CN108933219A - A kind of preparation method of lithium battery diaphragm - Google Patents
A kind of preparation method of lithium battery diaphragm Download PDFInfo
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- CN108933219A CN108933219A CN201811147152.9A CN201811147152A CN108933219A CN 108933219 A CN108933219 A CN 108933219A CN 201811147152 A CN201811147152 A CN 201811147152A CN 108933219 A CN108933219 A CN 108933219A
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- basement membrane
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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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- 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
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Abstract
The present invention provides a kind of preparation method of lithium battery diaphragm, including prepares aqueous slurry suddenly in two steps；The aqueous slurry of preparation is coated on basement membrane, low temperature drying to constant weight；And lithium battery diaphragm is obtained after high-temperature process and crosslinking.The lithium battery diaphragm obtained using preparation method provided by the invention, the peel strength of lithium battery diaphragm greatly improved, improve the caking property between coating and basement membrane, effectively improve the heat resistance of lithium battery diaphragm, the percent thermal shrinkage of diaphragm is reduced, thus safety problem caused by avoiding lithium battery from being heat-shrinked in use because of diaphragm.And the gas permeability of lithium battery diaphragm is uninfluenced, or even slightly improves, and ensure that ion passes through lithium battery in use.
Description
Technical field
The invention belongs to lithium battery diaphragm field, be related to a kind of lithium battery diaphragm preparation method more particularly to a kind of energy
Enough improve the preparation method of the lithium battery diaphragm of cohesive force between basement membrane and coating.
Background technique
In lithium battery structure, diaphragm is its crucial one of internal component, and the main function of diaphragm is make battery positive and negative
It is extremely separated, it prevents the two poles of the earth from contacting and leading to short circuit, furthermore also acts as the effect in electrolyte ion channel.Therefore, the performance of diaphragm
Determine interfacial structure, the internal resistance size of lithium battery, and the spies such as capacity, cycle-index and security performance for directly affecting battery
Property.
Since the electrolyte in lithium battery structure is organic system, it is therefore desirable to the diaphragm material of organic solvent-resistant, currently,
Generally use the polyolefin porous membrane of high-strength thin-film.The production technology of polyolefin porous membrane can be divided into dry method (fusion drawn
Method, MSCS) and two kinds of wet process (thermally induced phase separation, TIPS).Wherein, the basic process of wet process refers to polymer at high temperature
It is dissolved in the solvent of higher boiling, low volatility and forms homogeneous liquid, then cooling down, generation mutually separates, then with suitable reagent
High boiling solvent is extracted, by the dry porous membranes for obtaining certain planform.In diaphragm microporous barrier system
During making, uniaxial or biaxial stretching can be carried out before solvent extraction, and setting treatment is carried out after extraction and wind film forming, it can also
To be stretched after the extraction.
As lithium battery applications range constantly expands, from number to electric car, the various aspects such as electric tool.It obtains
High capacity provides big power, and a usual battery needs to be concatenated using dozens or even hundreds of battery core.Due to lithium electricity
There are potential explosion danger, the safety of diaphragm is quite important in pond.But no matter polyethylene, polypropylene or other thermoplasticity are high
Molecular material, when close to fusing point material can contraction distortion due to fusing, brought to the safety of power battery potential hidden
Suffer from.Domestic and international more companies and research institution are improved in terms of being all directed to diaphragm thermal stability, and the mode of mainstream is at present
It is coated with one layer of refractory layer in polyolefin-based film surface, refractory layer is mainly based on inorganic matter such as aluminium oxide.Chinese patent
CN201110002330.0 proposes a kind of technique in polyalkene diaphragm surface coated inorganic object, by the aluminium oxide of certain partial size/
Silica/zirconium oxide etc. is coated on membrane surface, and the temperature tolerance of diaphragm entirety is improved using the high temperature resistance of inorganic matter.Preparation
This diaphragm needs that inorganic matter and solvent, dispersing agent, glue and other auxiliary agents are configured to slurry first, then passes through coating
Slurry is coated in polyolefin base membrane by equipment, obtains the diaphragm of inorganic matter coating after dry.
According to the solvent type added when configuration slurry, such as inorganic solvent, organic solvent, and obtained slurry is divided into water
Property slurry and oil slurry.Wherein, oil slurry and polyolefin base membrane have better wellability, apply in the diaphragm being prepared
More preferably, the performance of diaphragm is more excellent, but there are high production cost, it is possible to create waste liquid exhaust gas for caking property between layer and basement membrane
It is endangered Deng environmental protection.Therefore improving the caking property between aqueous slurry and polyolefin base membrane is following main direction of studying.
The main path for improving caking property includes the dosage for selecting caking property more preferably glue and increasing glue.Wherein, it opens
The hair better glue of caking property needs to rethink the ingredient design of glue, while to take into account stability of the glue in lithium battery
And compatibility, difficulty are larger.Although and caking property between coating and basement membrane, excessive glue can be increased by increasing glue quantity
Water will cause the original hole blocking of basement membrane, to reduce the performance of battery.
Summary of the invention
In view of the foregoing defects the prior art has, provide one kind can be improved cohesive force between basement membrane and coating to the present invention
Lithium battery diaphragm preparation method.
The preparation method of lithium battery diaphragm provided by the invention, includes the following steps:
Step 1 prepares aqueous slurry；
It is wetting agent, the 20- of the particles of inorganic material of 20-60%, the dispersing agent of 0.5-5%, 0.1-10% by mass content
80% deionized water is mixed, and obtains dispersion liquid；
The binder that mass content is 0.3-5% is added in the dispersion liquid, continues stirring to being uniformly mixed, obtains
The aqueous slurry；
Step 2, the aqueous slurry that step 1 is prepared are coated on a thickness of 5-25 μm, porosity 30-80%
Basement membrane one or both sides, then dry under the conditions of 30-60 DEG C to constant weight, obtain coating basement membrane；
Step 3, the coating basement membrane that step 2 is prepared handle 10-300s under the conditions of certain temperature.Described one
The lower limit for determining temperature is the softening temperature of aqueous binders, guarantees that aqueous binders softening is flowable, the upper limit is the basement membrane
15 DEG C under fusing point, guarantee occurring without obvious melting phenomenon for basement membrane described in treatment process；
Step 4, crosslinking；
If temperature is lower than 15 DEG C under the fusing point of the substrate in fact for the crosslinking of the binder, with the bonding
For temperature under the crosslinking initial temperature of agent to the fusing point of the substrate between 15 DEG C as crosslinking temperature, prepared by processing step 3
The obtained coating basement membrane 5-30min after high-temperature process；
Or
Under room temperature, using electron energy 1-2Mev, the ray of flow velocity 2-5mA, radiation treatment step 3 be prepared through height
Temperature treated coating basement membrane 20-60s.
In a preferred embodiment, the step 1 are as follows: prepare aqueous slurry；
It is wetting agent, the 20- of the particles of inorganic material of 20-60%, the dispersing agent of 0.5-5%, 0.1-10% by mass content
80% deionized water passes through sand mill first and it is sanded, and keeps the inorganic matter evenly dispersed, is then sufficiently stirred, obtains
To dispersion liquid；
The binder that mass content is 0.3-5% is added in the dispersion liquid, continues stirring to being uniformly mixed, obtains
The aqueous slurry.
In a preferred embodiment, in the aqueous slurry each component mass content are as follows:
In a preferred embodiment, in the aqueous slurry each component mass content are as follows:
In a preferred embodiment, the particles of inorganic material includes magnesia, calcium oxide, silica, aluminium oxide, two
Zirconium oxide, boehmite, any one or a few combination in barium sulfate, preferably aluminium oxide, silica, appointing in boehmite
Meaning one or more combination.
In a preferred embodiment, the partial size D50 of the particles of inorganic material be 9nm-2000nm, as 10nm, 15nm,
1300nm, 1500nm, 1800nm etc., D90 < 4000nm, it is preferable that the partial size D50 of the particles of inorganic material is 20nm-
1000nm, such as 50nm, 80nm, 300nm, 500nm, 800nm, D90 < 2500nm.
In a preferred embodiment, the binder is aqueous binders, and the binder is to be prone to crosslinking
Binder, such as appointing in rubber binder, vinyl acetate class binder, epoxyn, polyurethanes binder
Anticipate one or more combination, the softening temperature of aqueous binders described in wherein at least one lower than the fusing point of the basement membrane under
15 DEG C, the fusing point of the preferably described binder is lower than 15 DEG C below the fusing point of the basement membrane.
In a preferred embodiment, the dispersing agent is n-butanol, cyclohexanol, ethyl alcohol, polyvinylpyrrolidone, carboxylic acid
The combination of one or more of salt, sulfonate, sulfuric acid ester salt.
In a preferred embodiment, the wetting agent includes ethyl alcohol, and propylene glycol, n-butanol, isopropanol, glycerol etc. is wherein
One or more, the wetting agent makes deionized water spread over solid material by reducing its surface tension or interfacial tension
Surface.
In a preferred embodiment, in order to control the viscosity of the aqueous slurry, carboxymethyl cellulose can also be added
The thickeners such as sodium, methyl hydroxyethylcellulose.
In order to improve the levelability of the aqueous slurry, levelling agent can also be added.
In order to control the quick abjection of bubble in the aqueous slurry, defoaming agent can also be added.
The beneficial effects of the present invention are: lithium battery diaphragm preparation process provided by the invention is used, it is specific by screening
Binder, and use corresponding preparation process, under the premise of not influencing lithium battery septum permeability, hence it is evident that improve lithium electricity
The adhesion strength of pond diaphragm floating coat and basement membrane, and percent thermal shrinkage declines to a great extent, hence it is evident that improve the stability of lithium battery diaphragm.
Specific embodiment
Illustrate preparation method of the invention in order to clearer, now in conjunction with specific embodiment to lithium battery provided by the invention
The preparation process of diaphragm is done described briefly below.But it should be recognized that specific embodiment provided by the invention is the present invention
The preferred embodiment of claimed preparation process, can't to the present invention claims protection scope formed any restrictions.
One, the preparation of lithium battery diaphragm
Embodiment 1
Step 1 prepares basement membrane and coating sizing-agent.
Ultra-high molecular weight polyethylene, the paraffin oil of 70 parts by weight, 0.3 parts by weight by 30 parts by weight molecular weight for 1,500,000
Four-[3- (3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters be sufficiently mixed after by double screw extruder squeeze
Out, extrusion temperature is 200 DEG C, and chill-roll temperature is 20 DEG C, obtains the basement membrane ontology with a thickness of 1400 μm.Then using stretching
5 times of machine longitudinal stretching, the temperature of longitudinal stretching machine is change of gradient.Then the temperature of 8 times of cross directional stretch, transverse drawing mill is
125℃.Stretched basement membrane is imported in extraction tank, is come into full contact in extraction tank with extractant methylene chloride, with extraction
Pore former, obtains wet basis film after extraction tank, and wet basis film, through drying, obtains in 35 DEG C of baking ovens with a thickness of 12um, porosity
40% basement membrane.
By the aluminum oxide micro-sphere that mass content is 32%, D50 is 800nm, the dehydrated alcohol that mass content is 5%, quality
The deionized water that content is 60% is mixed 0.5h, obtains dispersion liquid；The fourth that by mass content be 1%, fusing point is 110 DEG C
Atrolactamide is added in dispersion liquid, is continued to stir 1h to being uniformly mixed, is obtained the aqueous slurry that viscosity at 25 DEG C is 120cp.
Step 2, coating.
The aqueous slurry being prepared is coated on to the side for the basement membrane being prepared using gravure coating process, then 40
It is DEG C dry to constant weight, obtain the coating basement membrane that coating layer thickness is 4um.
Step 3, high-temperature process.
Coating basement membrane prepared by step 2 is stopped into 2min in 110 DEG C of baking ovens, obtains the coating basement membrane through high-temperature process.
Step 4, crosslinking.
Using GJ-2 type high frequency high voltage electron accelerator, under the conditions of electron energy 1.7Mev, a fluid stream 3mA, to irradiate step
The coating basement membrane 0.5min through high-temperature process of rapid 3 preparation, obtains lithium battery diaphragm provided by the invention.
Embodiment 2
Step 1 prepares basement membrane and coating sizing-agent.
Ultra-high molecular weight polyethylene, the paraffin oil of 75 parts by weight, 0.3 parts by weight by 25 parts by weight molecular weight for 1,500,000
Four-[3- (3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters be sufficiently mixed after by double screw extruder squeeze
Out, extrusion temperature is 200 DEG C, and chill-roll temperature is 20 DEG C, obtains the basement membrane ontology with a thickness of 1400 μm.Then using stretching
5 times of machine longitudinal stretching, the temperature of longitudinal stretching machine is change of gradient.Then the temperature of 8 times of cross directional stretch, transverse drawing mill is
125℃.Stretched basement membrane is imported in extraction tank, is come into full contact in extraction tank with extractant methylene chloride, with extraction
Pore former obtains wet basis film after extraction tank, wet basis film, through drying, obtains in 35 DEG C of baking ovens with a thickness of 12um, porosity
40% basement membrane.
By the aluminum oxide micro-sphere that mass content is 35%, D50 is 800nm, the ammonium polyacrylate that mass content is 3.5%
Salt, the deionized water that mass content is 60% are mixed 0.5h, obtain dispersion liquid；By mass content be 1.5%, fusing point is
100 DEG C of ethylene vinyl acetate copolymer is added in dispersion liquid, is continued to stir 1h to being uniformly mixed, is obtained viscosity at 25 DEG C
For the aqueous slurry of 160cp.
Step 2, coating.
The aqueous slurry being prepared is coated on to the side for the basement membrane being prepared using gravure coating process, then 36
It is DEG C dry to constant weight, obtain the coating basement membrane that coating layer thickness is 4um.
Step 3, high-temperature process.
Coating basement membrane prepared by step 2 is stopped into 2.5min in 100 DEG C of baking ovens, obtains the coating base through high-temperature process
Film.
Step 4, crosslinking.
Using GJ-2 type high frequency high voltage electron accelerator, under the conditions of electron energy 1.7Mev, a fluid stream 3mA, irradiation steps 3
The coating basement membrane 0.75min through high-temperature process of preparation, obtains lithium battery diaphragm provided by the invention.
Embodiment 3
Except the drying temperature after being coated in step 2 is 110 DEG C, remaining condition is same as Example 2.
Embodiment 4
Step 1 prepares basement membrane and coating sizing-agent.
Select dry method simple tension polypropylene diaphragm as substrate, thickness 20um, porosity 42%；
By the boehmite that mass content is 35%, D50 is 500nm, the isopropanol that mass content is 4.5%, mass content
For 59% deionized water, 0.5h is mixed, obtains dispersion liquid；The ethylene that by mass content be 1.5%, fusing point is 100 DEG C
Vinyl acetate co-polymer is added in dispersion liquid, continue under the conditions of 200rmp stir 1h to be uniformly mixed, when obtaining 25 DEG C
Viscosity is the aqueous slurry of 130cp.
Step 2, coating.
The aqueous slurry being prepared is coated on to the side for the basement membrane being prepared using gravure coating process, then 40
It is DEG C dry to constant weight, obtain the coating basement membrane that coating layer thickness is 4um.
Step 3, high-temperature process.
Coating basement membrane prepared by step 2 is stopped into 3min in 90 DEG C of baking ovens, obtains the coating basement membrane through high-temperature process.
Step 4, crosslinking.
It controls oven heat and heat roller temperature is 150 DEG C, the coating basement membrane through high-temperature process prepared by crosslinking treatment step 3
5min obtains lithium battery diaphragm provided by the invention.
Embodiment 5
Select dry method simple tension polypropylene diaphragm as substrate, thickness 20um, porosity 42%；
By the fumed silica that mass content is 32%, D50 is 100nm, the ethyl alcohol that mass content is 5%, quality contains
The deionized water that amount is 60% is mixed 0.5h, obtains dispersion liquid；It is 3% by mass content, fusing point is 130 DEG C natural
Elastomer latex is added in dispersion liquid, continues to stir 1h under the conditions of 200rmp to being uniformly mixed, viscosity is when obtaining 25 DEG C
The aqueous slurry of 120cp.
Step 2, coating.
The aqueous slurry being prepared is coated on to the side for the basement membrane being prepared using gravure coating process, then 40
It is DEG C dry to constant weight, obtain the coating basement membrane that coating layer thickness is 3um.
Step 3, high-temperature process.
Coating basement membrane prepared by step 2 is stopped into 1.5min in 130 DEG C of hot-airs, obtains lithium battery provided by the invention
Diaphragm.
Comparative example 1
Compared with Example 1, lack step 3 high-temperature process and step 4 is crosslinked, remaining is identical.
Comparative example 2
Compared with Example 2, lack step 3 high-temperature process and step 4 is crosslinked, remaining is identical.
Comparative example 3
Compared with Example 4, lack step 3 high-temperature process and step 4 is crosslinked, remaining is identical.
Comparative example 4
Ultra-high molecular weight polyethylene, the paraffin oil of 70 parts by weight, 0.3 parts by weight by 30 parts by weight molecular weight for 1,500,000
Four-[3- (3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters be sufficiently mixed after by double screw extruder squeeze
Out, extrusion temperature is 200 DEG C, and chill-roll temperature is 20 DEG C, obtains the basement membrane ontology with a thickness of 1400 μm.Then using stretching
5 times of machine longitudinal stretching, the temperature of longitudinal stretching machine is change of gradient.Then the temperature of 8 times of cross directional stretch, transverse drawing mill is
125℃.Stretched basement membrane ontology is imported in extraction tower, is come into full contact in extraction tower with extractant methylene chloride, with
Pore former is extracted, extractant of the basement membrane containing extractant through liquid sweeping roller scraper surface come out from extraction tower obtains wet basis film, wet
Basement membrane, through drying, obtains in 35 DEG C of baking ovens with a thickness of 12um, the basement membrane of porosity 40%.
By the aluminum oxide micro-sphere that mass content is 32%, D50 is 800nm, the dehydrated alcohol that mass content is 5%, quality
The deionized water that content is 62% is mixed 0.5h, obtains dispersion liquid；By mass content be 2%, fusing point is 110 DEG C third
Olefin(e) acid glue is added in dispersion liquid, is continued to stir 1h to being uniformly mixed, is obtained the aqueous slurry that viscosity at 25 DEG C is 206cp.
Step 2, coating.
The aqueous slurry being prepared is coated on to the side for the basement membrane being prepared using gravure coating process, then 40
It is DEG C dry to constant weight, obtain the coating basement membrane that coating layer thickness is 4um.
Step 3, high-temperature process.
Coating basement membrane prepared by step 2 is stopped into 2min in 110 DEG C of baking ovens, obtains the coating basement membrane through high-temperature process.
Step 4, crosslinking.
Using GJ-2 type high frequency high voltage electron accelerator, under the conditions of electron energy 1.7Mev, a fluid stream 3mA, irradiation steps 3
The coating basement membrane 0.5min through high-temperature process of preparation, obtains lithium battery diaphragm provided by the invention.
Two, the physicochemical property detection of lithium battery diaphragm
The physicochemical property of the lithium battery diaphragm of above-mentioned preparation is detected, specific detection data is as shown in table 1:
The physicochemical property of table 1, lithium battery diaphragm
Wherein, the calculation method or test method of each physical and chemical parameter are as follows:
1, it breathes freely and is worth: the time measurement for using ASTM standard to need by the air of 100cc, unit s/100cc.
2, puncture strength: the needle for being 1.0mm with the diameter that end is spherical surface (radius of curvature R=0.5mm), with 2.0mm/
Second speed the lithium battery diaphragm of preparation is pierced through, maximum, force is denoted as puncture strength when piercing through diaphragm, unit be gF (gram
Power).
3, percent thermal shrinkage: the diaphragm of square is put into 105 DEG C of baking oven 1 hour, then measuring diaphragm is (vertical in MD
To) shrinkage rates of TD (transverse direction) both direction.
It is respectively compared embodiment 1 and comparative example 1, embodiment 2 and comparative example 2, it is found that before guaranteeing other indexs
It puts, relative to comparative example 1,2, the peel strength between 1, the 2 lithium battery diaphragm coating being prepared of embodiment and basement membrane is bright
Aobvious to improve, if embodiment 1 is relative to comparative example 1, peel strength improves 4.43 times.Embodiment 2 relative to comparative example 2,
Peel strength improves 2.22 times.I.e. after Overheating Treatment and crosslinking, peel strength improves 2 times or more.
At the same time, the percent thermal shrinkage of lithium battery diaphragm but declines to a great extent, and if embodiment 1 is relative to comparative example 1, heat is received
Shrinkage has dropped 50% or more, and wherein TD percent thermal shrinkage has dropped nearly 70%.In addition, being obtained using preparation method provided by the invention
To the puncture strength of lithium battery diaphragm also have a certain upgrade, illustrate that the intensity of lithium battery diaphragm is bigger, the service life is longer.
This be primarily due to after Overheating Treatment the contact surface area between binder and basement membrane and particles of inorganic material by
Common point contact becomes face contact, and contact area increases, and causes cohesive force to be promoted, peel strength, which should mutually have, significantly to be promoted.
At the same time, binder forms network-like structure when crosslinking, the bonding of coating and basement membrane is further promoted, in addition, being crosslinked
Journey can also improve the intensity of binder network, and then promote diaphragm intensity.
In addition, by comparing ventilative value it can be found that compared with comparative example, using breathing freely for embodiment provided by the invention
It is worth slightly lower or substantially suitable.Those skilled in the art will be considered that high-temperature heat treatment can be such that binder melts during heating, accordingly
The lithium battery diaphragm for causing to be prepared gas permeability decline, value of breathing freely is corresponding to be risen.But the present invention is sent out by many experiments
Now after high-temperature process, the gas permeability of lithium battery diaphragm, which has no, to be decreased obviously, instead, some embodiments, such as embodiment 1-3 system
The gas permeability of standby obtained lithium battery diaphragm also slightly improves.Analyzing reason may be in high-temperature process and/or cross-linking process
A small amount of gas can be generated, gas passes through binder during volatilization, and binder is caused to form partial pore, and binder is formed
Microcellular structure have some improvement to the gas permeability of lithium battery diaphragm.
By comparing embodiment 2 and embodiment 3 it can be found that drying temperature excessively high in coating process can cause coating and
Cohesive force decline between basement membrane, this may be because high temperature will lead to solvent and quickly volatilize in coating process, and binder heat is received
Phenomena such as contracting too fast, and crimping, and reduce the caking property between coating and basement membrane.
Pass through the comparison of embodiment 4,5 and comparative example 3, it can be seen that can similarly play and mention by the way of heat cross-linking
High-peeling strength is reduced and is shunk, and improves the effect of diaphragm intensity.But binder needs to meet its crosslinking temperature should be molten lower than basement membrane
15 DEG C of requirement under point, although this is because high-temperature process melts binder natural emulsion because binder with
The fusing point of basement membrane is not much different, and during heat treatment, apparent closed pore occurs for basement membrane, and ventilative value reaches 1848, can not
Meet the use of lithium battery.
By the analysis result of comparative example 4 it is recognized that while it during preparing lithium battery diaphragm, joined high-temperature process
And cross-linking step, but the peel strength for the lithium battery diaphragm being prepared and be heat-shrinked and be not improved, this may mainly by
It is thermosetting adhesive in its selection, is cured during heating, performance is more stable, is crosslinked subsequent
Cheng Zhong, binder cannot form network-like structure, therefore very limited to the raising of lithium battery diaphragm peel strength.
The present invention is guaranteeing lithium battery by the way that high-temperature process and cross-linking step are added in the preparation process of lithium battery diaphragm
Under the premise of other performances of diaphragm, the peel strength of lithium battery diaphragm greatly improved, improve viscous between coating and basement membrane
Knot property, effectively improves the heat resistance of lithium battery diaphragm, reduces the percent thermal shrinkage of diaphragm, so that lithium battery be avoided to use
Safety problem caused by being heat-shrinked in the process because of diaphragm.And the gas permeability of lithium battery diaphragm is uninfluenced, or even slightly improves,
It ensure that ion passes through lithium battery in use.
Specific embodiments of the present invention are described in detail above, but it is merely an example, the present invention is simultaneously unlimited
It is formed on particular embodiments described above.To those skilled in the art, any couple of present invention carries out equivalent modifications and
Substitution is also all among scope of the invention.Therefore, without departing from the spirit and scope of the invention made by equal transformation and
Modification, all should be contained within the scope of the invention.
Claims (10)
1. a kind of preparation method of lithium battery diaphragm, which is characterized in that
Include the following steps:
Step 1 prepares aqueous slurry；
It is wetting agent, the 20-80% of the particles of inorganic material of 20-60%, the dispersing agent of 0.5-5%, 0.1-10% by mass content
Deionized water be mixed, obtain dispersion liquid；
The binder that mass content is 0.3-5% is added in the dispersion liquid, continues stirring to being uniformly mixed, obtains described
Aqueous slurry；
Step 2, the aqueous slurry that step 1 is prepared are coated on a thickness of 5-25 μm, and porosity is the base of 30-80%
Then the one or both sides of film are dried under the conditions of 30-60 DEG C to constant weight, coating basement membrane is obtained；
Step 3, the coating basement membrane that step 2 is prepared aqueous binders softening temperature to the basement membrane fusing point
Under handle 10-300s between 15 DEG C；
Step 4, crosslinking；
If the crosslinking initial temperature of the binder is lower than 15 DEG C under the fusing point of the basement membrane, with the crosslinking of the binder
The warp that temperature under initial temperature to the fusing point of the basement membrane between 15 DEG C is prepared as crosslinking temperature, processing step 3
Coating basement membrane 5-30min after high-temperature process；
Or
Under room temperature, using electron energy 1-2Mev, the ray of flow velocity 2-5mA, radiation treatment step 3 be prepared through high temperature at
Coating basement membrane 20-60s after reason.
2. preparation method according to claim 1, which is characterized in that the step 1 are as follows: prepare aqueous slurry；
It is wetting agent, the 20-80% of the particles of inorganic material of 20-60%, the dispersing agent of 0.5-5%, 0.1-10% by mass content
Deionized water pass through sand mill first it be sanded, keep the inorganic matter evenly dispersed, be then sufficiently stirred, divided
Dispersion liquid；
The binder that mass content is 0.3-5% is added in the dispersion liquid, continues stirring to being uniformly mixed, obtains described
Aqueous slurry.
3. preparation method according to claim 1, which is characterized in that the mass content of each component in the aqueous slurry
Are as follows:
4. preparation method according to claim 3, which is characterized in that the mass content of each component in the aqueous slurry
Are as follows:
5. preparation method according to claim 1, which is characterized in that the particles of inorganic material include magnesia, calcium oxide,
Silica, aluminium oxide, zirconium dioxide, boehmite, any one or a few combination in barium sulfate.
6. preparation method according to claim 1, which is characterized in that the partial size D50 of the particles of inorganic material is 9nm-
2000nm, D90 < 4000nm.
7. preparation method according to claim 1, which is characterized in that the binder is aqueous binders, the bonding
Agent is rubber binder, vinyl acetate class binder, epoxyn, any one in polyurethanes binder
Or several combinations, the softening temperature of at least one aqueous binders is lower than 15 DEG C under the fusing point of the basement membrane.
8. preparation method according to claim 3 or 4, which is characterized in that the dispersing agent is n-butanol, cyclohexanol, second
Alcohol, polyvinylpyrrolidone, one or more of carboxylate, sulfonate, sulfuric acid ester salt.
9. preparation method according to claim 1, which is characterized in that the wetting agent includes ethyl alcohol, propylene glycol, positive fourth
Alcohol, isopropanol, glycerol etc. is one such or several combinations.
10. preparation method according to claim 1, which is characterized in that the aqueous slurry further includes thickener, levelling
Any one or a few combination in agent, defoaming agent.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN113921992A (en) * | 2021-09-16 | 2022-01-11 | 河北金力新能源科技股份有限公司 | High-heat-resistance lithium battery diaphragm and preparation method and application thereof |
| CN115411453A (en) * | 2022-09-20 | 2022-11-29 | 河北金力新能源科技股份有限公司 | Lithium battery diaphragm with high insulation and low closed pore temperature and preparation method thereof |
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| CN113278310A (en) * | 2021-04-30 | 2021-08-20 | 惠州锂威新能源科技有限公司 | Composite ceramic particle and preparation method and application thereof |
| CN113921992A (en) * | 2021-09-16 | 2022-01-11 | 河北金力新能源科技股份有限公司 | High-heat-resistance lithium battery diaphragm and preparation method and application thereof |
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