90-105nm；The partial size of organic filler is 350-450nm in organic water borne dispersion liquid.
(2) 12 μm of clean pure PE diaphragms are infiltrated into configured coating by pulling machine, carry out lifting coating,
Setting decrease speed is 100mm/min, rate of climb 60mm/min.After diaphragm carries out lifting coating, room temperature is dry in air
Dry 15min, then 60 DEG C of dry 1h in vacuum drying oven.
The compound lithium ion battery separator prepared through the above method by substrate layer and is arranged in base as shown in Fig. 1
The inorganic/organic composite porous film layer of material layer surface is constituted, and substrate layer is PE film；Inorganic/organic composite porous film layer be containing
Inorganic SiO2The composite layer of nanoparticle and Kynoar (PVDF), inorganic/organic composite porous film layer is in substrate layer unilateral side
With a thickness of 3um or so, the Electronic Speculum test chart of compound lithium ion battery separator prepared by embodiment 1 is as shown in Figure 2.
Comparative example 1
Comparative example 1 is not make the PE diaphragm of any modification.
Embodiment 2
The preparation step of embodiment 2 is substantially the same manner as Example 1, and distinctive points are only that aqueous binders are acrylate
(AE)。
The compound lithium ion battery separator prepared through the above method, by substrate layer and the nothing that substrate layer surface is arranged in
Machine/organic composite porous film layer is constituted, and substrate layer is PE film；Inorganic/organic composite porous film layer is to contain inorganic SiO2Nanometer
The composite layer of particle and acrylate (AE), inorganic/organic composite porous film layer is in substrate layer unilateral side with a thickness of 3um or so.
Embodiment 3
The preparation step of embodiment 3 is substantially the same manner as Example 1, and distinctive points are only that aqueous binders are polyurethane
(PU)。
The compound lithium ion battery separator prepared through the above method, by substrate layer and the nothing that substrate layer surface is arranged in
Machine/organic composite porous film layer is constituted, and substrate layer is PE film；Inorganic/organic composite porous film layer is to contain inorganic SiO2Nanometer
The composite layer of particle and polyurethane (PU), inorganic/organic composite porous film layer is in substrate layer unilateral side with a thickness of 3um or so.
Function detection:
(1) test method:
A) air penetrability
Air penetrability is one of the important parameter for characterizing lithium ion battery separator cellular structure, is usually indicated with Gurley value,
Unit is the second (s).Its physical significance is under normal pressure state, and the air of designated volume passes through completely required for diaphragm specific region
Time.In this chapters and sections, 100mL air is used.Gurley value is bigger, illustrates the interstructural connectivity of diaphragm internal gutter
It is poorer；Otherwise Gurley value is smaller, illustrates that diaphragm internal gutter structure permeability is better.Experiment is come pair using UEC-1012-A
The air penetrability of diaphragm is tested.
B) liquid holdup
Liquid holdup refers to the ability that diaphragm duct keeps electrolyte, is lithium ion battery separator one important physics ginseng
Number, can explain the data of some chemical properties of diaphragm by the parameter, can also further speculate and analyze and be assembled into
The chemical properties parameter such as initial capacity and cycle life of half-cell.Experimentation is, by the diaphragm of slice, (diameter is
19mm) be fully immersed in 1h in organic electrolyte, weigh the mass change for impregnating front and back, by impregnate front and back it is of poor quality with it is first
The ratio of prothyl amount obtains liquid holdup.Calculation formula (2-1):
In formula: WiIt indicates to hold liquid quality after diaphragm impregnates electrolyte；W0Indicate the initial weight of dry diaphragm.
C) thermal stability
Thermal stability is an important factor for influencing cell safety.In the charge and discharge process of lithium ion battery, system temperature
It will continue to increase.(pure PE film is about 140 DEG C), the cellular structure of diaphragm near the fusing point that temperature rises to diaphragm material
It can occur to collapse and melt, carry out automatic shutoff, form the insulation polyalkene diaphragm of dense non-porous, terminate electrochemical reaction, it is ensured that
Cell safety.When experiment carries out, the PE diaphragm after before modified is placed in 130 DEG C of vacuum drying ovens, constant temperature is kept for 30 minutes.It will
The PE film of heat treatment front and back, which is placed on millimeter squared paper, carries out area measurement, and the front and back area measured substitutes into formula (2-
2) shrinking percentage of the diaphragm at 130 DEG C, can be obtained, to evaluate the security performance of lithium electric separator.Calculation formula is such as
Under:
Wherein: AiIndicate size of the diaphragm before heat treatment in room temperature；A0Indicate the area of thermally treated metacneme
Size.
D) ionic conductivity
Usually, parameter one of of the ionic conductivity (σ) as characterization diaphragm electrochemical performance, is very important.
Higher ionic conductivity, represent in system can free-moving zwitterion number it is more, this is for improving the initial of battery
Discharge capacity plays very big help.Using specific mold, pass through the ac impedance measurement of CHI660E electrochemical workstation
Program obtains system resistance value, by calculating to obtain the occurrence of ionic conductivity.The both ends of mold are stainless steel substrates, simulation
The working electrode of normal battery and to electrode will impregnate the lithium electric separator after electrolyte 12h and be packaged between two electrodes, forms
Stainless steel/diaphragm/stainless steel sandwich structure, and wrap up sealed membrane outside to block influence of the air to built-in system.It surveys
The parameter of examination is set as 1MHz-10mHz, room temperature (25 DEG C).It is as follows by the formula (2-3) of computing the resistor value ionic conductivity:
Wherein: l represents the thickness of diaphragm；S represents effective area of the diaphragm for ac impedance measurement；RsRepresentative passes through
The membrane electrical resistance value that ac impedance measurement program obtains.
E) transference number of ions
Transference number of ions (t hereinLi +) transport number that generally refers to lithium ion in system, by chronoamperometry and friendship
Two test programs of flow impedance combine, to obtain lithium ion transference number figure.The first two test is different therewith, in mold system, two
Piece lithium piece respectively as the working electrode of system and to electrode, centre to impregnate the diaphragm of electrolyte, thus formed lithium piece/every
Film/lithium piece sandwich structure.10mV voltage is applied to mold, the impedance of test polarization front and back and polarization current change, from
And corresponding resistance value and current value are obtained, it is substituted into formula (2-4):
Wherein: Δ V is polarizing voltage (10mV)；I0For initial current；IsFor steady-state current；R0For initial resistivity value；Rs
For steadying resistance value.
(2) test result:
Embodiment 1-3 and the lithium battery diaphragm of comparative example 1 are tested for the property according to the method described above, test result
As shown in table 1.
1 lithium battery diaphragm performance test data table of table
By above data, as can be seen that modified diaphragm occurs, air penetrability is increased, liquid holdup increases, puncture strength
The phenomenon that raising, ionic conductivity increase, main reason is that: air penetrability is characterization lithium ion battery separator cellular structure
One of important parameter usually indicates that unit is the second (s) with Gurley value.Its physical significance is designated volume under normal pressure state
Air pass through the time required for diaphragm specific region completely.In this chapters and sections, 100mL air is used.Gurley value is got over
Greatly, illustrate that the interstructural connectivity of diaphragm internal gutter is poorer；Otherwise Gurley value is smaller, illustrates diaphragm internal gutter structure
Permeability is better.Experiment tests the air penetrability of diaphragm using UEC-1012-A.The addition of organic binder increases
Liquid inhales the amount overlayed on diaphragm, therefore liquid holdup increases.After draw angle says that diaphragm reaches ultimate tensile strength fracture,
The binder on surface can also properly increase its tensile strength, say that the pure thorn of diaphragm one can rupture on puncture strength, then its surface
Coat one layer of slurry, when puncture first punctures the slurry on surface, could pierce through diaphragm, care for puncture strength and be greatly improved.Ion
Conductivity and transference number of ions are all related with electrolyte, and liquid holdup rises, therefore it is increased.
Embodiment 4
The preparation step of embodiment 4 is substantially the same manner as Example 1, and distinctive points are only that inorganic nano-particle is three oxidations
Two aluminum nanoparticles.
The compound lithium ion battery separator prepared through the above method, by substrate layer and the nothing that substrate layer surface is arranged in
Machine/organic composite porous film layer is constituted, and substrate layer is PE film；Inorganic/organic composite porous film layer is to receive containing aluminum oxide
The composite layer of rice corpuscles and Kynoar (PVDF), inorganic/organic composite porous film layer substrate layer it is unilateral with a thickness of
3um or so.
Embodiment 5
The preparation step of embodiment 5 is substantially the same manner as Example 1, and distinctive points are only that inorganic nano-particle for sial point
Son sieve nanoparticle.
The compound lithium ion battery separator prepared through the above method, by substrate layer and the nothing that substrate layer surface is arranged in
Machine/organic composite porous film layer is constituted, and substrate layer is PE film；Inorganic/organic composite porous film layer is to receive containing Si-Al molecular sieve
The composite layer of rice corpuscles and Kynoar (PVDF), inorganic/organic composite porous film layer substrate layer it is unilateral with a thickness of
3um or so.
Embodiment 6
(1) deionization coating preparation: is added in inorganic aqueous dispersion liquid, organic water borne dispersion liquid and surfactant
It stirs 3 hours and is uniformly mixed in water, coating is made；Wherein, inorganic aqueous dispersion liquid is the water nano SiO of 30% solid content2
Dispersion liquid；Organic water borne dispersion liquid is Kynoar (PVDF) dispersion liquid of 5% solid content；Surfactant is alkyl phenol
Polyoxyethylene ether；Wherein, the additional amount of inorganic aqueous dispersion liquid is 30wt%, and the additional amount of organic water borne dispersion liquid is
10wt%, the additional amount of surfactant are 0.5wt%, and the additional amount of deionized water is 59.5wt%.Inorganic aqueous dispersion liquid
The partial size of middle inorganic particulate is 30-80nm, and the partial size of organic filler is 250-400nm in organic water borne dispersion liquid.
(2) 12 μm of clean pure PE diaphragms are infiltrated into configured coating by pulling machine, carry out lifting coating,
Setting decrease speed is 100mm/min, rate of climb 60mm/min.After diaphragm carries out lifting coating, room temperature is dry in air
Dry 20min, then 100 DEG C of dry 0.5h in vacuum drying oven.
The compound lithium ion battery separator prepared through the above method, by substrate layer and the nothing that substrate layer surface is arranged in
Machine/organic composite porous film layer is constituted, and substrate layer is PE film；Inorganic/organic composite porous film layer is to contain inorganic SiO2Nanometer
The composite layer of particle and Kynoar (PVDF), inorganic/organic composite porous film layer is in substrate layer unilateral side with a thickness of 2um
Left and right.
Embodiment 7
(1) deionization coating preparation: is added in inorganic aqueous dispersion liquid, organic water borne dispersion liquid and surfactant
It stirs 3 hours and is uniformly mixed in water, coating is made；Wherein, inorganic aqueous dispersion liquid is the water nano SiO of 70% solid content2
Dispersion liquid；Organic water borne dispersion liquid is the acrylate dispersion liquid of 10% solid content；Surfactant is carboxylic acid potassium type anion
Fluorocarbon surfactant FC-5；Wherein, the additional amount of inorganic aqueous dispersion liquid is 35wt%, the addition of organic water borne dispersion liquid
Amount is 15wt%, and the additional amount of surfactant is 2wt%, and the additional amount of deionized water is 48wt%.Inorganic aqueous dispersion liquid
The partial size of middle inorganic particulate is 120-150nm.The partial size of organic filler is 100-200nm in organic water borne dispersion liquid.
(2) 12 μm of clean pure PE diaphragms are infiltrated into configured coating by pulling machine, carry out lifting coating,
Setting decrease speed is 100mm/min, rate of climb 60mm/min.After diaphragm carries out lifting coating, room temperature is dry in air
Dry 30min, then 80 DEG C of dry 1.5h in vacuum drying oven.
The compound lithium ion battery separator prepared through the above method, by substrate layer and the nothing that substrate layer surface is arranged in
Machine/organic composite porous film layer is constituted, and substrate layer is PE film；Inorganic/organic composite porous film layer is to contain inorganic SiO2Nanometer
The composite layer of particle and acrylate, inorganic/organic composite porous film layer is in substrate layer unilateral side with a thickness of 2um or so.
Embodiment 8
(1) deionization coating preparation: is added in inorganic aqueous dispersion liquid, organic water borne dispersion liquid and surfactant
It stirs 3 hours and is uniformly mixed in water, coating is made；Wherein, inorganic aqueous dispersion liquid is the water nano SiO of 60% solid content2
Dispersion liquid；Organic water borne dispersion liquid is the polyurethane dispersing liquid of 10% solid content；Surfactant is aliphatic acid polyethenoxy
Ester；Wherein, the additional amount of inorganic aqueous dispersion liquid is 25wt%, and the additional amount of organic water borne dispersion liquid is 13wt%, and surface is living
Property agent additional amount be 2wt%, the additional amount of deionized water is 60wt%.The partial size of inorganic particulate in inorganic aqueous dispersion liquid
For 10-50nm.The partial size of organic filler is 200-350nm in organic water borne dispersion liquid.
(2) 12 μm of clean pure PE diaphragms are infiltrated into configured coating by pulling machine, carry out lifting coating,
Setting decrease speed is 100mm/min, rate of climb 60mm/min.After diaphragm carries out lifting coating, room temperature is dry in air
Dry 25min, then 90 DEG C of dry 1h in vacuum drying oven.
The compound lithium ion battery separator prepared through the above method, by substrate layer and the nothing that substrate layer surface is arranged in
Machine/organic composite porous film layer is constituted, and substrate layer is PE film；Inorganic/organic composite porous film layer is to contain inorganic SiO2Nanometer
The composite layer of particle and polyurethane, inorganic/organic composite porous film layer is in substrate layer unilateral side with a thickness of 1um or so.
Embodiment 9
(1) deionization coating preparation: is added in inorganic aqueous dispersion liquid, organic water borne dispersion liquid and surfactant
It stirs 3 hours and is uniformly mixed in water, coating is made；Wherein, inorganic aqueous dispersion liquid is the water nano SiO of 35% solid content2
Dispersion liquid；Organic water borne dispersion liquid is the acrylate dispersion liquid of 20% solid content；Surfactant is carboxylic acid potassium type anion
Fluorocarbon surfactant FC-5；Wherein, the additional amount of inorganic aqueous dispersion liquid is 50t%, the additional amount of organic water borne dispersion liquid
For 20wt%, the additional amount of surfactant is 3wt%, and the additional amount of deionized water is 27wt%.In inorganic aqueous dispersion liquid
The partial size of inorganic particulate is 60-100nm；The partial size of organic filler is 300-500nm in organic water borne dispersion liquid.
(2) 12 μm of clean pure PE diaphragms are infiltrated into configured coating by pulling machine, carry out lifting coating,
Setting decrease speed is 100mm/min, rate of climb 60mm/min.After diaphragm carries out lifting coating, room temperature is dry in air
Dry 30min, then 80 DEG C of dry 1.5h in vacuum drying oven.
The compound lithium ion battery separator prepared through the above method, by substrate layer and the nothing that substrate layer surface is arranged in
Machine/organic composite porous film layer is constituted, and substrate layer is PE film；Inorganic/organic composite porous film layer is to contain inorganic SiO2Nanometer
The composite layer of particle and acrylate, inorganic/organic composite porous film layer is in substrate layer unilateral side with a thickness of 4um or so.
Embodiment 10
(1) deionization coating preparation: is added in inorganic aqueous dispersion liquid, organic water borne dispersion liquid and surfactant
It stirs 3 hours and is uniformly mixed in water, coating is made；Wherein, inorganic aqueous dispersion liquid is three oxygen of water nano of 35% solid content
Change two aluminium dispersion liquids；Organic water borne dispersion liquid is the acrylate dispersion liquid of 20% solid content；Surfactant is amine oxide type
Cation fluorine carbon surface active agent FC-08；Wherein, the additional amount of inorganic aqueous dispersion liquid is 40t%, organic water borne dispersion liquid
Additional amount be 15wt%, the additional amount of surfactant is 3wt%, and the additional amount of deionized water is 42wt%.It is inorganic aqueous
The partial size of inorganic particulate is 50-100nm in dispersion liquid；The partial size of organic filler is 200-400nm in organic water borne dispersion liquid.
(2) 12 μm of clean pure PE diaphragms are infiltrated into configured coating by pulling machine, carry out lifting coating,
Setting decrease speed is 100mm/min, rate of climb 60mm/min.After diaphragm carries out lifting coating, room temperature is dry in air
Dry 30min, then 60 DEG C of dry 1.5h in vacuum drying oven.
The compound lithium ion battery separator prepared through the above method, by substrate layer and the nothing that substrate layer surface is arranged in
Machine/organic composite porous film layer is constituted, and substrate layer is PE film；Inorganic/organic composite porous film layer is containing inorganic three oxidation two
The composite layer of aluminum nanoparticles and acrylate, inorganic/organic composite porous film layer is in substrate layer unilateral side with a thickness of the left side 3um
It is right.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications
It should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of compound lithium ion battery separator, it is characterized in that: by substrate layer and the inorganic/organic of substrate layer surface is arranged in
Compound porous film layer is constituted, and the substrate layer is polyolefin porous membrane；The inorganic/organic composite porous film layer is containing inorganic
The composite layer of nanoparticle and aqueous binders, the inorganic/organic composite porous film layer is in substrate layer unilateral side with a thickness of 1-
4um。
2. a kind of compound lithium ion battery separator according to claim 1, it is characterised in that: the polyolefin porous membrane
For one of polyethylene porous film, polypropylene porous membrane or polypropylene, polyethylene/polypropylene composite materials porous membrane, institute
State polyolefin porous membrane with a thickness of 7-16 μm.
3. a kind of compound lithium ion battery separator according to claim 1, it is characterised in that: the inorganic nano-particle
For one of silicon dioxide granule, aluminum oxide particle or Si-Al molecular sieve；The aqueous binders are aqueous polyvinylidene fluorine
One of ethylene, acrylate or dispersion liquid of polyurethane.
4. a kind of preparation method of compound lithium ion battery separator according to claim 1 to 3, which is characterized in that
The following steps are included:
(1) coating preparation: inorganic aqueous dispersion liquid, organic water borne dispersion liquid and surfactant are added in deionized water and stirred
Mix uniformly mixed, obtained coating；
(2) preparation of compound lithium ion battery separator: by substrate layer infiltration into configured coating, lifting coating is carried out
Afterwards, drying at room temperature certain time in air, then in vacuum drying oven under certain temperature it is dry after a certain period of time, be made compound
Type lithium ion battery separator.
5. a kind of preparation method of compound lithium ion battery separator according to claim 4, it is characterised in that: the painting
Each component and its weight percentage in material are as follows:
6. a kind of preparation method of compound lithium ion battery separator according to claim 4, it is characterised in that: the nothing
Machine aqueous liquid dispersion is the dispersion liquid of inorganic nano-particle in water, wherein inorganic nano-particle in inorganic aqueous dispersion liquid
Solid content is 30%-70%；The partial size of inorganic particulate in the inorganic aqueous dispersion liquid is 10-150nm.
7. a kind of preparation method of compound lithium ion battery separator according to claim 4, it is characterised in that: described to have
Machine aqueous liquid dispersion is the dispersion liquid of aqueous binders in water, wherein aqueous binders consolidates in organic water borne dispersion liquid
Content is 5%-20%；The partial size of organic filler is 100-500nm in the organic water borne dispersion liquid.
8. a kind of preparation method of compound lithium ion battery separator according to claim 4, it is characterised in that: described
Surfactant is one of nonionic surfactant and fluorocarbon surfactant；The nonionic surfactant is specific
Are as follows: one of non-ionic polyacrylamide, alkyl phenol polyoxyethylene ether or polyoxyethylene carboxylate, the fluorocarbon surface are living
Property agent specifically: alcohol amine salt type anion fluorocarbon surfactant INTECHEM-01, carboxylic acid potassium type anion fluoro-carbon surface active
One of agent FC-5 or amine oxide type cation fluorine carbon surface active agent FC-08.
9. a kind of preparation method of compound lithium ion battery separator according to claim 4, it is characterised in that: described to mention
Draw the condition of coating are as follows: decrease speed 100mm/min, the rate of climb 60mm/min of lifting.
10. a kind of preparation method of compound lithium ion battery separator according to claim 4, it is characterised in that: in sky
The time of drying at room temperature is 15-30min in gas；Drying condition in vacuum drying oven: vacuum drying temperature is 60-100 DEG C, very
Empty drying time are as follows: 0.5-1.5h.
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| CN111192992A (en) * | 2020-01-20 | 2020-05-22 | 武汉中兴创新材料技术有限公司 | Preparation method and device of ultrathin coating diaphragm |
| CN111509296A (en) * | 2020-04-17 | 2020-08-07 | 合肥国轩高科动力能源有限公司 | Composite all-solid-state polymer electrolyte and preparation method thereof |
| CN115149207A (en) * | 2022-07-19 | 2022-10-04 | 浙江大学 | Composite diaphragm coated by anionic porous material, method thereof and secondary battery |
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