CN104183805B - A kind of preparation method of ceramic-coated separator - Google Patents
A kind of preparation method of ceramic-coated separator Download PDFInfo
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- CN104183805B CN104183805B CN201310198195.0A CN201310198195A CN104183805B CN 104183805 B CN104183805 B CN 104183805B CN 201310198195 A CN201310198195 A CN 201310198195A CN 104183805 B CN104183805 B CN 104183805B
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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
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/14—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silica
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- C—CHEMISTRY; METALLURGY
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
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- C—CHEMISTRY; METALLURGY
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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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
Abstract
The present invention relates to a kind of preparation method of the diaphragm material with ceramic coating of lithium ion battery.Including steps such as ceramic slurry preparation, barrier film pretreatment, accurate coating, drying；Prepared product has the characteristics of ceramic coating is fine and close, uniform, bonding is firm, barrier film thermal contraction is small, has positive effect to improving lithium ion battery safety performance, extension battery life.
Description
Technical field
The present invention relates to a kind of ceramic-coated separator of lithium ion battery, belong to new energy materialses field.
Background technology
Since lithium ion battery to 1990s, notebook computer, digital camera, mobile phone have been widely used in it
Deng portable electric appts.Simultaneously also by large-scale application in electric automobile, large-scale energy-storage system.
Lithium ion battery be current industrialization secondary battery in performance it is best, with energy density is high, the life-span
The good characteristic such as long, power density is big, is the preferred energy-storage battery of current electric automobile.But lithium-ion-power cell（It is general to hold
Measure the higher lithium ion battery for fields such as electric automobiles of larger, power and be referred to as lithium-ion-power cell）Safety issue（Deposit
Catching fire, the hidden danger such as explode）People is still allowed to be satisfied with not to the utmost.
The barrier film of lithium ion battery is to influence one of key factor of its security.The barrier film used at present predominantly PP
（Polypropylene）、PE（Polyethylene）The microporous membrane of material, its general thickness is more than ten~tens microns；Under normal circumstances, it is electrolysed
Lithium ion in liquid can be passed freely through to meet the work requirements that electrode material is embedded in deintercalation, when battery generation short circuit, overcharged
Etc. abnormal conditions when, battery can generate heat, after temperature is more than 90 DEG C, and the micropore of barrier film can shrink until closing, to block accident
Further expand.But it is due to thermal inertia, even if diaphragm micro-hole is closed, battery will not also rest on 90 DEG C, but can be raised to more
High temperature, particularly when occurring serious short circuit or high current is overcharged, temperature can rise to more than 170 DEG C, or even 200 DEG C！This
When barrier film will occur it is overall significantly shrink, so as to cause the direct large area short circuit of both positive and negative polarity of battery, the temperature of battery will be made
Further rise, finally causes the serious accident such as catch fire, explode.
Research shows, shows that coated with ceramic coating can effectively improve the shrinkage of barrier film in barrier film, so as to significantly carry
The security performance of high battery.Due to ceramics（Aluminum oxide, silica, zirconium oxide, magnesia etc.）Property is stable, does not decompose, non-ignitable
Burn, do not shrink, be coated on barrier film, " skeleton " can be played a part of, so that the contraction of barrier film is prevented, therefore ceramics are applied
Layer barrier film can significantly improve the security of lithium-ion-power cell.
Ceramic powders in the slurry of current ceramic-coated separator mainly use alundum (Al2O3), its have performance it is stable,
The low advantage of price, can play a part of providing " skeleton " to barrier film.
Because the diaphragm material of lithium ion battery is polypropylene or vinyl polymer material, these materials and aqueous colloidal
Existing wetability is poor, therefore has the report using organic gel system, such as patent 201210166837.4《High safety Ceramic Composite lithium
Ion barrier film and its lithium battery》It is middle use by solvent of 1-METHYLPYRROLIDONE, polyacrylate or Kynoar be
The adhering method of bonding agent.But organic colloid is tied to form that this is higher, there is organic matter volatilization in drying, have certain pollution, need to take
Environmental practice, and organic gel has been filled with the micropore of portion septum matrix, causes micropore to diminish, tail off, thus influence barrier film from
Sub- conduction property.
, again can be poor due to the wetability of glue and barrier film if being bonded using water-base cement system, cause ceramic particle difficult
To be uniformly distributed on barrier film, and bonding force is weak, and coating easily comes off.
The present invention is using nanometer/ultrafine ceramic powder and deionized water as raw material, by itself and bonding agent, wetting agent, dispersant
Etc. being combined together, water-base cement slurries are made in the high-strength scattered means being combined using high-speed stirred and ultrasonic wave, it is ensured that water
Property colloid system dispersion effect and adhesive effect, overcome and be difficult to effectively divide nanometer/ultrafine ceramic powder using normal agitation
The drawbacks of dissipating；Alundum (Al2O3) and magnesia composite ceramics system are used in preferred scheme simultaneously, not only alundum (Al2O3)
Can play a part of to barrier film " skeleton ", and magnesia can also with present in battery system micro-moisture formation acid in
With and improve battery life.Take ozone to handle barrier film base material before the coating, make the wetability of barrier film and water-base cement obvious
Improve, overcome because barrier film base material and ceramic coating caused by water-base cement system wetability difference are uneven, adhesive strength is low
Defect.Slurries are coated on barrier film using accurate coating technique again, ceramic-coated separator production is obtained after drying, winding
Product.Above-mentioned measure enables ceramic coating to cover uniformly, securely in diaphragm matrix so that the thermal contraction performance of barrier film is obtained
To being obviously improved, the security performance to lithium ion battery is significantly improved.
The content of the invention
It is an object of the invention to provide a kind of preparation side of the diaphragm material with ceramic coating of lithium ion battery
Method.
The preparation method of diaphragm material of the present invention with ceramic coating be：Barrier film base material is polypropylene, the list of polyethylene
Layer or their more than one layer composite membrane；9~40 μm of thickness；Preparation technology includes ceramic slurry preparation, barrier film pretreatment, precision
Coating three big steps of drying：
（1）Ceramic slurry is prepared
1. at the same time in the vacuum with supersonic oscillations function, high speed, planet stirring equipment（0~3000r/min of rotating speed
Adjustable, ultrasonic frequency 20kHz vibrations）Add deionized water and granularity for 0.05~1.0 μm of alundum (Al2O3), zirconium oxide,
The weight of one or more kinds of ceramic powders in silica, magnesia, zinc oxide, titanium dioxide, ceramic powder and deionized water
Than for（5~30）：（95~70）, high-speed stirred（Rotating speed is more than 1000r/min）Supersonic oscillations 0.5~2 hour simultaneously；
2. add in Sodium Polyacrylate, many sodium metaphosphates, sodium orthophosphate, sodium metasilicate, lauryl sodium sulfate, ammoniacal liquor
One or more kinds of mixtures, addition is the 0.5~5% of slurry；High-speed stirred（Rotating speed is more than 1000r/min）Simultaneously
Supersonic oscillations 0.5~2 hour；
3. 1-METHYLPYRROLIDONE, alcohol, propylene carbonate, glycerine, dimethyl sulfoxide (DMSO), polyoxyethylene alkylphenol are added
One or more kinds of mixtures in ether, polyoxyethylene aliphatic alcohol ether, polyvinyl alcohol, addition for slurry 0.5~
10%；High-speed stirred（Rotating speed is more than 1000r/min）Supersonic oscillations 0.5~2 hour simultaneously；
4. the carboxy styrene-butadiene rubber of slurry amount 0.5~10% is added（SBR）（50% emulsion is configured in advance）, add slurry
The sodium carboxymethylcellulose of amount 0.3~5%（CMC）（2% solution is configured in advance）；High-speed stirred（Rotating speed is more than 1000r/
min）Supersonic oscillations 0.5~2 hour simultaneously；
5. rotating speed is turned down to 500 below r/min, supersonic oscillations are closed, vacuum is opened, 0.5~1 hour is stirred, so
Close afterwards after Vacuum Balance atmospheric pressure and release slurry to cross 200 mesh sieves standby.
（2）Barrier film is pre-processed
In order to improve the wettability of barrier film and slurry, barrier film is handled using 0.5~5L/min of flow ozone,
5~120 seconds processing times.
（3）Precision coating drying
Pretreated barrier film is placed on micro- gravure coater, the slurry prepared is placed in the hopper of micro- gravure coater
In, it is coated, coating speed is controlled in 2~20m/min；Coating layer thickness is supervised online using laser or gamma thickness gage
Survey and control, it is ensured that coating layer thickness it is uniform, control coating layer thickness for 1~5 μm；Drying, winding after coating is finished product.
Described ceramic slurry preparing process, it is characterised in that described alundum (Al2O3), zirconium oxide, silica, oxidation
It is preferred to use one or more kinds of mixing in alundum (Al2O3), magnesia and zinc oxide in magnesium, zinc oxide, titanium dioxide
Thing；More preferably using alundum (Al2O3) and the mixture of magnesia, alundum (Al2O3) and magnesia ratio are（7~
9.5）：（3~0.5）.
Described ceramic slurry preparing process, it is characterised in that described CMC can also use hydroxypropyl methyl cellulose
（HPMC）Instead of addition is the 0.5~10% of slurry.
Described ceramic slurry preparing process, is further characterized in that used SBR and CMC can also polyvinyl alcohol（PVA）
Or a kind of replacement in LA132, L133, L134 lithium ion battery bonding agent, addition is the 0.5~10% of slurry.
Described accurate coating process, it is characterised in that can be using silk-screen printing, transfer type coating or squash type coating
Technology generations replace micro- gravure coating process.
The present invention is using nanometer/ultrafine ceramic powder and deionized water as raw material, by itself and bonding agent, wetting agent, dispersant
Etc. being combined together, water-base cement slurries are made in the high-strength scattered means being combined using high-speed stirred and ultrasonic wave, it is ensured that water
Property colloid system dispersion effect and adhesive effect, do not pollute, overcome and be difficult to nanometer/ultrafine ceramic powder using normal agitation
Last effectively scattered the drawbacks of；Alundum (Al2O3) and magnesia composite ceramics system, not only three are used in preferred scheme simultaneously
Al 2 O can play a part of " skeleton " to barrier film, and magnesia can also be with micro-moisture shape present in battery system
Into acid neutralize and improve battery life.Take ozone to handle barrier film base material before the coating, make the profit of barrier film and water-base cement
It is moist to significantly improve, overcome because barrier film base material and ceramic coating caused by water-base cement system wetability difference are uneven, viscous
Connect the defect of low intensity.Slurries are coated on barrier film using accurate coating technique again, ceramic coating is obtained after drying, winding
Separator product.Above-mentioned measure enables ceramic coating to cover uniformly, securely in diaphragm matrix so that the thermal contraction of barrier film
Performance be improved significantly, security performance and life-span to lithium ion battery are all significantly improved.
Brief description of the drawings
The ceramic-coated separator stereoscan photograph that Fig. 1 is prepared for the present invention, it can be seen that coating uniform.
Fig. 2 is ceramic-coated separator stereoscan photograph prepared by comparative example, it can be seen that its coating is substantially uneven.
Embodiment
Embodiment 1
（1）Ceramic slurry is prepared
1. at the same time in the vacuum with supersonic oscillations function, high speed, planet stirring equipment（0~3000r/min of rotating speed
Adjustable, ultrasonic frequency 20kHz vibrations）It is 0.2 μm of silica, ceramic powder and deionized water to add deionized water and granularity
Weight ratio be 30：70,3000r/min high-speed stirreds supersonic oscillations 0.5 hour simultaneously；
2. the Sodium Polyacrylate of slurry amount 5% is added, 3000r/min high-speed stirreds supersonic oscillations 0.5 hour simultaneously；
3. the glycerine of slurry amount 0.5% is added, 3000r/min high-speed stirreds supersonic oscillations 2 hours simultaneously；
4. the carboxy styrene-butadiene rubber of slurry amount 10% is added（SBR）（50% emulsion is configured in advance）, add slurry amount 5%
Sodium carboxymethylcellulose（CMC）（2% solution is configured in advance）；Supersonic oscillations 2 are small simultaneously for 3000r/min high-speed stirreds
When；
5. rotating speed is turned down to 500 r/min, supersonic oscillations are closed, vacuum is opened, stirred 0.5 hour, is then shut off true
Slurry is released after empty balancing Atmospheric pressure, and to cross 200 mesh sieves standby.
（2）Barrier film is pre-processed
In order to improve the wettability of barrier film and slurry, use flow 0.5L/min ozone to thickness for 12 μm poly- third
Alkene single-layer septum is handled, 120 seconds processing times.
（3）Precision coating drying
Pretreated barrier film is placed on micro- gravure coater, the slurry prepared is placed in the hopper of micro- gravure coater
In, it is coated, coating speed is controlled in 10m/min；Coating layer thickness is monitored on-line using laser or gamma thickness gage
With control, it is ensured that coating layer thickness it is uniform, control coating layer thickness be 2 μm；Drying, winding after coating is finished product.
Prepared ceramic-coated separator is traditionally made into 40Ah ferric phosphate lithium cells, and tests its performance.
The battery performance of the present embodiment product is shown in Table 1.
Embodiment 2
（1）Ceramic slurry is prepared
1. at the same time in the vacuum with supersonic oscillations function, high speed, planet stirring equipment（0~3000r/min of rotating speed
Adjustable, ultrasonic frequency 20kHz vibrations）Add zirconium oxide that deionized water and silica that granularity is 0.8 μm, granularity are 1.0,
Granularity is 0.4 zinc oxide（Weight ratio is 7：2.5：0.5）, ceramic powder（Silica, zirconium oxide, zinc oxide mix）With go from
The weight ratio of sub- water is 10：90,2000r/min high-speed stirreds supersonic oscillations 1 hour simultaneously；
2. the sodium orthophosphate, sodium metasilicate, lauryl sodium sulfate of slurry amount 0.5% are added（Weight compares 1：1：1）,
2000r/min high-speed stirreds supersonic oscillations 1 hour simultaneously；
3. the 1-METHYLPYRROLIDONE, alcohol, propylene carbonate of slurry amount 10% are added（Weight compares 1：1：1）,
2000r/min high-speed stirreds supersonic oscillations 1 hour simultaneously；
4. the LA133 glue of slurry amount 6% is added；2000r/min high-speed stirreds supersonic oscillations 2 hours simultaneously；
5. rotating speed is turned down to 400 r/min, supersonic oscillations are closed, vacuum is opened, and is stirred 1 hour, is then shut off vacuum
Slurry is released after balancing Atmospheric pressure, and to cross 200 mesh sieves standby.
（2）Barrier film is pre-processed
In order to improve the wettability of barrier film and slurry, use flow 2L/min ozone to thickness for 25 μm of polypropylene
Single-layer septum is handled, 80 seconds processing times.
（3）Precision coating drying
Pretreated barrier film is placed in transfer coater, the slurry prepared is placed in the hopper of transfer coater, is entered
Row coating, coating speed is controlled in 2m/min；On-line monitoring and control is carried out to coating layer thickness using laser or gamma thickness gage,
Ensure the uniform of coating layer thickness, it is 5 μm to control coating layer thickness；Drying, winding after coating is finished product.
Prepared ceramic-coated separator is traditionally made into 40Ah ferric phosphate lithium cells, and tests its performance.
The battery performance of the present embodiment product is shown in Table 1.
Embodiment 3
（1）Ceramic slurry is prepared
1. at the same time in the vacuum with supersonic oscillations function, high speed, planet stirring equipment（0~3000r/min of rotating speed
Adjustable, ultrasonic frequency 20kHz vibrations）It is 0.05 to add deionized water and alundum (Al2O3) and granularity that granularity is 0.4 μm
Magnesia（Weight compares 9：1）, ceramic powder（The mixture of alundum (Al2O3) and magnesia）Weight ratio with deionized water is 5：
95,1500r/min high-speed stirreds supersonic oscillations 2 hours simultaneously；
2. many sodium metaphosphates and ammoniacal liquor of slurry amount 3% are added（Weight compares 3：1）, 1500r/min high-speed stirreds simultaneously surpass
Sonication 2 hours；
3. dimethyl sulfoxide (DMSO), polyoxyethylated alkyl phenol, polyoxyethylene aliphatic alcohol ether, the polyethylene of slurry amount 5% are added
Alcohol（Weight compares 1：1：1：0.5）, 1500r/min high-speed stirreds supersonic oscillations 2 hours simultaneously；
4. the LA134 glue of slurry amount 1% is added；1500r/min high-speed stirreds supersonic oscillations 1 hour simultaneously；
5. rotating speed is turned down to 400 r/min, supersonic oscillations are closed, vacuum is opened, stirred 0.5 hour, is then shut off true
Slurry is released after empty balancing Atmospheric pressure, and to cross 200 mesh sieves standby.
（2）Barrier film is pre-processed
In order to improve the wettability of barrier film and slurry, use flow 5L/min ozone to thickness for 40 μm poly- third
Three layers of composite diaphragm of alkene/polyethylene/polypropylene are handled, 10 seconds processing times.
（3）Precision coating drying
Pretreated barrier film is placed on screen process press, the slurry prepared is placed in the hopper of screen process press, is entered
Row coating, coating speed is controlled in 18m/min；Coating layer thickness is monitored on-line and controlled using laser or gamma thickness gage
System, it is ensured that coating layer thickness it is uniform, control coating layer thickness for 1.5 μm；Drying, winding after coating is finished product.
Prepared ceramic-coated separator is traditionally made into 40Ah ferric phosphate lithium cells, and tests its performance.
The stereoscan photograph of the present embodiment product is as shown in figure 1, the battery performance manufactured with it is shown in Table 1.
Comparative example 1
（1）Ceramic slurry is prepared
1. deionized water and the alundum (Al2O3) that granularity is 0.4 μm and the oxygen that granularity is 0.05 are added in normal agitation machine
Change magnesium（Weight compares 9：1）, ceramic powder（The mixture of alundum (Al2O3) and magnesia）Weight ratio with deionized water is 5：95,
1000r/min is stirred 2 hours；
2. many sodium metaphosphates and ammoniacal liquor of slurry amount 3% are added（Weight compares 3：1）, 1000r/min stirrings 2 hours；
3. dimethyl sulfoxide (DMSO), polyoxyethylated alkyl phenol, polyoxyethylene aliphatic alcohol ether, the polyethylene of slurry amount 5% are added
Alcohol（Weight compares 1：1：1：0.5）, 1000r/min stirrings 2 hours；
4. the LA134 glue of slurry amount 1% is added；1000r/min is stirred 1 hour；
5. rotating speed is turned down to 400 r/min, is stirred 0.5 hour, and then releasing slurry, to cross 200 mesh sieves standby.
（2）Precision coating drying
Thickness not treated by ozone is placed in silk screen for 40 μm three layers of composite diaphragm of polypropylene, polyethylene/polypropylene
On printing machine, the slurry prepared is placed in the hopper of screen process press, is coated, and coating speed is controlled in 18m/min；Using
Laser or gamma thickness gage carry out on-line monitoring and control to coating layer thickness, it is ensured that uniform, the control coating layer thickness of coating layer thickness
For 1.5 μm；Drying, winding after coating is finished product.
Prepared ceramic-coated separator is traditionally made into 40Ah ferric phosphate lithium cells, and tests its performance.
The stereoscan photograph of this comparative example product is as shown in figure 1, the battery performance manufactured with it is shown in Table 1.
Comparative example 2
It is 40 μm three layers of composite diaphragm of polypropylene, polyethylene/polypropylene according to tradition by the thickness without any processing
Technique makes 40Ah ferric phosphate lithium cells, and battery performance is shown in Table 1.
Without the general of any processing it can be seen from above-described embodiment and the battery performance and stereoscan photograph of comparative example
Battery safety prepared by logical barrier film is worst, the life-span is most short（Comparative example 2）；By slurry preparation method of the present invention,
The ceramic-coated separator of barrier film preprocess method manufacture, its coating is substantially uneven, made battery safety and life-span
Less than the performance of the battery prepared according to present invention process；The ceramic coating prepared especially with the optimal technique of the present invention every
Film, the effect with coating uniform, battery is prepared using it as barrier film has best security performance and cycle life.
Table 1
Note：70 DEG C of cycle life test conditions：2.5~3.6V of voltage range, electric current 1C, which fill 1C, to be put；Capacity attenuation is to 80%
When terminate test.
Claims (3)
1. a kind of preparation method of the diaphragm material with ceramic coating of lithium ion battery, it is characterised in that barrier film base material
For polypropylene, the individual layer of polyethylene or their more than two layers composite membranes；9~40 μm of thickness；Preparation method includes ceramic slurry
Prepare, barrier film is pre-processed, three big steps of accurate coating drying：
（1）Ceramic slurry is prepared
1. there is the true of supersonic oscillations function while 0~3000r/min of rotating speed is adjustable, ultrasonic frequency 20kHz vibrates
In sky, high speed, planet stirring equipment, it is 0.05~1.0 μm of alundum (Al2O3), zirconium oxide, oxygen to add deionized water and granularity
The weight of one or two or more kinds of ceramic powders in SiClx, magnesia, zinc oxide, titanium dioxide, ceramic powders and deionized water
Than for（5~30）：（95~70）, high-speed stirred, rotating speed is more than 1000r/min, while supersonic oscillations 0.5~2 hour；
2. the one kind added in Sodium Polyacrylate, many sodium metaphosphates, sodium orthophosphate, sodium metasilicate, lauryl sodium sulfate, ammoniacal liquor
Or more than two kinds of mixture, addition is the 0.5~5% of slurry；High-speed stirred, rotating speed is more than 1000r/min, while ultrasonic
Ripple vibrates 0.5~2 hour；
3. add 1-METHYLPYRROLIDONE, alcohol, propylene carbonate, glycerine, dimethyl sulfoxide (DMSO), polyoxyethylated alkyl phenol,
One or two or more kinds of mixtures in polyoxyethylene aliphatic alcohol ether, polyvinyl alcohol, addition is the 0.5~10% of slurry；
High-speed stirred, rotating speed is more than 1000r/min, while supersonic oscillations 0.5~2 hour；
4. the carboxy styrene-butadiene rubber of slurry amount 0.5~10% is added（SBR）, carboxy styrene-butadiene rubber（SBR）50% breast is configured in advance
Liquid, or add the polyvinyl alcohol of slurry amount 0.5~10%（PVA）, one kind in LA132, L133, L134；Add slurry amount 0.3
~5% sodium carboxymethylcellulose（CMC）, sodium carboxymethylcellulose（CMC）2% solution is configured in advance；Or addition is material
0.5~10% hydroxypropyl methyl cellulose of slurry（HPMC）, polyvinyl alcohol（PVA）, one kind in LA132, L133, L134；It is high
Speed stirring, rotating speed is more than 1000r/min, while supersonic oscillations 0.5~2 hour；
5. rotating speed is turned down to 500 below r/min, supersonic oscillations are closed, vacuum is opened, and is stirred 0.5~1 hour, Ran Houguan
Close after Vacuum Balance atmospheric pressure and release slurry to cross 200 mesh sieves standby；
（2）Barrier film is pre-processed
In order to improve the wettability of barrier film and slurry, barrier film is handled using 0.5~5L/min of flow ozone, handled
5~120 seconds time；
（3）Precision coating drying
Pretreated barrier film is placed on micro- gravure coater, the slurry prepared is placed in the hopper of micro- gravure coater, is entered
Row coating, coating speed is controlled in 2~20m/min；Using laser or gamma thickness gage coating layer thickness is carried out on-line monitoring with
Control, it is ensured that coating layer thickness it is uniform, control coating layer thickness for 1~5 μm；Drying, winding after coating is finished product.
2. a kind of preparation method of the diaphragm material with ceramic coating of lithium ion battery as claimed in claim 1, its
It is characterised by, described ceramic powders use one or two or more kinds of mixtures in alundum (Al2O3), magnesia and zinc oxide.
3. a kind of preparation method of the diaphragm material with ceramic coating of lithium ion battery as claimed in claim 2, its
It is characterised by, described ceramic powders use the mixture of alundum (Al2O3) and magnesia, alundum (Al2O3) and magnesia ratio
For（7~9.5）：（3~0.5）.
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| CN106299208B (en) * | 2016-10-12 | 2018-12-25 | 河北金力新能源科技股份有限公司 | A kind of preparation method of high temperature resistant low-resistivity lithium ion battery separator |
| CN106684438B (en) * | 2017-02-07 | 2020-01-24 | 上海璞泰来新能源科技股份有限公司 | Lithium battery capable of rapidly detecting safety |
| CN106784542B (en) * | 2017-02-13 | 2019-08-06 | 河北金力新能源科技股份有限公司 | A kind of lithium ion battery separator and preparation method thereof of a variety of coatings of high temperature resistant |
| CN107302075B (en) * | 2017-07-03 | 2020-03-17 | 河北金力新能源科技股份有限公司 | Preparation method of self-cooling anti-obturator lithium ion battery diaphragm |
| CN107611326A (en) * | 2017-09-22 | 2018-01-19 | 广东工业大学 | Cyclodextrin ceramic diaphragm coating slurry and lithium ion battery separator and lithium ion battery |
| CN108807813B (en) * | 2018-05-25 | 2021-10-08 | 欣旺达电动汽车电池有限公司 | Lithium ion battery, diaphragm and preparation method thereof |
| CN113991249B (en) | 2018-06-06 | 2024-03-08 | 宁德新能源科技有限公司 | Separator and electrochemical device |
| WO2020000164A1 (en) * | 2018-06-26 | 2020-01-02 | 深圳市星源材质科技股份有限公司 | Composite lithium battery separator and preparation method therefor |
| CN109300861B (en) * | 2018-09-28 | 2021-03-02 | 苏州清陶新能源科技有限公司 | Silicon oxide-based communication substrate and preparation process and application thereof |
| CN109411673A (en) * | 2018-09-28 | 2019-03-01 | 上海恩捷新材料科技有限公司 | Lithium ion battery separator slurry and preparation method and lithium ion battery separator |
| CN114231105A (en) * | 2021-12-10 | 2022-03-25 | 河北金力新能源科技股份有限公司 | Low-moisture high-insulation lithium ion battery diaphragm and preparation method thereof |
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