CN107369804A - A kind of preparation method of lithium battery security diaphragm material - Google Patents
A kind of preparation method of lithium battery security diaphragm material Download PDFInfo
- Publication number
- CN107369804A CN107369804A CN201710663950.6A CN201710663950A CN107369804A CN 107369804 A CN107369804 A CN 107369804A CN 201710663950 A CN201710663950 A CN 201710663950A CN 107369804 A CN107369804 A CN 107369804A
- Authority
- CN
- China
- Prior art keywords
- parts
- microporous barrier
- preparation
- lithium battery
- ceramic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- 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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Cell Separators (AREA)
Abstract
The present invention discloses a kind of preparation method of lithium battery security diaphragm material, with the polypropylene containing part super high molecular weight and the polypropylene mixed melting containing part super high molecular weight, then melting extrusion tabletting, microporous barrier one is prepared by cross directional stretch after tabletting, microporous barrier two is prepared by longitudinal stretching after tabletting；With 80 parts of water, 20~50 parts of pretreatment inorganic particulates, 5~8 parts of epoxyns, 10~18 parts of acrylic monomers, 2~5 parts of methyl methacrylates, 8~10 parts of hydroxyethyl methacrylates, 0.15~0.2 part of initiator, 0.3~0.4 part of crosslinking agent prepare ceramic slurry；The coated ceramic slurry between microporous barrier one and microporous barrier two, it is finally hydrophilic treated that blowout disk is prepared.The present invention solves existing ceramic composite membrane imbibition, liquid-keeping property poor performance, and ceramic particle disperses uneven, and ceramic coating layer is difficult to smear the problem of uniform.
Description
Technical field
The present invention relates to lithium ion battery barrier film production field, and in particular to a kind of system of lithium battery security diaphragm material
Preparation Method.
Background technology
Lithium ion battery is mainly made up of positive electrode, negative material, electrolyte, barrier film, five big material of exterior packaging material.
Wherein one of the important component of diaphragm material as lithium ion battery, receives much concern, it is positive and negative that barrier film is placed in battery always
Microporous film between pole, its major function are to separate lithium battery both positive and negative polarity, avoid short circuit, while provide freely for clang ion
Passage, realize closed-loop path.In addition, lithium ion battery separator be it is a kind of there is nanometer level microporous high molecular functional membrane material,
It is required that its associated materials not other with lithium battery system electrolyte inside etc. occurs chemical reaction and influences diaphragm material hydraulic performance decline
And electrolyte composition changes and causes battery performance to decline, therefore the quality of diaphragm material quality directly influences the electricity of lithium battery
The Key Performance Indicators such as current capacity, cycle life.
Because the fusing point of traditional polypropylene diaphragm and polyethylene diagrams is relatively low, respectively 158 DEG C and 125 DEG C, therefore
Both barrier films are easily deformed upon or even melted in the case that battery overheats so that short circuit, Er Qieju occur for both positive and negative polarity
Propylene barrier film and polyethylene diagrams can not effectively prevent the puncture of Li dendrite body so that short circuit occurs for both positive and negative polarity.On improving
Situation is stated, occurs ceramic composite membrane on the market, ceramic composite membrane is the side of a conventional polypropylene barrier film or polyethylene diagrams
Coated ceramic coating.This kind of composite membrane is on the one hand the wellability of ceramic coating and lithium battery electrolytes there is also some shortcomings
It is poor, influence imbibition, the liquid-keeping property of barrier film；On the other hand it is uneven to be that ceramic particle disperses in the slurry, and ceramic slurry
Material is difficult to uniformly smear on basement membrane.
The content of the invention
The present invention provides a kind of preparation method of lithium battery security diaphragm material, is inhaled to solve existing ceramic composite membrane
Liquid, liquid-keeping property poor performance, ceramic particle disperse uneven, and ceramic coating layer is difficult to smear the problem of uniform.
In order to solve the above technical problems, the present invention adopts the following technical scheme that：
A kind of preparation method of lithium battery security diaphragm material, comprises the following steps：
S1. in terms of parts by weight, 100 parts of polypropylene and 80~160 parts of polyethylene blends are taken and then at 240~260 DEG C
Melting extrusion is granulated, and is then cooled down, and material grain is upset and melting extrusion is granulated to obtain coating materials again, by coating materials in 260~280 DEG C
Lower fusion extrusion casting is in blocks, and film forming is then extruded at 200~220 DEG C, and last room temperature cools down to obtain former film；
S2. the cross directional stretch at 3~10 DEG C of the former film in a piece of S1 is taken, then shape 20~30min at 40~60 DEG C
Obtain microporous barrier one, take the longitudinal stretching at 3~10 DEG C of the former film in a piece of S1, then at 40~60 DEG C sizing 20~
30min obtains microporous barrier two, will apply one layer of ceramic layer in the upside of microporous barrier one, then composite micro porous film two on ceramic layer, so
Slowly extruding excludes ceramic slurry unnecessary in ceramic layer and the 15min that shapes at 60 DEG C afterwards, and finally cooling obtains composite membrane；
S3. composite membrane is placed in 30~60min of immersion in hydrophilic processing liquid, then dries, finally obtain blowout disk；Institute
State hydrophilic processing liquid count in parts by weight including：100 parts of water, 5~10 parts of hydrogen peroxide, 3~7 portions of fluorocarbon surfactants.
Further, the ceramic slurry count in parts by weight including：80 parts of water, 20~50 parts of pretreatment inorganic particulates, 5
~8 parts of epoxyns, 10~18 parts of acrylic monomers, 2~5 parts of methyl methacrylates, 8~10 parts of methacrylic acids
Hydroxyl ethyl ester, 0.15~0.2 part of initiator, 0.3~0.4 part of crosslinking agent.
Further, the preparation method of the pretreatment inorganic particulate is：
It is in 25~30% Aqueous Solutions of Polyethylene Glycol, with 200~500r/min's that inorganic particulate is immersed in into mass fraction
Rotating speed stirs 1~2h, then filtering drying, and the inorganic particulate is silica, alundum (Al2O3), titanium dioxide, calcium sulfate
In one or more.
Further, it is 20~25% ultrahigh molecular weight polypropylenes containing mass fraction in the polypropylene, is left part
Containing mass fraction it is 20~25% ultra-high molecular weight polyethylenes in the polyethylene, remaining part is for high component polypropylene
High score weight northylen.
Further, the particle diameter of the pretreatment inorganic particulate is 0.1~3 μm.
Beneficial effects of the present invention：
(1) present invention completes uniformly to mix, poly- third using polypropylene and polyethylene as raw material by the extrusion of mixed melting twice
The film mechanical performance that the composite of alkene and polyethylene is prepared is better than polypropylene screen and polyethylene film；The present invention is in draw direction
Composite ceramic coat among different two panels films, microporous barrier one and microporous barrier two can make up unidirectional tensile resistance mutually not
Foot so that the unidirectional tensile resistance of composite membrane is better than common stretching composite membrane in the same direction, and this composite construction can also be prevented simultaneously
Only lithium Zhi Jing passes through composite membrane by duct, enhances the anti-puncture ability of composite membrane, the hole wall and microporous barrier two of microporous barrier one
Moving towards for hole wall is different, and the duct of ceramic coating is intersected with microporous barrier one, microporous barrier two, therefore ceramic coating, the and of microporous barrier one
Microporous barrier two forms three-dimensional net structure, and three-dimensional net structure can improve the liquid-keeping property of composite membrane.
(2) ceramic coating of the invention sizing is to press to realize by upper and lower two layers of polymers film, therefore can accurately be controlled
The thickness of composite membrane processed, while can also control the thickness of ceramic coating uniform, this complex method is also beneficial to membrane material simultaneously
Follow-up cut out processing.
(3) present invention is handled by hydrophilic processing liquid, can be had enhancing imbibition and liquid-keeping property, is advantageous to the big multiplying power of lithium battery
Electric discharge.
(4) ceramic slurry epoxy resin adhesive of the present invention is used for the viscosity for adjusting slurry so that slurry is in coating
With suitable mobility and viscosity, ceramic slurry passes through acrylic monomers, methyl methacrylate monomer and methacrylic acid
The polymerization of hydroxyl ethyl ester monomer carrys out fixed inorganic particle and bonding film layer up and down, and polymer has the imbibition of strength and protects liquid energy
Power.
(5) inorganic particulate of the invention is wrapped up with polyethylene glycol so that inorganic particulate can uniformly divide in ceramic slurry
Dissipate, can effectively prevent particle aggregation.
(6) contain 20~25% ultrahigh molecular weight polypropylenes in polypropylene of the invention, contain mass fraction in polyethylene
For 20~25% ultra-high molecular weight polyethylenes, ultrahigh molecular weight polypropylene and ultra-high molecular weight polyethylene can improve the molten of material
Point, so as to improve the fusing-off temperature of membrane material.
Brief description of the drawings
Fig. 1 is the structural representation of the present invention.
Symbol description in figure：Microporous barrier 1, ceramic layer 2, microporous barrier 23.
Embodiment
For ease of more fully understanding the present invention, it is illustrated by following instance, these examples belong to the protection of the present invention
Scope, but do not limit the scope of the invention.
Embodiment 1
A kind of preparation method of lithium battery security diaphragm material, comprises the following steps：
S1. inorganic particulate is pre-processed：It is 25% to gather that the alundum (Al2O3) that particle mean size is 0.1 μm is immersed in into mass fraction
In glycol water, 2h is stirred with 200r/min rotating speed, then filtering drying；
S2. configure ceramic slurry, ceramic slurry count in parts by weight including：80 parts of water, 50 parts of pretreatment inorganic particulates, 5
Part epoxyn, 12 parts of acrylic monomers, 3 parts of methyl methacrylates, 9 parts of hydroxyethyl methacrylates, 0.15 part
Initiator, 0.3 part of crosslinking agent.
S3. in terms of parts by weight, 100 parts of polypropylene and 100 parts of polyethylene blends and then the melting extrusion at 250 DEG C are taken
Be granulated, then cool down, material grain is upset and melting extrusion is granulated to obtain coating materials again, by coating materials at 260 DEG C melting extrusion stream
Prolong in flakes, film forming is then extruded at 220 DEG C, last room temperature cools down to obtain former film；
S4. the cross directional stretch at 4 DEG C of the former film in a piece of S1 is taken, the 30min that then shaped at 60 DEG C obtains microporous barrier one
1, the longitudinal stretching at 4 DEG C of the former film in a piece of S1 is taken, the 30min that then shaped at 60 DEG C obtains microporous barrier 23, will be in micropore
The upside of film 1 applies one layer of ceramic layer 2, then the composite micro porous film 23 on ceramic layer 2, and then slowly extruding excludes at 60 DEG C
Unnecessary ceramic slurry and the 15min that shapes in ceramic layer 2, finally cooling obtain composite membrane；
S5. composite membrane is placed in hydrophilic processing liquid and soaks 30min, then dried, finally obtain blowout disk；The parent
Water process liquid count in parts by weight including：100 parts of water, 10 parts of hydrogen peroxide, 5 portions of fluorocarbon surfactants.
Containing mass fraction it is 20% ultrahigh molecular weight polypropylene in the polypropylene, it is high component poly- third to be left part
Alkene, containing mass fraction it is 25% ultra-high molecular weight polyethylene in the polyethylene, it is high score weight northylen to be left part.
Embodiment 2
A kind of preparation method of lithium battery security diaphragm material, comprises the following steps：
S1. inorganic particulate is pre-processed：Alundum (Al2O3) and silica that particle mean size is 2 μm are immersed in mass fraction
In 28% Aqueous Solutions of Polyethylene Glycol, to stir 1.5h with 400r/min rotating speed, then filtering drying；
S2. configure ceramic slurry, ceramic slurry count in parts by weight including：80 parts of water, 30 parts of pretreatment inorganic particulates, 6
Part epoxyn, 18 parts of acrylic monomers, 5 parts of methyl methacrylates, 8 parts of hydroxyethyl methacrylates, 0.18 part
Initiator, 0.35 part of crosslinking agent.
S3. in terms of parts by weight, take 100 parts of polypropylene and 80 parts of polyethylene blends then at 240 DEG C melting extrusion make
Grain, is then cooled down, and material grain is upset and melting extrusion is granulated to obtain coating materials again, by coating materials at 270 DEG C fusion extrusion casting
In flakes, film forming is then extruded at 210 DEG C, last room temperature cools down to obtain former film；
S4. the cross directional stretch at 3 DEG C of the former film in a piece of S1 is taken, the 25min that then shaped at 50 DEG C obtains microporous barrier one
1, the longitudinal stretching at 3 DEG C of the former film in a piece of S1 is taken, the 25min that then shaped at 50 DEG C obtains microporous barrier 23, will be in micropore
The upside of film 1 applies one layer of ceramic layer 2, then the composite micro porous film 23 on ceramic layer 2, and then slowly extruding excludes at 60 DEG C
Unnecessary ceramic slurry and the 15min that shapes in ceramic layer 2, finally cooling obtain composite membrane；
S5. composite membrane is placed in hydrophilic processing liquid and soaks 60min, then dried, finally obtain blowout disk；The parent
Water process liquid count in parts by weight including：100 parts of water, 8 parts of hydrogen peroxide, 7 portions of fluorocarbon surfactants.
Containing mass fraction it is 23% ultrahigh molecular weight polypropylene in the polypropylene, it is high component poly- third to be left part
Alkene, containing mass fraction it is 20% ultra-high molecular weight polyethylene in the polyethylene, it is high score weight northylen to be left part.
Embodiment 3
A kind of preparation method of lithium battery security diaphragm material, comprises the following steps：
S1. inorganic particulate is pre-processed：It is 30% poly- second that the alundum (Al2O3) that particle mean size is 3 μm is immersed in into mass fraction
In two alcohol solutions, 1h is stirred with 500r/min rotating speed, then filtering drying；
S2. configure ceramic slurry, ceramic slurry count in parts by weight including：80 parts of water, 20 parts of pretreatment inorganic particulates, 8
Part epoxyn, 10 parts of acrylic monomers, 2 parts of methyl methacrylates, 10 parts of hydroxyethyl methacrylates, 0.2 part
Initiator, 0.4 part of crosslinking agent.
S3. in terms of parts by weight, 100 parts of polypropylene and 160 parts of polyethylene blends and then the melting extrusion at 260 DEG C are taken
Be granulated, then cool down, material grain is upset and melting extrusion is granulated to obtain coating materials again, by coating materials at 280 DEG C melting extrusion stream
Prolong in flakes, film forming is then extruded at 200 DEG C, last room temperature cools down to obtain former film；
S4. the cross directional stretch at 10 DEG C of the former film in a piece of S1 is taken, the 20min that then shaped at 40 DEG C obtains microporous barrier one
1, the longitudinal stretching at 10 DEG C of the former film in a piece of S1 is taken, the 20min that then shaped at 40 DEG C obtains microporous barrier 23, will be micro-
The upside of pore membrane 1 applies one layer of ceramic layer 2, then the composite micro porous film 23 on ceramic layer 2, and then slowly extruding is arranged at 60 DEG C
Except ceramic slurry and the 15min that shapes unnecessary in ceramic layer 2, finally cooling obtains composite membrane；
S5. composite membrane is placed in hydrophilic processing liquid and soaks 45min, then dried, finally obtain blowout disk；The parent
Water process liquid count in parts by weight including：100 parts of water, 5 parts of hydrogen peroxide, 4 portions of fluorocarbon surfactants.
Containing mass fraction it is 25% ultrahigh molecular weight polypropylene in the polypropylene, it is high component poly- third to be left part
Alkene, containing mass fraction it is 22% ultra-high molecular weight polyethylene in the polyethylene, it is high score weight northylen to be left part.
Embodiment 4
A kind of preparation method of lithium battery security diaphragm material, comprises the following steps：
S1. inorganic particulate is pre-processed：Alundum (Al2O3), titanium dioxide and the calcium sulfate immersion for being 2.5 μm by particle mean size
In mass fraction is 30% Aqueous Solutions of Polyethylene Glycol, 1h is stirred with 400r/min rotating speed, then filtering drying；
S2. configure ceramic slurry, ceramic slurry count in parts by weight including：80 parts of water, 45 parts of pretreatment inorganic particulates, 8
Part epoxyn, 16 parts of acrylic monomers, 2 parts of methyl methacrylates, 10 parts of hydroxyethyl methacrylates, 0.16 part
Initiator, 0.4 part of crosslinking agent.
S3. in terms of parts by weight, 100 parts of polypropylene and 120 parts of polyethylene blends and then the melting extrusion at 260 DEG C are taken
Be granulated, then cool down, material grain is upset and melting extrusion is granulated to obtain coating materials again, by coating materials at 270 DEG C melting extrusion stream
Prolong in flakes, film forming is then extruded at 200 DEG C, last room temperature cools down to obtain former film；
S4. the cross directional stretch at 10 DEG C of the former film in a piece of S1 is taken, the 20min that then shaped at 60 DEG C obtains microporous barrier one
1, the longitudinal stretching at 10 DEG C of the former film in a piece of S1 is taken, the 20min that then shaped at 60 DEG C obtains microporous barrier 23, will be micro-
The upside of pore membrane 1 applies one layer of ceramic layer 2, then the composite micro porous film 23 on ceramic layer 2, and then slowly extruding is arranged at 60 DEG C
Except ceramic slurry and the 15min that shapes unnecessary in ceramic layer 2, finally cooling obtains composite membrane；
S5. composite membrane is placed in hydrophilic processing liquid and soaks 45min, then dried, finally obtain blowout disk；The parent
Water process liquid count in parts by weight including：100 parts of water, 7 parts of hydrogen peroxide, 4 portions of fluorocarbon surfactants.
Containing mass fraction it is 25% ultrahigh molecular weight polypropylene in the polypropylene, it is high component poly- third to be left part
Alkene, containing mass fraction it is 25% ultra-high molecular weight polyethylene in the polyethylene, it is high score weight northylen to be left part.
Embodiment 5
A kind of preparation method of lithium battery security diaphragm material, comprises the following steps：
S1. inorganic particulate is pre-processed：It is 26% poly- second two that the silica that particle mean size is 3 μm is immersed in into mass fraction
In alcohol solution, 2h is stirred with 400r/min rotating speed, then filtering drying；
S2. configure ceramic slurry, ceramic slurry count in parts by weight including：80 parts of water, 40 parts of pretreatment inorganic particulates, 8
Part epoxyn, 16 parts of acrylic monomers, 2 parts of methyl methacrylates, 10 parts of hydroxyethyl methacrylates, 0.19 part
Initiator, 0.35 part of crosslinking agent.
S3. in terms of parts by weight, 100 parts of polypropylene and 100 parts of polyethylene blends and then the melting extrusion at 260 DEG C are taken
Be granulated, then cool down, material grain is upset and melting extrusion is granulated to obtain coating materials again, by coating materials at 275 DEG C melting extrusion stream
Prolong in flakes, film forming is then extruded at 215 DEG C, last room temperature cools down to obtain former film；
S4. taking the former film in a piece of S1, cross directional stretch, the 25min that then shaped at 45 DEG C obtain microporous barrier one at 5 DEG C
1, taking the former film in a piece of S1, longitudinal stretching, the 20min that then shaped at 40 DEG C obtain microporous barrier 23 at 5 DEG C, will be in micropore
The upside of film 1 applies one layer of ceramic layer 2, then the composite micro porous film 23 on ceramic layer 2, and then slowly extruding excludes at 60 DEG C
Unnecessary ceramic slurry and the 15min that shapes in ceramic layer 2, finally cooling obtain composite membrane；
S5. composite membrane is placed in hydrophilic processing liquid and soaks 45min, then dried, finally obtain blowout disk；The parent
Water process liquid count in parts by weight including：100 parts of water, 10 parts of hydrogen peroxide, 3 portions of fluorocarbon surfactants.
Containing mass fraction it is 25% ultrahigh molecular weight polypropylene in the polypropylene, it is high component poly- third to be left part
Alkene, containing mass fraction it is 20% ultra-high molecular weight polyethylene in the polyethylene, it is high score weight northylen to be left part.
Embodiment 6
A kind of preparation method of lithium battery security diaphragm material, comprises the following steps：
S1. inorganic particulate is pre-processed：It is 28% poly- second that the alundum (Al2O3) that particle mean size is 3 μm is immersed in into mass fraction
In two alcohol solutions, 1h is stirred with 200r/min rotating speed, then filtering drying；
S2. configure ceramic slurry, ceramic slurry count in parts by weight including：80 parts of water, 35 parts of pretreatment inorganic particulates, 6
Part epoxyn, 15 parts of acrylic monomers, 3 parts of methyl methacrylates, 8 parts of hydroxyethyl methacrylates, 0.15 part
Initiator, 0.33 part of crosslinking agent.
S3. in terms of parts by weight, 100 parts of polypropylene and 130 parts of polyethylene blends and then the melting extrusion at 260 DEG C are taken
Be granulated, then cool down, material grain is upset and melting extrusion is granulated to obtain coating materials again, by coating materials at 280 DEG C melting extrusion stream
Prolong in flakes, film forming is then extruded at 200 DEG C, last room temperature cools down to obtain former film；
S4. the cross directional stretch at 3 DEG C of the former film in a piece of S1 is taken, the 30min that then shaped at 50 DEG C obtains microporous barrier one
1, the longitudinal stretching at 10 DEG C of the former film in a piece of S1 is taken, the 20min that then shaped at 40 DEG C obtains microporous barrier 23, will be micro-
The upside of pore membrane 1 applies one layer of ceramic layer 2, then the composite micro porous film 23 on ceramic layer 2, and then slowly extruding is arranged at 60 DEG C
Except ceramic slurry and the 15min that shapes unnecessary in ceramic layer 2, finally cooling obtains composite membrane；
S5. composite membrane is placed in hydrophilic processing liquid and soaks 45min, then dried, finally obtain blowout disk；The parent
Water process liquid count in parts by weight including：100 parts of water, 6 parts of hydrogen peroxide, 6 portions of fluorocarbon surfactants.
Containing mass fraction it is 20% ultrahigh molecular weight polypropylene in the polypropylene, it is high component poly- third to be left part
Alkene, containing mass fraction it is 20% ultra-high molecular weight polyethylene in the polyethylene, it is high score weight northylen to be left part.
Comparative example 1
A kind of preparation method of lithium battery security diaphragm material, comprises the following steps：
S1. in terms of parts by weight, 100 parts of polypropylene and 100 parts of polyethylene blends and then the melting extrusion at 250 DEG C are taken
Be granulated, then cool down, material grain is upset and melting extrusion is granulated to obtain coating materials again, by coating materials at 260 DEG C melting extrusion stream
Prolong in flakes, film forming is then extruded at 220 DEG C, last room temperature cools down to obtain former film；
S2. the cross directional stretch at 4 DEG C of the former film in a piece of S1 is taken, the 30min that then shaped at 60 DEG C obtains microporous barrier one,
The longitudinal stretching at 4 DEG C of the former film in a piece of S1 is taken, the 30min that then shaped at 60 DEG C obtains microporous barrier two, will be in microporous barrier
One upside composite micro porous film two obtains composite membrane；
S3. composite membrane is placed in hydrophilic processing liquid and soaks 30min, then dried, finally obtain blowout disk；The parent
Water process liquid count in parts by weight including：100 parts of water, 10 parts of hydrogen peroxide, 5 portions of fluorocarbon surfactants.
Containing mass fraction it is 20% ultrahigh molecular weight polypropylene in the polypropylene, it is high component poly- third to be left part
Alkene, containing mass fraction it is 25% ultra-high molecular weight polyethylene in the polyethylene, it is high score weight northylen to be left part.
Comparative example 2
S1. inorganic particulate is pre-processed：It is 25% to gather that the alundum (Al2O3) that particle mean size is 0.1 μm is immersed in into mass fraction
In glycol water, 2h is stirred with 200r/min rotating speed, then filtering drying；
S2. configure ceramic slurry, ceramic slurry count in parts by weight including：80 parts of water, 50 parts of pretreatment inorganic particulates, 5
Part epoxyn, 12 parts of acrylic monomers, 3 parts of methyl methacrylates, 9 parts of hydroxyethyl methacrylates, 0.15 part
Initiator, 0.3 part of crosslinking agent.
S3. in terms of parts by weight, 100 parts of polypropylene and 100 parts of polyethylene blends and then the melting extrusion at 250 DEG C are taken
Be granulated, then cool down, material grain is upset and melting extrusion is granulated to obtain coating materials again, by coating materials at 260 DEG C melting extrusion stream
Prolong in flakes, film forming is then extruded at 220 DEG C, last room temperature cools down to obtain former film；
S4. the cross directional stretch at 4 DEG C of the former film in a piece of S1 is taken, the 30min that then shaped at 60 DEG C obtains microporous barrier one,
One layer of ceramic slurry will be applied in the upside of microporous barrier one, then shape 15min at 60 DEG C, and finally cooling obtains composite membrane；
S5. composite membrane is placed in hydrophilic processing liquid and soaks 30min, then dried, finally obtain blowout disk；The parent
Water process liquid count in parts by weight including：100 parts of water, 10 parts of hydrogen peroxide, 5 portions of fluorocarbon surfactants.
Containing mass fraction it is 20% ultrahigh molecular weight polypropylene in the polypropylene, it is high component poly- third to be left part
Alkene, containing mass fraction it is 25% ultra-high molecular weight polyethylene in the polyethylene, it is high score weight northylen to be left part.
Performance test
To embodiment 1~6, comparative example 1 and the sample of comparative example 2 are pierced through with electronic universal tester, record puncture intensity；Will
Embodiment 1~6, comparative example 1 and the sample of comparative example 2 are immersed in 30min in lithium battery electrolytes, surface electrolysis of being gone out after taking-up
Liquid, measure and record its imbibition ability, electrolyte is 1mol/L LiPF6/EC:DEC:DEC=1:1:1 (V/V/V) solution；Adopt
The closed pore temperature of embodiment 1~6, comparative example 1 and the sample of comparative example 2 is determined with the sudden change of resistivity method of UL2591-2009 standards, it is real
It is as shown in the table to test data.
| Barrier film sample | Anti-puncture intensity (N) | Pick up (%) | Closed pore temperature (DEG C) |
| Embodiment 1 | 6.3 | 168 | 175 |
| Embodiment 2 | 6.1 | 163 | 181 |
| Embodiment 3 | 6.0 | 165 | 177 |
| Embodiment 4 | 6.5 | 170 | 183 |
| Embodiment 5 | 6.2 | 161 | 178 |
| Embodiment 6 | 6.1 | 176 | 171 |
| Comparative example 1 | 4.9 | 128 | 158 |
| Comparative example 2 | 5.8 | 140 | 166 |
It can be seen from upper table, the anti-puncture intensity of comparative example 1 of no ceramic layer is minimum, and ceramic layer can effectively strengthen the anti-of barrier film
Puncture intensity；The barrier film pick up of three-decker is more than the pick up of two-layer separator, and the pick up of comparative example 2 is more than comparative example 1,
There is the absorbent of polymer and the ceramic layer of inorganic particulate composition strong；Ceramic layer is effectively improved the closed pore temperature of barrier film.
Protection scope of the present invention is not limited merely to above-described embodiment, and all technical schemes for belonging under thinking of the present invention are equal
Belong to protection scope of the present invention.It should be pointed out that for those skilled in the art, the present invention is not being departed from
Some improvements and modifications under the premise of principle, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (5)
1. a kind of preparation method of lithium battery security diaphragm material, it is characterised in that comprise the following steps：
S1. in terms of parts by weight, 100 parts of polypropylene and 80~160 parts of polyethylene blends is taken and then are melted at 240~260 DEG C
Extruding pelletization, then cool down, material grain is upset and melting extrusion is granulated to obtain coating materials again, coating materials is melted at 260~280 DEG C
It is in blocks to melt extrusion curtain coating, film forming is then extruded at 200~220 DEG C, last room temperature cools down to obtain former film；
S2. the cross directional stretch at 3~10 DEG C of the former film in a piece of S1 is taken, the 20~30min that then shaped at 40~60 DEG C is obtained
Microporous barrier one (1), the longitudinal stretching at 3~10 DEG C of the former film in a piece of S1 is taken, then shape 20~30min at 40~60 DEG C
Microporous barrier two (3) is obtained, one layer of ceramic layer (2) will be applied on the upside of microporous barrier one (1), it is then composite microporous on ceramic layer (2)
Film two (3), then slowly extruding excludes ceramic slurry unnecessary in ceramic layer (2) and the 15min that shapes at 60 DEG C, finally cools down
Obtain composite membrane；
S3. composite membrane is placed in 30~60min of immersion in hydrophilic processing liquid, then dries, finally obtain blowout disk；The parent
Water process liquid count in parts by weight including：100 parts of water, 5~10 parts of hydrogen peroxide, 3~7 portions of fluorocarbon surfactants.
A kind of 2. preparation method of lithium battery security diaphragm material according to claim 1, it is characterised in that the pottery
Porcelain slurry count in parts by weight including：80 parts of water, 20~50 parts of pretreatment inorganic particulates, 5~8 parts of epoxyns, 10
~18 parts of acrylic monomers, 2~5 parts of methyl methacrylates, 8~10 parts of hydroxyethyl methacrylates, 0.15~0.2 part of initiation
Agent, 0.3~0.4 part of crosslinking agent.
3. the preparation method of a kind of lithium battery security diaphragm material according to claim 2, it is characterised in that described pre-
Processing inorganic particulate preparation method be：
It is in 25~30% Aqueous Solutions of Polyethylene Glycol, with 200~500r/min rotating speed that inorganic particulate is immersed in into mass fraction
1~2h is stirred, then filtering drying, the inorganic particulate is in silica, alundum (Al2O3), titanium dioxide, calcium sulfate
It is one or more of.
4. the preparation method of a kind of lithium battery security diaphragm material according to claim 1, it is characterised in that described poly-
Containing mass fraction it is 20~25% ultrahigh molecular weight polypropylenes in propylene, remaining part is high component polypropylene, the poly- second
Containing mass fraction it is 20~25% ultra-high molecular weight polyethylenes in alkene, it is high score weight northylen to be left part.
A kind of 5. preparation method of lithium battery security diaphragm material according to Claims 2 or 3, it is characterised in that institute
The particle diameter for stating pretreatment inorganic particulate is 0.1~3 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710663950.6A CN107369804A (en) | 2017-08-06 | 2017-08-06 | A kind of preparation method of lithium battery security diaphragm material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710663950.6A CN107369804A (en) | 2017-08-06 | 2017-08-06 | A kind of preparation method of lithium battery security diaphragm material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107369804A true CN107369804A (en) | 2017-11-21 |
Family
ID=60309171
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710663950.6A Pending CN107369804A (en) | 2017-08-06 | 2017-08-06 | A kind of preparation method of lithium battery security diaphragm material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107369804A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108123086A (en) * | 2017-11-16 | 2018-06-05 | 深圳市博盛新材料有限公司 | A kind of method and lithium ion battery separator for preparing lithium ion battery separator |
| CN108305978A (en) * | 2018-01-09 | 2018-07-20 | 深圳中兴创新材料技术有限公司 | A kind of lithium ion battery composite separation membrane and preparation method thereof |
| CN108305972A (en) * | 2017-12-29 | 2018-07-20 | 深圳中兴创新材料技术有限公司 | A kind of ceramic-coated separator and preparation method and application |
| CN109860474A (en) * | 2018-12-07 | 2019-06-07 | 上海空间电源研究所 | A kind of active membrane and preparation method thereof |
| CN110265611A (en) * | 2018-03-12 | 2019-09-20 | 江苏海基新能源股份有限公司 | High-multiplying-power battery diaphragm and lithium ion secondary battery |
| CN112582749A (en) * | 2020-12-11 | 2021-03-30 | 重庆金美新材料科技有限公司 | Safe lithium ion battery diaphragm, preparation method and lithium ion battery |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101369645A (en) * | 2008-09-23 | 2009-02-18 | 天津力神电池股份有限公司 | Method of manufacturing diaphragm used for high security lithium ion secondary battery |
| CN101702428A (en) * | 2009-11-10 | 2010-05-05 | 东莞新能源科技有限公司 | Porous polyolefine isolating film |
| CN102263220A (en) * | 2011-06-22 | 2011-11-30 | 广东博特动力能源有限公司 | Preparation method for battery diaphragm |
| CN105355811A (en) * | 2015-10-29 | 2016-02-24 | 乐凯胶片股份有限公司 | Polyolefin microporous membrane, making method thereof, and lithium ion battery |
| CN105374969A (en) * | 2015-10-28 | 2016-03-02 | 惠州市吉美泰电子科技有限公司 | Lithium battery diaphragm with interlayer, lithium battery and manufacturing method of lithium battery diaphragm |
-
2017
- 2017-08-06 CN CN201710663950.6A patent/CN107369804A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101369645A (en) * | 2008-09-23 | 2009-02-18 | 天津力神电池股份有限公司 | Method of manufacturing diaphragm used for high security lithium ion secondary battery |
| CN101702428A (en) * | 2009-11-10 | 2010-05-05 | 东莞新能源科技有限公司 | Porous polyolefine isolating film |
| CN102263220A (en) * | 2011-06-22 | 2011-11-30 | 广东博特动力能源有限公司 | Preparation method for battery diaphragm |
| CN105374969A (en) * | 2015-10-28 | 2016-03-02 | 惠州市吉美泰电子科技有限公司 | Lithium battery diaphragm with interlayer, lithium battery and manufacturing method of lithium battery diaphragm |
| CN105355811A (en) * | 2015-10-29 | 2016-02-24 | 乐凯胶片股份有限公司 | Polyolefin microporous membrane, making method thereof, and lithium ion battery |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108123086A (en) * | 2017-11-16 | 2018-06-05 | 深圳市博盛新材料有限公司 | A kind of method and lithium ion battery separator for preparing lithium ion battery separator |
| CN108305972A (en) * | 2017-12-29 | 2018-07-20 | 深圳中兴创新材料技术有限公司 | A kind of ceramic-coated separator and preparation method and application |
| CN108305978A (en) * | 2018-01-09 | 2018-07-20 | 深圳中兴创新材料技术有限公司 | A kind of lithium ion battery composite separation membrane and preparation method thereof |
| CN108305978B (en) * | 2018-01-09 | 2022-08-02 | 深圳中兴新材技术股份有限公司 | Lithium ion battery composite diaphragm and preparation method thereof |
| CN110265611A (en) * | 2018-03-12 | 2019-09-20 | 江苏海基新能源股份有限公司 | High-multiplying-power battery diaphragm and lithium ion secondary battery |
| CN110265611B (en) * | 2018-03-12 | 2024-03-08 | 江苏海基新能源股份有限公司 | High-rate battery diaphragm and lithium ion secondary battery |
| CN109860474A (en) * | 2018-12-07 | 2019-06-07 | 上海空间电源研究所 | A kind of active membrane and preparation method thereof |
| CN109860474B (en) * | 2018-12-07 | 2022-04-05 | 上海空间电源研究所 | Active diaphragm and preparation method thereof |
| CN112582749A (en) * | 2020-12-11 | 2021-03-30 | 重庆金美新材料科技有限公司 | Safe lithium ion battery diaphragm, preparation method and lithium ion battery |
| CN112582749B (en) * | 2020-12-11 | 2022-09-13 | 重庆金美新材料科技有限公司 | Safe lithium ion battery diaphragm, preparation method and lithium ion battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107369804A (en) | A kind of preparation method of lithium battery security diaphragm material | |
| CN103066231B (en) | Method for preparing high temperature resistant composite separator by lithium ion battery | |
| CN105932203B (en) | A kind of preparation method of the porosity lithium ion battery separator with inierpeneirating network structure | |
| CN107316968A (en) | A kind of sticky battery diaphragm and the lithium ion battery using the barrier film | |
| CN103102717B (en) | Water-based ceramic coating for lithium ion battery and application thereof | |
| CN103618059B (en) | A kind of macromolecule inorganic coating lithium ion battery separator and preparation method thereof | |
| CN102529247B (en) | Inorganic/organic composite porous lithium battery diaphragm and preparation method thereof | |
| Li et al. | Research on a gel polymer electrolyte for Li-ion batteries | |
| CN108711605A (en) | A kind of composite battery separator film, preparation method and battery | |
| CN107221625B (en) | The gel electrolyte and preparation method of the high nano combined POSS- polyacrylate-coated improved polyalkene diaphragm of thermomechanical property | |
| US20150280197A1 (en) | Composite Porous Separator And Electrochemical Device | |
| WO2022161088A1 (en) | Coating material for light-weight lithium ion battery separator, preparation method therefor, and light-weight lithium ion battery composite separator | |
| CN104766937B (en) | A kind of environment-friendlylithium lithium ion battery membrane and preparation method thereof | |
| CN106784529A (en) | A kind of lithium ion battery separator and preparation method thereof | |
| CN104183805B (en) | A kind of preparation method of ceramic-coated separator | |
| CN106159173A (en) | Composite membrane of polymer prepared by a kind of composite membrane of polymer and preparation method thereof, the method, gel electrolyte, lithium ion battery | |
| CN206210904U (en) | A kind of lithium ion battery barrier film | |
| WO2012061963A1 (en) | Porous membrane and preparation method thereof | |
| CN104953070A (en) | Isolating membrane for lithium ion secondary battery | |
| CN108933219B (en) | A kind of preparation method of lithium battery diaphragm | |
| CN109461871A (en) | A kind of multilayer polyolefine microporous film of dissymmetrical structure and its preparation method and application | |
| CN106816627A (en) | Composite plastic crystal polymer electrolyte material and preparation method thereof | |
| CN103531735A (en) | Polyolefin multilayer micro porous diaphragm for lithium ion battery and preparation method of polyolefin multilayer micro porous diaphragm | |
| CN105895962B (en) | A kind of preparation facilities and preparation method of gel polymer lithium ion battery | |
| CN101826606A (en) | Polytetrafluoroethylene lithium-ion battery separator and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20171121 |