CN109411682A - A kind of lithium battery diaphragm of high thermal stability and preparation method thereof - Google Patents
A kind of lithium battery diaphragm of high thermal stability and preparation method thereof Download PDFInfo
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- CN109411682A CN109411682A CN201811507148.9A CN201811507148A CN109411682A CN 109411682 A CN109411682 A CN 109411682A CN 201811507148 A CN201811507148 A CN 201811507148A CN 109411682 A CN109411682 A CN 109411682A
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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
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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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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- 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
- H01M50/44—Fibrous 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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Abstract
The present invention relates to technical field of lithium batteries, more particularly to a kind of lithium battery diaphragm and preparation method thereof of high thermal stability, lithium battery diaphragm prepared by the present invention is made of polyimides nucleopore membranes, ceramic layer and Electrospun nano-fibers layer, the present invention is successively applied in the upper of basement membrane coated with ceramic layer and Electrospun nano-fibers layer using the polyimides with high heat resistance and high-insulativity as basement membrane；Porous aluminas has preferable thermal conductivity in ceramic layer, can in time conduct the heat on diaphragm, avoids diaphragm and is locally heat-shrinked excessive caused short circuit；Layers of nanofibers can be improved membrane surface uniform pore diameter degree by electrostatic spinning, improve the thermal stability of lithium battery diaphragm, and can combine closely with ceramic layer, avoid falling off for porous aluminas in ceramic layer；Lithium battery diaphragm prepared by the present invention has the characteristics that thermal stability is good, heat-conducting effect is excellent.
Description
Technical field
The present invention relates to technical field of lithium batteries, and in particular to a kind of lithium battery diaphragm of high thermal stability and its preparation side
Method.
Background technique
In the structure of lithium battery, diaphragm is crucial one of interior layer assembly.The performance of diaphragm determines the interface knot of battery
Structure, internal resistance etc. directly affect the characteristics such as capacity, circulation and the security performance of battery, and the diaphragm haveing excellent performance is to raising battery
Comprehensive performance play an important role.The main function of diaphragm is to separate the positive and negative electrode of battery, prevents the two poles of the earth from connecing
Touching and it is short-circuit, additionally have the function of electrolyte ion capable of being made to pass through.Diaphragm material is nonconducting, physicochemical properties
Have a great impact to the performance of battery.The type of battery is different, and the diaphragm of use is also different.It is serial for lithium battery, due to
Electrolyte is organic solvent system, thus needs the diaphragm material of organic solvent-resistant, general using the poly- of high-strength thin-film
Alkene perforated membrane.
The lithium ion battery separator of existing market is mainly polyolefin (based on PE, PP) microporous barrier, polyalkene diaphragm
The fusing point of bulk material is relatively low, and about 130 DEG C~165 DEG C, near the heated melting temperature for reaching diaphragm material of battery
When, diaphragm will appear apparent dimensional contraction, generate hole, cause positive and negative anodes to contact and short-circuit, and then initiation cells burst is quick-fried
Fried accident.
Summary of the invention
The invention discloses a kind of thermal safety height, the lithium electricity for the high thermal stability that thermal stability is good, heat-conducting effect is excellent
Pond diaphragm and preparation method thereof, it is mentioned above to solve the problems, such as.
In order to achieve the above purpose, the following technical solution is employed by the present invention:
A kind of lithium battery diaphragm of high thermal stability, the lithium battery diaphragm is by polyimides nucleopore membranes, ceramic layer and Static Spinning
Silk layers of nanofibers constitute, the lithium battery diaphragm with a thickness of 50-80 μm.
Preferably, the polyimides nucleopore membranes: ceramic layer: the thickness ratio of Electrospun nano-fibers layer is 5-8:1-3:
3-7。
Preferably, conductive coating is coated respectively in two planes of the lithium battery diaphragm, the slurry of the conductive coating is by weight
Measure percentage scale following component, binder 1-10%, dispersing agent 1-5%, solvent 75-87% and carbon material 5-20%, the carbon materials
Material is the carbon pipe and flake graphite that weight ratio is 1:1-1:5, and the binder is the hydroxypropyl first that weight ratio is 1:1:1-2:3:5
Base cellulose, butadiene-styrene rubber cream, polyethylene glycol oxide；The dispersing agent be weight ratio be 1:1-1:5 modification polyoxyethylene ether and
Polyvinylpyrrolidone；The solvent is water, and the presence of conductive coating can further enhance the safety and temperature of lithium battery
Property.
A kind of lithium battery diaphragm of high thermal stability, preparation method includes the following steps:
A, the preparation of polyimides nucleopore membranes
At 70-90 DEG C, Kapton is put into sodium hydroxide etching liquid and is impregnated, it, will after impregnating 25-40min
Kapton takes out and is cleaned, dried with deionized water, obtains polyimides nucleopore membranes；
B, the preparation of ceramic layer
30-65 parts of porous aluminas, 0.5-1.2 parts of dispersing agents, 0.3-0.5 portions of suspension stabilizers and 1.2-1.5 parts of surfaces are living
Property agent is added to together in 50-80 parts of deionized water, and is stirred 30-45min with the speed of 180-250r/min, is obtained
Aqueous ceramic slurry is coated on the side of polyimides nucleopore membranes as anilox roll aqueous ceramic slurry by made from, then existed
30-50min is dried at a temperature of 60-85 DEG C, and ceramic layer is made；
C, the preparation of Electrospun nano-fibers layer
Polymer material is added to progress heating stirring dissolution in dimethyl acetamide, obtained polymer material solution is infused
Enter electrostatic spinning machine, adjust the distance between spinning syringe needle and receiver board, start electrostatic spinning, electrostatic spinning solution formation is penetrated
Stream is sprayed on ceramic layer, and then the precipitating drying 90-150min at 80-95 DEG C, is made Electrospun nano-fibers layer, obtains
The lithium battery diaphragm of high thermal stability.
Preferably, porous aluminas described in step b is by aluminium based metal organic frame compound in 800-1200 DEG C of temperature
It is made after the lower calcining 12-30h of degree.
Preferably, the aluminium based metal organic frame compound selects MIL-53 (Al), MIL-100 (Al), MIL-101
(Al) any one or more in.
Preferably, dispersing agent described in step b is lauryl sodium sulfate, dodecyl sodium sulfate, calgon, gathers
Any one or more in acrylic acid, ammonium polyacrylate salt, octylphenolpolyoxyethylene and polyethylene glycol.
Preferably, suspension stabilizer described in step b is 2- acrylamide -2- methacrylic sulfonic acid, N, N- dimethyl propylene
Acrylamide, acrylic acid terpolymer in any one or two kinds.
Preferably, surfactant described in step b is methacrylic acid hydroxypropyl sulfonic acid sodium, sodium hydroxymethane sulfonate and 4-
Any one or more in hydroxyethyl piperazineethanesulfonic acid sodium.
Preferably, the polymer material of Electrospun nano-fibers layer described in step c selects polyacrylonitrile, polyamides sub-
Any one in amine, Kynoar or two kinds.
Preferably, in step c electrostatic spinning spinning syringe needle internal diameter be 0.5-3.5 mm, voltage be 5-35 kV, syringe needle with
The distance of reception device is 3-40 cm, and spinning temperature is 30-90 DEG C, and spinning flow is 2-10 ml/h.
Using above-mentioned technical solution, the beneficial effect that the present invention reaches is:
The present invention is successively applied in the upper of basement membrane coated with ceramic layer using the polyimides with high heat resistance and high-insulativity as basement membrane
With Electrospun nano-fibers layer；Porous aluminas has preferable thermal conductivity in ceramic layer, can be in time by the heat on diaphragm
Amount is conducted, and is avoided diaphragm and is locally heat-shrinked excessive caused short circuit；Electrostatic spinning by layers of nanofibers can improve every
Film surface uniform pore diameter degree improves the thermal stability of lithium battery diaphragm, and can combine closely with ceramic layer, avoids in ceramic layer
Porous aluminas falls off；Lithium battery diaphragm prepared by the present invention is high with thermal safety, thermal stability is good, heat-conducting effect is excellent
The characteristics of, the problems such as existing lithium battery diaphragm thermal stability is poor, safety is poor can be overcome well.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention,
Technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is the present invention one
Divide embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making
Every other embodiment obtained, shall fall within the protection scope of the present invention under the premise of creative work.
Embodiment 1:
A kind of lithium battery diaphragm of high thermal stability, lithium battery diaphragm are received by polyimides nucleopore membranes, ceramic layer and electrostatic spinning
Rice fibrous layer constitute, the lithium battery diaphragm with a thickness of 50 μm.
Polyimides nucleopore membranes: ceramic layer: the thickness ratio of Electrospun nano-fibers layer is 5:2:3.
A kind of lithium battery diaphragm of high thermal stability, preparation method includes the following steps:
A, the preparation of polyimides nucleopore membranes
At 70 DEG C, Kapton is put into sodium hydroxide etching liquid and is impregnated, after impregnating 35min, by polyamides Asia
Amine film takes out and is cleaned, dried with deionized water, obtains polyimides nucleopore membranes；
B, the preparation of ceramic layer
30 parts of porous aluminas, 0.9 part of dispersing agent, 0.3 portion of suspension stabilizer are added to 60 together with 1.2 parts of surfactants
In the deionized water of part, and 30min is stirred with the speed of 200r/min, obtains aqueous ceramic slurry, it will by anilox roll
Aqueous ceramic slurry obtained is coated on the side of polyimides nucleopore membranes, then 60 DEG C at a temperature of dry 30min, be made
Ceramic layer；
C, the preparation of Electrospun nano-fibers layer
Polymer material is added to progress heating stirring dissolution in dimethyl acetamide, obtained polymer material solution is infused
Enter electrostatic spinning machine, adjust the distance between spinning syringe needle and receiver board, start electrostatic spinning, electrostatic spinning solution formation is penetrated
Stream is sprayed on ceramic layer, and then the precipitating drying 110min at 80 DEG C, is made Electrospun nano-fibers layer, it is steady to obtain high fever
Qualitative lithium battery diaphragm.
Porous aluminas is by aluminium based metal organic frame compound in 800-1200 DEG C of temperature lower calcination 12- in step b
It is made after 30h.
Aluminium based metal organic frame compound selects MIL-53 (Al), MIL-100 (Al), any in MIL-101 (Al)
It is one or more.
Dispersing agent is lauryl sodium sulfate, dodecyl sodium sulfate, calgon, polyacrylic acid, poly- third in step b
Any one or more in enoic acid ammonium salt, octylphenolpolyoxyethylene and polyethylene glycol.
Suspension stabilizer is 2- acrylamide -2- methacrylic sulfonic acid, N, N- dimethylacrylamide, propylene in step b
Any one or two kinds in the terpolymer of acid.
Surfactant is methacrylic acid hydroxypropyl sulfonic acid sodium, sodium hydroxymethane sulfonate and 4- hydroxyethyl piperazine in step b
Any one or more in ethanesulfonic acid sodium.
The polymer material of Electrospun nano-fibers layer selects polyacrylonitrile, polyimides, Kynoar in step c
In any one or two kinds.
The spinning syringe needle internal diameter of electrostatic spinning is 0.5 mm in step c, and voltage is 25 kV, syringe needle and reception device away from
From for 3cm, spinning temperature is 30 DEG C, and spinning flow is 8 ml/h.
Embodiment 2:
A kind of lithium battery diaphragm of high thermal stability, lithium battery diaphragm are received by polyimides nucleopore membranes, ceramic layer and electrostatic spinning
Rice fibrous layer constitute, the lithium battery diaphragm with a thickness of 65 μm.
Be coated respectively with conductive coating in two planes of the lithium battery diaphragm, conductive coating with a thickness of 2 μm, it is described conductive to apply
Following component, binder 8%, dispersing agent 2%, solvent 85% and carbon material 5, the carbon materials are measured by the percentage by weight in the slurry of layer
Material is carbon pipe and flake graphite that weight ratio is 1:1, the binder be weight ratio be 1:1:1 hydroxypropyl methyl cellulose,
Butadiene-styrene rubber cream, polyethylene glycol oxide；The dispersing agent is the modification polyoxyethylene ether and polyvinylpyrrolidine that weight ratio is 1:1
Ketone；The solvent is water.
Polyimides nucleopore membranes: ceramic layer: the thickness ratio of Electrospun nano-fibers layer is 7:3:4.
A kind of lithium battery diaphragm of high thermal stability, preparation method includes the following steps:
A, the preparation of polyimides nucleopore membranes
At 75 DEG C, Kapton is put into sodium hydroxide etching liquid and is impregnated, after impregnating 40min, by polyamides Asia
Amine film takes out and is cleaned, dried with deionized water, obtains polyimides nucleopore membranes；
B, the preparation of ceramic layer
35 parts of porous aluminas, 0.5 part of dispersing agent, 0.4 portion of suspension stabilizer are added to 70 together with 1.3 parts of surfactants
In the deionized water of part, and 35min is stirred with the speed of 220r/min, obtains aqueous ceramic slurry, it will by anilox roll
Aqueous ceramic slurry obtained is coated on the side of polyimides nucleopore membranes, then 65 DEG C at a temperature of dry 45min, be made
Ceramic layer；
C, the preparation of Electrospun nano-fibers layer
Polymer material is added to progress heating stirring dissolution in dimethyl acetamide, obtained polymer material solution is infused
Enter electrostatic spinning machine, adjust the distance between spinning syringe needle and receiver board, start electrostatic spinning, electrostatic spinning solution formation is penetrated
Stream is sprayed on ceramic layer, and then the precipitating drying 90min at 85 DEG C, is made Electrospun nano-fibers layer, it is steady to obtain high fever
Qualitative lithium battery diaphragm.
Porous aluminas is by aluminium based metal organic frame compound in 800-1200 DEG C of temperature lower calcination 12- in step b
It is made after 30h.
Aluminium based metal organic frame compound selects MIL-53 (Al), MIL-100 (Al), any in MIL-101 (Al)
It is one or more.
Dispersing agent is lauryl sodium sulfate, dodecyl sodium sulfate, calgon, polyacrylic acid, poly- third in step b
Any one or more in enoic acid ammonium salt, octylphenolpolyoxyethylene and polyethylene glycol.
Suspension stabilizer is 2- acrylamide -2- methacrylic sulfonic acid, N, N- dimethylacrylamide, propylene in step b
Any one or two kinds in the terpolymer of acid.
Surfactant is methacrylic acid hydroxypropyl sulfonic acid sodium, sodium hydroxymethane sulfonate and 4- hydroxyethyl piperazine in step b
Any one or more in ethanesulfonic acid sodium.
The polymer material of Electrospun nano-fibers layer selects polyacrylonitrile, polyimides, Kynoar in step c
In any one or two kinds.
The spinning syringe needle internal diameter of electrostatic spinning is 1.5 mm in step c, and voltage 5kV, syringe needle is at a distance from reception device
For 15 cm, spinning temperature is 40 DEG C, and spinning flow is 6 ml/h.
Embodiment 3:
A kind of lithium battery diaphragm of high thermal stability, lithium battery diaphragm are received by polyimides nucleopore membranes, ceramic layer and electrostatic spinning
Rice fibrous layer constitute, the lithium battery diaphragm with a thickness of 70 μm.
Be coated respectively with conductive coating in two planes of the lithium battery diaphragm, conductive coating with a thickness of 5 μm, it is described conductive to apply
Following component, binder 5%, dispersing agent 3%, solvent 82% and carbon material 10%, the carbon is measured by the percentage by weight in the slurry of layer
Material is the carbon pipe and flake graphite that weight ratio is 1:5, and the binder is the hydroxypropyl methyl fiber that weight ratio is 2:3:5
Element, butadiene-styrene rubber cream, polyethylene glycol oxide；The dispersing agent is the modification polyoxyethylene ether and polyvinyl pyrrole that weight ratio is 1:5
Alkanone；The solvent is water.
Polyimides nucleopore membranes: ceramic layer: the thickness ratio of Electrospun nano-fibers layer is 6:1:5.
A kind of lithium battery diaphragm of high thermal stability, preparation method includes the following steps:
A, the preparation of polyimides nucleopore membranes
At 80 DEG C, Kapton is put into sodium hydroxide etching liquid and is impregnated, after impregnating 25min, by polyamides Asia
Amine film takes out and is cleaned, dried with deionized water, obtains polyimides nucleopore membranes；
B, the preparation of ceramic layer
45 parts of porous aluminas, 1.2 parts of dispersing agents, 0.3 portion of suspension stabilizer are added to 50 together with 1.3 parts of surfactants
In the deionized water of part, and 40min is stirred with the speed of 180r/min, obtains aqueous ceramic slurry, it will by anilox roll
Aqueous ceramic slurry obtained is coated on the side of polyimides nucleopore membranes, then 70 DEG C at a temperature of dry 40min, be made
Ceramic layer；
C, the preparation of Electrospun nano-fibers layer
Polymer material is added to progress heating stirring dissolution in dimethyl acetamide, obtained polymer material solution is infused
Enter electrostatic spinning machine, adjust the distance between spinning syringe needle and receiver board, start electrostatic spinning, electrostatic spinning solution formation is penetrated
Stream is sprayed on ceramic layer, and then the precipitating drying 120min at 90 DEG C, is made Electrospun nano-fibers layer, it is steady to obtain high fever
Qualitative lithium battery diaphragm.
Porous aluminas is by aluminium based metal organic frame compound in 800-1200 DEG C of temperature lower calcination 12- in step b
It is made after 30h.
Aluminium based metal organic frame compound selects MIL-53 (Al), MIL-100 (Al), any in MIL-101 (Al)
It is one or more.
Dispersing agent is lauryl sodium sulfate, dodecyl sodium sulfate, calgon, polyacrylic acid, poly- third in step b
Any one or more in enoic acid ammonium salt, octylphenolpolyoxyethylene and polyethylene glycol.
Suspension stabilizer is 2- acrylamide -2- methacrylic sulfonic acid, N, N- dimethylacrylamide, propylene in step b
Any one or two kinds in the terpolymer of acid.
Surfactant is methacrylic acid hydroxypropyl sulfonic acid sodium, sodium hydroxymethane sulfonate and 4- hydroxyethyl piperazine in step b
Any one or more in ethanesulfonic acid sodium.
The polymer material of Electrospun nano-fibers layer selects polyacrylonitrile, polyimides, Kynoar in step c
In any one or two kinds.
The spinning syringe needle internal diameter of electrostatic spinning is 2.0 mm in step c, and voltage is 15 kV, syringe needle and reception device away from
From for 25 cm, spinning temperature is 50 DEG C, and spinning flow is 10 ml/h.
Embodiment 4:
A kind of lithium battery diaphragm of high thermal stability, lithium battery diaphragm are received by polyimides nucleopore membranes, ceramic layer and electrostatic spinning
Rice fibrous layer constitute, the lithium battery diaphragm with a thickness of 78 μm.
Polyimides nucleopore membranes: ceramic layer: the thickness ratio of Electrospun nano-fibers layer is 8:3:6.
A kind of lithium battery diaphragm of high thermal stability, preparation method includes the following steps:
A, the preparation of polyimides nucleopore membranes
At 85 DEG C, Kapton is put into sodium hydroxide etching liquid and is impregnated, after impregnating 30min, by polyamides Asia
Amine film takes out and is cleaned, dried with deionized water, obtains polyimides nucleopore membranes；
B, the preparation of ceramic layer
55 parts of porous aluminas, 0.7 part of dispersing agent, 0.5 portion of suspension stabilizer are added to 75 together with 1.4 parts of surfactants
In the deionized water of part, and 45min is stirred with the speed of 240r/min, obtains aqueous ceramic slurry, it will by anilox roll
Aqueous ceramic slurry obtained is coated on the side of polyimides nucleopore membranes, then 75 DEG C at a temperature of dry 35min, be made
Ceramic layer；
C, the preparation of Electrospun nano-fibers layer
Polymer material is added to progress heating stirring dissolution in dimethyl acetamide, obtained polymer material solution is infused
Enter electrostatic spinning machine, adjust the distance between spinning syringe needle and receiver board, start electrostatic spinning, electrostatic spinning solution formation is penetrated
Stream is sprayed on ceramic layer, and then the precipitating drying 150min at 95 DEG C, is made Electrospun nano-fibers layer, it is steady to obtain high fever
Qualitative lithium battery diaphragm.
Porous aluminas is by aluminium based metal organic frame compound in 800-1200 DEG C of temperature lower calcination 12- in step b
It is made after 30h.
Aluminium based metal organic frame compound selects MIL-53 (Al), MIL-100 (Al), any in MIL-101 (Al)
It is one or more.
Dispersing agent is lauryl sodium sulfate, dodecyl sodium sulfate, calgon, polyacrylic acid, poly- third in step b
Any one or more in enoic acid ammonium salt, octylphenolpolyoxyethylene and polyethylene glycol.
Suspension stabilizer is 2- acrylamide -2- methacrylic sulfonic acid, N, N- dimethylacrylamide, propylene in step b
Any one or two kinds in the terpolymer of acid.
Surfactant is methacrylic acid hydroxypropyl sulfonic acid sodium, sodium hydroxymethane sulfonate and 4- hydroxyethyl piperazine in step b
Any one or more in ethanesulfonic acid sodium.
The polymer material of Electrospun nano-fibers layer selects polyacrylonitrile, polyimides, Kynoar in step c
In any one or two kinds.
The spinning syringe needle internal diameter of electrostatic spinning is 2.5 mm in step c, and voltage 30kV, syringe needle is at a distance from reception device
For 35 cm, spinning temperature is 70 DEG C, and spinning flow is 2ml/h.
Embodiment 5:
A kind of lithium battery diaphragm of high thermal stability, lithium battery diaphragm are received by polyimides nucleopore membranes, ceramic layer and electrostatic spinning
Rice fibrous layer constitute, the lithium battery diaphragm with a thickness of 80 μm.
Polyimides nucleopore membranes: ceramic layer: the thickness ratio of Electrospun nano-fibers layer is 7:2:7.
A kind of lithium battery diaphragm of high thermal stability, preparation method includes the following steps:
A, the preparation of polyimides nucleopore membranes
At 90 DEG C, Kapton is put into sodium hydroxide etching liquid and is impregnated, after impregnating 25min, by polyamides Asia
Amine film takes out and is cleaned, dried with deionized water, obtains polyimides nucleopore membranes；
B, the preparation of ceramic layer
65 parts of porous aluminas, 0.8 part of dispersing agent, 0.4 portion of suspension stabilizer are added to 80 together with 1.5 parts of surfactants
In the deionized water of part, and 45min is stirred with the speed of 250r/min, obtains aqueous ceramic slurry, it will by anilox roll
Aqueous ceramic slurry obtained is coated on the side of polyimides nucleopore membranes, then 85 DEG C at a temperature of dry 50min, be made
Ceramic layer；
C, the preparation of Electrospun nano-fibers layer
Polymer material is added to progress heating stirring dissolution in dimethyl acetamide, obtained polymer material solution is infused
Enter electrostatic spinning machine, adjust the distance between spinning syringe needle and receiver board, start electrostatic spinning, electrostatic spinning solution formation is penetrated
Stream is sprayed on ceramic layer, and then the precipitating drying 140min at 95 DEG C, is made Electrospun nano-fibers layer, it is steady to obtain high fever
Qualitative lithium battery diaphragm.
Porous aluminas is by aluminium based metal organic frame compound in 800-1200 DEG C of temperature lower calcination 12- in step b
It is made after 30h.
Aluminium based metal organic frame compound selects MIL-53 (Al), MIL-100 (Al), any in MIL-101 (Al)
It is one or more.
Dispersing agent is lauryl sodium sulfate, dodecyl sodium sulfate, calgon, polyacrylic acid, poly- third in step b
Any one or more in enoic acid ammonium salt, octylphenolpolyoxyethylene and polyethylene glycol.
Suspension stabilizer is 2- acrylamide -2- methacrylic sulfonic acid, N, N- dimethylacrylamide, propylene in step b
Any one or two kinds in the terpolymer of acid.
Surfactant is methacrylic acid hydroxypropyl sulfonic acid sodium, sodium hydroxymethane sulfonate and 4- hydroxyethyl piperazine in step b
Any one or more in ethanesulfonic acid sodium.
The polymer material of Electrospun nano-fibers layer selects polyacrylonitrile, polyimides, Kynoar in step c
In any one or two kinds.
The spinning syringe needle internal diameter of electrostatic spinning is 3.5 mm in step c, and voltage is 35 kV, syringe needle and reception device away from
From for 40 cm, spinning temperature is 90 DEG C, and spinning flow is 4ml/h.
It is detected, the electrolyte retention of the composite lithium battery membrane being prepared is up to 315%, and hot closed temperature is up to 280
DEG C, 500 DEG C are warming up to, diaphragm will not be broken through, tensile strength 45MPa, and puncture strength 378g/mil, 0.5C circulating battery holds
Conservation rate is measured up to 98%, percent thermal shrinkage is 0.07% under conditions of 140 DEG C/h.
Performance test
Performance detection is carried out to the lithium battery diaphragm in various embodiments of the present invention.Testing result is as follows:
Table 1
。
As can be seen that lithium battery diaphragm transverse and longitudinal shrinking percentage prepared by each embodiment is close from testing result, it is heat-shrinked
Very little has preferable heat-conducting effect and thermal stability.
The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although with reference to the foregoing embodiments
Invention is explained in detail, those skilled in the art should understand that: it still can be to aforementioned each implementation
Technical solution documented by example is modified or equivalent replacement of some of the technical features；And these modification or
Replacement, the spirit and scope for technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution.
Claims (10)
1. a kind of lithium battery diaphragm of high thermal stability, which is characterized in that the lithium battery diaphragm is by polyimides nucleopore membranes, pottery
Enamel coating and Electrospun nano-fibers layer are constituted, the lithium battery diaphragm with a thickness of 50-80 μm.
2. a kind of lithium battery diaphragm of high thermal stability according to claim 1, it is characterised in that: the lithium battery diaphragm
Two planes on be coated respectively with conductive coating.
3. a kind of preparation method of the lithium battery diaphragm of high thermal stability, feature described in any one of claim 1-2
Be, preparation method the following steps are included:
A, the preparation of polyimides nucleopore membranes
At 70-90 DEG C, Kapton is put into sodium hydroxide etching liquid and is impregnated, it, will after impregnating 25-40min
Kapton takes out and is cleaned, dried with deionized water, obtains polyimides nucleopore membranes；
B, the preparation of ceramic layer
30-65 parts of porous aluminas, 0.5-1.2 parts of dispersing agents, 0.3-0.5 portions of suspension stabilizers and 1.2-1.5 parts of surfaces are living
Property agent is added to together in 50-80 parts of deionized water, and is stirred 30-45min with the speed of 180-250r/min, is obtained
Aqueous ceramic slurry is coated on the side of polyimides nucleopore membranes as anilox roll aqueous ceramic slurry by made from, then existed
30-50min is dried at a temperature of 60-85 DEG C, and ceramic layer is made；
C, the preparation of Electrospun nano-fibers layer
Polymer material is added to progress heating stirring dissolution in dimethyl acetamide, obtained polymer material solution is infused
Enter electrostatic spinning machine, adjust the distance between spinning syringe needle and receiver board, start electrostatic spinning, electrostatic spinning solution formation is penetrated
Stream is sprayed on ceramic layer, and then the precipitating drying 90-150min at 80-95 DEG C, is made Electrospun nano-fibers layer, obtains
The lithium battery diaphragm of high thermal stability.
4. a kind of preparation method of the lithium battery diaphragm of high thermal stability according to claim 3, it is characterised in that: step
Porous aluminas described in b is made after 800-1200 DEG C of temperature lower calcination 12-30h by aluminium based metal organic frame compound
?.
5. a kind of preparation method of the lithium battery diaphragm of high thermal stability according to claim 4, it is characterised in that: described
Aluminium based metal organic frame compound select MIL-53 (Al), MIL-100 (Al), in MIL-101 (Al) any one or it is more
Kind.
6. a kind of preparation method of the lithium battery diaphragm of high thermal stability according to claim 3, it is characterised in that: step
Dispersing agent described in b is lauryl sodium sulfate, dodecyl sodium sulfate, calgon, polyacrylic acid, ammonium polyacrylate
Any one or more in salt, octylphenolpolyoxyethylene and polyethylene glycol.
7. a kind of preparation method of the lithium battery diaphragm of high thermal stability according to claim 3, it is characterised in that: step
Suspension stabilizer described in b is 2- acrylamide -2- methacrylic sulfonic acid, N, N- dimethylacrylamide, the ternary of acrylic acid
Any one in copolymer or two kinds.
8. a kind of preparation method of the lithium battery diaphragm of high thermal stability according to claim 3, it is characterised in that: step
Surfactant described in b is methacrylic acid hydroxypropyl sulfonic acid sodium, sodium hydroxymethane sulfonate and 4- hydroxyethyl piperazineethanesulfonic acid sodium
In any one or more.
9. a kind of preparation method of the lithium battery diaphragm of high thermal stability according to claim 3, it is characterised in that: step
The polymer materials of Electrospun nano-fibers layer described in c selects polyacrylonitrile, polyimides, any in Kynoar
It is one or two kinds of.
10. a kind of preparation method of the lithium battery diaphragm of high thermal stability according to claim 3, it is characterised in that: step
The spinning syringe needle internal diameter of electrostatic spinning is 0.5-3.5 mm in rapid c, and voltage is 5-35 kV, and syringe needle is at a distance from reception device
3-40 cm, spinning temperature are 30-90 DEG C, and spinning flow is 2-10 ml/h.
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