CN109860483A - Diaphragm coating liquid and preparation method thereof, diaphragm and preparation method thereof and secondary cell - Google Patents
Diaphragm coating liquid and preparation method thereof, diaphragm and preparation method thereof and secondary cell Download PDFInfo
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- CN109860483A CN109860483A CN201910135040.XA CN201910135040A CN109860483A CN 109860483 A CN109860483 A CN 109860483A CN 201910135040 A CN201910135040 A CN 201910135040A CN 109860483 A CN109860483 A CN 109860483A
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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 invention belongs to technical field of secondary batteries, it is related to a kind of diaphragm coating liquid and preparation method thereof, diaphragm and preparation method thereof and secondary cell.A kind of production method of diaphragm coating liquid provided by the invention, it include: the first dispersion liquid that polyetherimide solution, binder and pore creating material are provided and formed, the second dispersion liquid that inorganic particle, dispersing agent and organic solvent are formed is provided, first dispersion liquid is mixed with the second dispersion liquid, separation, obtains diaphragm coating liquid.This method can retain original stability of polyetherimide solution to greatest extent, while this method makes diaphragm coating liquid have good thermal contraction performance by addition inorganic particle.The performance of basement membrane can totally be improved using diaphragm coating liquid made from the above method.In addition, the present invention also provides diaphragm comprising above-mentioned diaphragm coating liquid and preparation method thereof and secondary cells.
Description
Technical field
The invention belongs to technical field of secondary batteries, in particular to a kind of diaphragm coating liquid and preparation method thereof, every
Film and preparation method thereof and secondary cell.
Background technique
Diaphragm is one layer of porous membrane for separating the positive and negative polarities in battery, only allows certain specific ions logical
It crosses.In the structure of battery, diaphragm is the most key one of material, and the performance of diaphragm determines the interfacial structure of battery, interior
Resistance etc., directly affects capacity, circulation and the security performance of battery.Comprehensive performance of the diaphragm haveing excellent performance for raising battery
It plays an important role.
In the prior art, the stability of diaphragm is not high, and percent thermal shrinkage is big, easily causes the short circuit of battery, causes safety and asks
Topic.
In consideration of it, at least one of the present invention is specifically proposed to solve the above problems.
Summary of the invention
The first object of the present invention is to provide a kind of production method of diaphragm coating liquid, and this method can protect to greatest extent
Original stability of polyetherimide solution is stayed, while by addition inorganic particle, making diaphragm coating liquid that there is good heat to receive
Contracting performance.
The second object of the present invention is to provide a kind of using diaphragm coating liquid made from the above method, the diaphragm coating liquid
The performance of basement membrane can totally be improved.
The third object of the present invention is to provide a kind of diaphragm including above-mentioned diaphragm coating liquid, the diaphragm percent thermal shrinkage
It is small, high mechanical strength.
The fourth object of the present invention is to provide a kind of production method of above-mentioned diaphragm, and this method is easy to operate, feasibility
By force.
The fifth object of the present invention is to provide a kind of secondary cell including above-mentioned diaphragm, the safety of the secondary cell
It can be good.
To achieve the above object, the technical solution adopted by the present invention are as follows:
According to an aspect of the present invention, a kind of production method of diaphragm coating liquid is provided, comprising:
The first dispersion liquid that polyetherimide solution, binder and pore creating material are formed is provided；
The second dispersion liquid that inorganic particle, dispersing agent and organic solvent are formed is provided；
First dispersion liquid is mixed with the second dispersion liquid, separates, obtains diaphragm coating liquid；
Wherein, the quality of the polyetherimide solution accounts for the 5%-10% of the diaphragm coating liquid gross mass；
The quality of the inorganic particle accounts for the 15%-30% of the diaphragm coating liquid gross mass.
As further preferred technical solution, the quality of the pore creating material accounts for the 5%- of the diaphragm coating liquid gross mass
15%；
Preferably, the quality of the binder accounts for the 1%-3% of the diaphragm coating liquid gross mass；
Preferably, the quality of the dispersing agent accounts for the 0.5%-3% of the diaphragm coating liquid gross mass.
As further preferred technical solution, the inorganic particle includes aluminium oxide, barium titanate, magnesium hydroxide or titanium dioxide
In silicon any one or at least two combination；
Preferably, the organic solvent include N-Methyl pyrrolidone, dimethyl acetamide, n,N-Dimethylformamide or
In person's repefral any one or at least two combination；
Preferably, the pore creating material includes any one in dimethyl carbonate, ethyl acetate, hexamethylene or dimethyl phosphate
Kind or at least two combination；
Preferably, the binder includes any one in Kynoar, polyvinylpyrrolidone or polyvinyl alcohol
Or at least two combination；
Preferably, the dispersing agent includes vinyl bis-stearamides and/or oxidized polyethylene wax.
As further preferred technical solution, the polyetherimide solution includes polyetherimide and lytic agent, described
Lytic agent includes in N-Methyl pyrrolidone, dimethyl acetamide, n,N-Dimethylformamide or repefral
Any one or at least two combination.
As further preferred technical solution, the polyetherimide is to pass through pretreated polyetherimide, described pre-
Processing includes drying；
Preferably, the temperature of the drying is 110-150 DEG C；
Preferably, the time of the drying is 2-4h.
According to another aspect of the present invention, a kind of diaphragm coating liquid is provided, using the production of the diaphragm coating liquid
Method is made.
According to another aspect of the present invention, a kind of diaphragm is provided, is formed including basement membrane and by the diaphragm coating liquid
Coating liquid layer；
Preferably, the basement membrane includes polyethylene or polypropylene.
According to another aspect of the present invention, the production method of diaphragm described in one kind is provided, comprising: apply the diaphragm
The surface that covering liquid is coated in the basement membrane carries out the step of pore-creating solidification and post-processing.
As further preferred technical solution, the cured mode of pore-creating includes extraction, the extractant packet of the extraction
Include inorganic extractant and/or organic extractant；
Preferably, the inorganic extractant includes water；
Preferably, the organic extractant includes N-Methyl pyrrolidone, dimethyl acetamide, n,N-Dimethylformamide
Or in repefral any one or at least two combination；
Preferably, the number of the extraction is 2-4 times.
According to another aspect of the present invention, a kind of secondary cell is provided, including the diaphragm or the diaphragm
Diaphragm made from production method.
Compared with prior art, the beneficial effects of the present invention are:
1, a kind of production method of diaphragm coating liquid provided by the invention, this method can retain polyetherimide to greatest extent
Original stability of amine aqueous solution, while by addition inorganic particle, make diaphragm coating liquid that there is good thermal contraction performance.
2, a kind of diaphragm coating liquid provided by the invention is made using the above method.The diaphragm coating liquid can be effectively
The percent thermal shrinkage for reducing basement membrane, can totally improve the performance of basement membrane.
3, a kind of diaphragm provided by the invention, including the coating liquid layer that above-mentioned diaphragm coating liquid is formed, which is heat-shrinked
Rate is small, high mechanical strength.
4, the production method of a kind of diaphragm provided by the invention, this method is easy to operate, and feasibility is strong, and diaphragm is applied
Covering liquid improves the Function of basement membrane percent thermal shrinkage to maximum.
5, a kind of secondary cell provided by the invention, including above-mentioned diaphragm are low since the diaphragm has high stability
Percent thermal shrinkage, and then greatly improve the security performance of secondary cell.
Detailed description of the invention
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art
Embodiment or attached drawing needed to be used in the description of the prior art be briefly described, it should be apparent that, it is described below
Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor
It puts, is also possible to obtain other drawings based on these drawings.
Fig. 1 is the SEM figure that the diaphragm coating liquid that the embodiment of the present invention 1 provides is coated in the diaphragm obtained in polyethylene based film
Piece.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiments and examples, but this field skill
Art personnel will be understood that following embodiments and embodiment are merely to illustrate the present invention, and are not construed as limiting model of the invention
It encloses.Based on the embodiments of the present invention, obtained by those of ordinary skill in the art without making creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.The person that is not specified actual conditions, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
It should be understood that
In the present invention, if without particularly illustrating, all embodiments mentioned in this article and preferred implementation method
It can be combined with each other to form new technical solution.
In the present invention, if without particularly illustrating, all technical characteristics and preferred feature mentioned in this article can be with
Intercombination forms new technical solution.
" range " disclosed in this invention can be respectively one or more lower limits and one in the form of lower and upper limit
A or multiple upper limits.
In the present invention, unless otherwise indicated, each reaction or operating procedure can be carried out sequentially, can not also be in sequence
It carries out.Preferably, method herein is that sequence carries out.
Unless otherwise indicated, profession used herein and meaning phase known to scientific term and one skilled in the art
Together.In addition, any method similar to or equal to what is recorded or material can also be applied in the present invention.
In a first aspect, providing a kind of production method of diaphragm coating liquid at least one embodiment, comprising:
The first dispersion liquid that polyetherimide solution, binder and pore creating material are formed is provided；
The second dispersion liquid that inorganic particle, dispersing agent and organic solvent are formed is provided；
First dispersion liquid is mixed with the second dispersion liquid, separates, obtains diaphragm coating liquid；
Wherein, the quality of polyetherimide solution accounts for the 5%-10% of diaphragm coating liquid gross mass；
The quality of inorganic particle accounts for the 15%-30% of diaphragm coating liquid gross mass.
For the problem that battery diaphragm stability is not high, percent thermal shrinkage is big in the prior art, the present invention provides one kind every
The production method of film coating liquid, this method can retain original stability of polyetherimide solution to greatest extent, pass through simultaneously
Inorganic particle is added, makes diaphragm coating liquid that there is good thermal contraction performance.
Polyetherimide (Polyetherimide, abbreviation PEI) is amber transparent solid, without adding any additive
There are intrinsic anti-flammability and low smoke intensity, oxygen index (OI) 47%, combustion rating is UL94-V-0 grades, density 1.28-1.42g/
cm3.PEI has very strong high-temperature stability, even the PEI of non-reinforcing type, still has good toughness and intensity.PEI is also
With very low shrinking percentage, good anti-flammability, anti-chemical reaction and mechanical property.In addition, the glass transition temperature of PEI
It is very high, up to 215 DEG C, can be used for a long time under 160-180 DEG C of operating temperature.Therefore the present invention utilizes the superior thermostabilization of PEI
Property and mechanical property make heat-resisting diaphragm coating liquid, and then improve the security performance of basement membrane.
Inorganic particle is added in diaphragm coating liquid, the skeleton structure of basement membrane can be increased, plays the role of support, improves base
The thermal contraction performance of film.
It is to be appreciated that polyetherimide could preferably play its high stable after necessarily being formed polyetherimide solution
The characteristic of property；The effect of binder is the surface for enabling the diaphragm coating liquid of production to be preferably attached to basement membrane；Dispersing agent
Effect is that inorganic particle is enable preferably to disperse to make the diaphragm coating liquid of production more uniform in organic solvent；Pore creating material
Effect is to make the diaphragm coating liquid of production that can generate a some holes in subsequent diaphragm manufacturing process, this some holes ensures ion energy
It enough passes through diaphragm and electrochemical reaction occurs.
Polyetherimide and the suitable accounting of inorganic particle can ensure the diaphragm coating fluidity of production in diaphragm coating liquid
It can be optimal.Typical but unrestricted, the quality of polyetherimide solution accounts for diaphragm coating liquid gross mass, such as can be 5%,
6%, 7%, 8%, 9% or 10%；The quality of inorganic particle accounts for diaphragm coating liquid gross mass, such as can be 15%, 17%,
19%, 20%, 22%, 25%, 27% or 30%.
In a preferred embodiment, the quality of pore creating material accounts for the 5%-15% of diaphragm coating liquid gross mass；
Preferably, the quality of binder accounts for the 1%-3% of diaphragm coating liquid gross mass；
Preferably, the quality of dispersing agent accounts for the 0.5%-3% of diaphragm coating liquid gross mass.
Typical but unrestricted, the quality of pore creating material accounts for diaphragm coating liquid gross mass, such as can be 5%, 8%, 9%,
10%, 12%, 13% or 15%；The quality of binder accounts for diaphragm coating liquid gross mass, such as can be 1%, 2% or 3%；Point
The quality of powder accounts for the 0.5%, 1%, 1.5%, 2% or 3% of diaphragm coating liquid gross mass.
It should be noted that the content that above-mentioned pore creating material, binder and dispersing agent account for diaphragm coating liquid gross mass respectively is same
Sample provides advantageous guarantee for the improvement of diaphragm coating liquid performance.
In a preferred embodiment, inorganic particle includes in aluminium oxide, barium titanate, magnesium hydroxide or silica
Any one or at least two combination；
Preferably, organic solvent includes N-Methyl pyrrolidone, dimethyl acetamide, n,N-Dimethylformamide or neighbour
In rutgers any one or at least two combination；
Preferably, pore creating material include in dimethyl carbonate, ethyl acetate, hexamethylene or dimethyl phosphate any one or
At least two combination；
Preferably, binder include in Kynoar, polyvinylpyrrolidone or polyvinyl alcohol any one or extremely
Few two kinds of combination；
Preferably, dispersing agent includes vinyl bis-stearamides and/or oxidized polyethylene wax.
It can make diaphragm coating liquid that there is good thermal contraction performance by adding inorganic particle, improve the performance of basement membrane.Allusion quotation
Type but unrestricted, inorganic particle can be aluminium oxide, can be barium titanate, can be magnesium hydroxide, can also be titanium dioxide
Silicon.
N-Methyl pyrrolidone (N-Methyl pyrrolidone, NMP) is colorless and transparent oily, micro- to have having for amine smell
Solvent.Its volatility is low, and thermal stability, chemical stability are good, can volatilize with water vapour, in lithium electricity, medicine, pesticide, face
It is widely applied in the industries such as material, cleaning agent, insulating materials.
Dimethyl acetamide (Dimethylacetamide, DMAC) is a kind of colorless and transparent organic solvent, can with water,
Alcohols, ethers or esters equal solvent arbitrarily mix.
N,N-Dimethylformamide (N, N-Dimethylformamide, DMF) is colorless and transparent, a kind of to have many uses
Organic solvent has good solvability and chemical stability to a variety of organic compounds and inorganic compound.
Repefral (Dimethylphthalate, DMP) is yellowish oily organic solvent, slightly fragrant
Fragrance, can be with the immiscible organic solvents such as ethyl alcohol, ether, not soluble in water and petroleum ether.
It should be noted that the organic solvent also can choose other common organic solvents of this field, as long as this has
Solvent and above-mentioned four kinds of organic solvents or its organic solvent being mixed to form have similar performance.
The present invention is not particularly limited the type of pore creating material, binder and dispersing agent.It is typical but unrestricted, pore-creating
Agent can choose dimethyl carbonate, can choose ethyl acetate, can choose hexamethylene, can choose dimethyl phosphate, may be used also
With the mixture of dimethyl carbonate and ethyl acetate；Binder can choose Kynoar, can choose polyvinylpyrrolidine
Ketone, it is also an option that polyvinyl alcohol；Dispersing agent can choose vinyl bis-stearamides, can choose oxidized polyethylene wax, also
It can choose the mixture of vinyl bis-stearamides and oxidized polyethylene wax.
In a preferred embodiment, polyetherimide solution includes polyetherimide and lytic agent, lytic agent packet
It includes any one in N-Methyl pyrrolidone, dimethyl acetamide, n,N-Dimethylformamide or repefral
Kind or at least two combination.
It is to be appreciated that polyetherimide is solid, need for polyetherimide to be dissolved in competence exertion in lytic agent
The characteristic of its high stability.Typical but unrestricted, lytic agent can choose N-Methyl pyrrolidone, dimethyl acetamide, N,
Dinethylformamide or repefral.
In a preferred embodiment, polyetherimide is to pass through pretreated polyetherimide, and pretreatment includes
It is dry；
Preferably, dry temperature is 110-150 DEG C；
Preferably, the dry time is 2-4h.
It is to be appreciated that above-mentioned pretreated purpose is to remove the moisture that may contain in polyetherimide, it is ensured that after
Continuous diaphragm coating liquid manufacturing process is gone on smoothly.It is typical but unrestricted, it is removed in polyetherimide by the way of dry
The moisture that may contain.The dry time can be 2h, 3h or 4h；Dry temperature can be 110 DEG C, and 120 DEG C, 130 DEG C,
140 DEG C or 150 DEG C.
Second aspect provides a kind of diaphragm coating liquid at least one embodiment, using above-mentioned diaphragm coating liquid
Production method is made.
The percent thermal shrinkage of basement membrane can be effectively reduced using diaphragm coating liquid made from the above method, can totally be improved
The performance of basement membrane.
The third aspect provides a kind of diaphragm at least one embodiment, including basement membrane and above-mentioned diaphragm coating liquid shape
At coating liquid layer；
Preferably, basement membrane includes polyethylene or polypropylene.
Diaphragm percent thermal shrinkage provided by the invention including above-mentioned diaphragm coating liquid is small, high mechanical strength, good combination property.
It should be noted that the coating that diaphragm provided by the invention is mainly formed by basement membrane and its surface upper diaphragm coating liquid
Liquid layer composition, is not particularly limited the material of basement membrane, typical but unrestricted, basement membrane can be polyethylene, be also possible to
Polypropylene.
It is mainly further described in detail by taking polyethylene as an example below the present invention, it is understood, however, that, basement membrane
Including but not limited to polyethylene.
Fourth aspect provides a kind of production method of above-mentioned diaphragm, comprising: apply diaphragm at least one embodiment
The surface that covering liquid is coated in basement membrane carries out the step of pore-creating solidification and post-processing.
The production method of above-mentioned diaphragm provided by the invention, easy to operate, feasibility is strong, diaphragm coating liquid can be improved base
The Function of film percent thermal shrinkage to maximum.
The diaphragm after progress pore-creating solidification is dried for standby it should be noted that above-mentioned post-processing is meant that.It is typical but
Unrestricted, the temperature of drying can be 50 DEG C, 60 DEG C or 70 DEG C；The time of drying can be 7h, 8h or 9h.
In a preferred embodiment, the cured mode of pore-creating includes extraction, and the extractant of extraction includes inorganic extraction
Take agent and/or organic extractant；
Preferably, inorganic extractant includes water；
Preferably, organic extractant include N-Methyl pyrrolidone, dimethyl acetamide, n,N-Dimethylformamide or
In repefral any one or at least two combination；
Preferably, the number of extraction is 2-4 times.
It should be noted that the cured purpose of pore-creating be make be coated in epilamellar diaphragm coating liquid generate a some holes, and
Existing polyetherimide is attached on the surface of basement membrane in liquid form before being allowed to, and plays the effect of its high stability.
Present invention mode cured for pore-creating does not have particular/special requirement, as long as reaching above-mentioned purpose.For example, pore-creating is solid
The mode slective extraction of change, typical but unrestricted, the number of extraction can be 2 times, 3 times or 4 times；Required extractant can be with
It is inorganic solvent, such as water；It is also possible to organic solvent, such as N-Methyl pyrrolidone, dimethyl acetamide, phthalic acid
Dimethyl ester or n,N-Dimethylformamide；It can also be and used after preparing organic solvent according to a certain percentage with inorganic solvent.
5th aspect, provides a kind of secondary cell at least one embodiment, including above-mentioned diaphragm or it is above-mentioned every
Diaphragm made from the production method of film.
A kind of secondary cell provided by the invention, due to including the above-mentioned diaphragm with high stability, low heat shrinkage,
Security performance also has significant improvement.The secondary cell includes lithium ion battery, sodium-ion battery, lithium-sulfur cell or potassium
Ion battery etc..
Combined with specific embodiments below, comparative example, experimental example and attached drawing, the invention will be further described.
Embodiment 1
The production method for present embodiments providing a kind of diaphragm coating liquid, comprising the following steps:
(1) by 75g polyetherimide 110 DEG C at a temperature of dry 3h, then 50 DEG C at a temperature of, by the poly- of drying
Etherimide is dissolved in the N-Methyl pyrrolidone of 1.92L, obtains polyetherimide solution；
(2) 30g Kynoar powder is added in polyetherimide solution, then stirring adds 150g to dissolving
Dimethyl carbonate stirs until the polyetherimide dissolution being precipitated, obtains the first dispersion liquid；
(3) 1.5g vinyl bis-stearamides are added in the N-Methyl pyrrolidone of 300mL, are stirred evenly, then
450g alumina particle is added, it is fully dispersed, obtain the second dispersion liquid；
(4) the first dispersion liquid is mixed with the second dispersion liquid, is stirred until homogeneous, obtain mixed liquor, then by mixed liquor mistake
(80-120 mesh) discharging is filtered, diaphragm coating liquid is obtained；
Wherein, the quality of polyetherimide solution accounts for the 5% of diaphragm coating liquid gross mass, the quality of alumina particle account for every
The 15% of film coating liquid gross mass, the quality of dimethyl carbonate account for the 5% of diaphragm coating liquid gross mass, the quality of Kynoar
The 1% of diaphragm coating liquid gross mass is accounted for, the quality of vinyl bis-stearamides accounts for the 0.5% of diaphragm coating liquid gross mass.
Embodiment 2
The production method for present embodiments providing a kind of diaphragm coating liquid, comprising the following steps:
(1) by 300g polyetherimide 150 DEG C at a temperature of dry 2h, then 60 DEG C at a temperature of, by drying
Polyetherimide is dissolved in the dimethyl acetamide of 600mL, obtains polyetherimide solution；
(2) 90g polyvinylpyrrolidonepowder powder is added in polyetherimide solution, then stirring is added to dissolving
450mL ethyl acetate stirs until the polyetherimide dissolution being precipitated, obtains the first dispersion liquid；
(3) 90g oxidized polyethylene wax is added in the N-Methyl pyrrolidone of 600mL, is stirred evenly, then added
900g barium titanate particles, it is fully dispersed, obtain the second dispersion liquid；
(4) the first dispersion liquid is mixed with the second dispersion liquid, is stirred until homogeneous, obtain mixed liquor, then by mixed liquor mistake
(80-120 mesh) discharging is filtered, diaphragm coating liquid is obtained；
Wherein, the quality of polyetherimide solution accounts for the 10% of diaphragm coating liquid gross mass, and the quality of barium titanate particles accounts for
The 30% of diaphragm coating liquid gross mass, the quality of ethyl acetate account for the 15% of diaphragm coating liquid gross mass, polyvinylpyrrolidone
Quality account for the 3% of diaphragm coating liquid gross mass, the quality of oxidized polyethylene wax accounts for the 3% of diaphragm coating liquid gross mass.
Embodiment 3
The production method for present embodiments providing a kind of diaphragm coating liquid, comprising the following steps:
(1) by 240g polyetherimide 130 DEG C at a temperature of dry 4h, then 80 DEG C at a temperature of, by drying
Polyetherimide is dissolved in the dimethyl acetamide of 1.4L, obtains polyetherimide solution；
(2) 60g pva powder is added in polyetherimide solution, then stirring adds 300g phosphorus to dissolving
Dimethyl phthalate stirs until the polyetherimide dissolution being precipitated, obtains the first dispersion liquid；
(3) 30g vinyl bis-stearamides are added in the repefral of 400mL, are stirred evenly, then
600g silica dioxide granule is added, it is fully dispersed, obtain the second dispersion liquid；
(4) the first dispersion liquid is mixed with the second dispersion liquid, is stirred until homogeneous, obtain mixed liquor, then by mixed liquor mistake
(80-120 mesh) discharging is filtered, diaphragm coating liquid is obtained；
Wherein, the quality of polyetherimide solution accounts for the 8% of diaphragm coating liquid gross mass, and the quality of silica dioxide granule accounts for
The 20% of diaphragm coating liquid gross mass, the quality of dimethyl phosphate account for the 10% of diaphragm coating liquid gross mass, the matter of polyvinyl alcohol
Amount accounts for the 2% of diaphragm coating liquid gross mass, and the quality of vinyl bis-stearamides accounts for the 1% of diaphragm coating liquid gross mass.
Embodiment 4
The production method for present embodiments providing a kind of diaphragm coating liquid, in addition to changing the step polyetherimide in (1)
Amount is 300g, and the quality of polyetherimide solution is made to account for the 10% of diaphragm coating liquid gross mass, remaining preparation step and embodiment 1
It is identical.
Embodiment 5
The production method for present embodiments providing a kind of diaphragm coating liquid, in addition to changing the step alumina particle in (3)
Amount is 900g, and the quality of alumina particle is made to account for the 30% of diaphragm coating liquid gross mass, remaining preparation step and 1 phase of embodiment
Together.
Embodiment 6
The production method for present embodiments providing a kind of diaphragm coating liquid, in addition to by alumina particle 450g in step (3)
Replace with barium titanate particles 450g, the quality of barium titanate particles made to account for the 5% of diaphragm coating liquid gross mass, remaining preparation step with
Embodiment 1 is identical.
Embodiment 7
The production method for present embodiments providing a kind of diaphragm coating liquid, in addition to by alumina particle 450g in step (3)
Magnesium hydroxide particle 450g is replaced with, the quality of magnesium hydroxide particle is made to account for the 5% of diaphragm coating liquid gross mass, remaining preparation step
It is rapid same as Example 1.
Embodiment 8
The production method for present embodiments providing a kind of diaphragm coating liquid, in addition to changing the step Kynoar powder in (2)
The amount at end is 90g, and the quality of Kynoar is made to account for the 3% of diaphragm coating liquid gross mass, remaining preparation step and 1 phase of embodiment
Together.
Embodiment 9
The production method for present embodiments providing a kind of diaphragm coating liquid, in addition to changing the step dimethyl carbonate in (2)
Amount is 450g, and the quality of dimethyl carbonate is made to account for the 15% of diaphragm coating liquid gross mass, remaining preparation step and 1 phase of embodiment
Together.
Embodiment 10
The production method for present embodiments providing a kind of diaphragm coating liquid, it is double stearic in addition to changing the step (3) medium vinyl
The amount of amide is 90g, and the quality of vinyl bis-stearamides is made to account for the 3% of diaphragm coating liquid gross mass, remaining preparation step with
Embodiment 1 is identical.
Comparative example 1
This comparative example provides a kind of production method of diaphragm coating liquid, in addition to being in N- in no step (1), step (2)
Kynoar powder is added in methyl pyrrolidone, stirs to dissolving, then adds 150g dimethyl carbonate, stirring to analysis
Until polyetherimide dissolution out, the first dispersion liquid is obtained, remaining preparation step is same as Example 1.
Comparative example 2
This comparative example provides a kind of production method of diaphragm coating liquid, in addition to not adding alumina particle in step (3),
Remaining preparation step is same as Example 1.
Comparative example 3
This comparative example provides a kind of production method of diaphragm coating liquid, in addition to being in N- in no step (1), step (2)
Kynoar powder is added in methyl pyrrolidone, step does not add alumina particle in (3), remaining preparation step and implementation
Example 1 is identical.
Experimental example
(1) extract liquor is prepared
N-Methyl pyrrolidone and deionized water are mixed respectively with volume ratio for the ratio of 3:2,1:1,2:3, obtained
To the first extract liquor, the second extract liquor and third extract liquor.
(2) diaphragm is made
The obtained diaphragm coating liquid of above-described embodiment 1-10 and comparative example 1-3 is respectively coated with the speed of 8-15m/min
In polyethylene based film, then successively coextraction 3 times, connect by the first extract liquor, the second extract liquor and the extraction of third extract liquor
Be washed with deionized, then in 60 DEG C of drying 8h, finally obtain diaphragm.Wherein, Fig. 1 is what the embodiment of the present invention 1 provided
Diaphragm coating liquid is coated in the SEM picture of the diaphragm obtained in polyethylene based film；Table 1 is embodiment 1-10 in experimental example of the present invention
The relevant parameter of obtained diaphragm and polyethylene based film in polyethylene based film is coated in the diaphragm coating liquid that comparative example 1-3 is provided
Contrast table.
The diaphragm coating liquid that table 1 embodiment 1-10 and comparative example 1-3 are provided is coated in the diaphragm obtained in polyethylene based film
With the relevant parameter contrast table of polyethylene based film
Note: the appearance of each diaphragm and polyethylene based film that this experimental example obtains is ash or white
From table 1 it follows that the production method of diaphragm coating liquid provided by the invention can retain polyethers to greatest extent
Original stability of imide solution makes diaphragm coating liquid have good thermal contraction performance by adding inorganic particle.Its
In, compared with polyethylene based film, diaphragm percent thermal shrinkage provided by the invention reduces by 50%, and needle pierces enhanced strength 5%.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of production method of diaphragm coating liquid characterized by comprising
The first dispersion liquid that polyetherimide solution, binder and pore creating material are formed is provided；
The second dispersion liquid that inorganic particle, dispersing agent and organic solvent are formed is provided；
First dispersion liquid is mixed with the second dispersion liquid, separates, obtains diaphragm coating liquid；
Wherein, the quality of the polyetherimide solution accounts for the 5%-10% of the diaphragm coating liquid gross mass；
The quality of the inorganic particle accounts for the 15%-30% of the diaphragm coating liquid gross mass.
2. the production method of diaphragm coating liquid according to claim 1, which is characterized in that the quality of the pore creating material accounts for institute
State the 5%-15% of diaphragm coating liquid gross mass；
Preferably, the quality of the binder accounts for the 1%-3% of the diaphragm coating liquid gross mass；
Preferably, the quality of the dispersing agent accounts for the 0.5%-3% of the diaphragm coating liquid gross mass.
3. the production method of diaphragm coating liquid according to claim 1, which is characterized in that the inorganic particle includes oxidation
In aluminium, barium titanate, magnesium hydroxide or silica any one or at least two combination；
Preferably, the organic solvent includes N-Methyl pyrrolidone, dimethyl acetamide, n,N-Dimethylformamide or neighbour
In rutgers any one or at least two combination；
Preferably, the pore creating material include in dimethyl carbonate, ethyl acetate, hexamethylene or dimethyl phosphate any one or
At least two combination；
Preferably, the binder include in Kynoar, polyvinylpyrrolidone or polyvinyl alcohol any one or extremely
Few two kinds of combination；
Preferably, the dispersing agent includes vinyl bis-stearamides and/or oxidized polyethylene wax.
4. the production method of diaphragm coating liquid according to claim 1-3, which is characterized in that the polyetherimide
Amine aqueous solution includes polyetherimide and lytic agent；
The lytic agent includes N-Methyl pyrrolidone, dimethyl acetamide, n,N-Dimethylformamide or phthalic acid
In dimethyl ester any one or at least two combination.
5. the production method of diaphragm coating liquid according to claim 4, which is characterized in that the polyetherimide is to pass through
Pretreated polyetherimide, the pretreatment include drying；
Preferably, the temperature of the drying is 110-150 DEG C；
Preferably, the time of the drying is 2-4h.
6. a kind of diaphragm coating liquid, which is characterized in that using the production side of the described in any item diaphragm coating liquids of claim 1-5
Method is made.
7. a kind of diaphragm, which is characterized in that including basement membrane and the coating liquid formed by diaphragm coating liquid as claimed in claim 6
Layer；
Preferably, the basement membrane includes polyethylene or polypropylene.
8. the production method of diaphragm as claimed in claim 7 characterized by comprising the diaphragm coating liquid is coated in institute
The step of stating the surface progress pore-creating solidification and post-processing of basement membrane.
9. the production method of diaphragm according to claim 8, which is characterized in that the cured mode of pore-creating includes extraction
It takes, the extractant of the extraction includes inorganic extractant and/or organic extractant；
Preferably, the inorganic extractant includes water；
Preferably, the organic extractant include N-Methyl pyrrolidone, dimethyl acetamide, n,N-Dimethylformamide or
In repefral any one or at least two combination；
Preferably, the number of the extraction is 2-4 times.
10. a kind of secondary cell, which is characterized in that including described in diaphragm as claimed in claim 7 or claim 8 or 9 every
Diaphragm made from the production method of film.
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| CN201910135040.XA CN109860483B (en) | 2019-02-28 | 2019-02-28 | Separator coating liquid and manufacturing method thereof, separator and manufacturing method thereof, and secondary battery |
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| CN201910135040.XA CN109860483B (en) | 2019-02-28 | 2019-02-28 | Separator coating liquid and manufacturing method thereof, separator and manufacturing method thereof, and secondary battery |
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Cited By (1)
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|---|---|---|---|---|
| CN112635914A (en) * | 2020-12-21 | 2021-04-09 | 中材锂膜有限公司 | Lithium ion battery diaphragm with heat resistance and high mechanical strength and preparation method thereof |
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| CN109860483B (en) | 2022-07-05 |
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