CN109021275A - A kind of preparation method of the polymer film of polymer/metallic salt - Google Patents
A kind of preparation method of the polymer film of polymer/metallic salt Download PDFInfo
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- CN109021275A CN109021275A CN201810751797.7A CN201810751797A CN109021275A CN 109021275 A CN109021275 A CN 109021275A CN 201810751797 A CN201810751797 A CN 201810751797A CN 109021275 A CN109021275 A CN 109021275A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
- C09D133/12—Homopolymers or copolymers of methyl methacrylate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/327—Aluminium phosphate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/328—Phosphates of heavy metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
Abstract
The present invention relates to a kind of preparation methods of the polymer film of polymer/metallic salt, it is characterized by: according to volume ratio (0.1~10): acetone and dimethylformamide are mixed to prepare mixed solution by 1 ratio, the coating agent of 0.33~2% weight of mixed solution weight is added, add the polymethyl methacrylate of 0.33~2% weight, 10~50min of supersonic oscillations；8~12 h are stirred at 50~90 DEG C, and thick liquid is made.Under chlorine, fluorine gas, hydrogen fluoride, formaldehyde or formic acid atmosphere, basement membrane is handled with method of radiating, is coated with thick liquid, coating film is made by vacuum drying or forced air drying.Cost of material of the present invention is lower, preparation process is simple, it is easy to operate, time-consuming is few, the coating film of preparation is used for battery system, and the internal resistance of cell can be obviously reduced, and is significantly improved with the matching of the materials such as anode, cathode, electrolyte, the cycle performance for improving battery, lays a good foundation for industrialization.
Description
Technical field
The present invention relates to a kind of preparation methods of the polymer film of polymer/metallic salt, and in particular to one kind can be used for lithium electricity
Pond, lithium ion battery, polymer battery and supercapacitor coating film preparation method, belong to the technology of battery diaphragm preparation
Field.
Technical background
In lithium-ion battery system, diaphragm plays prevention electrical communication between anode and cathode, and the effect of ion is connected.Every
Film has important role to battery performance and safe handling.According to the difference of diaphragm production technology, battery diaphragm can be divided into dry method
Film, wet process film and composite membrane.
In abuse conditions, lithium ion battery is likely to be at 100~300 DEG C of high temperature section, polyethylene (PE), polypropylene
(PP), polyolefin composite film (e.g., PP/PE/PP, PE/PP) or other polyolefin films the meeting contraction distortion under this high-temperature region, makes
At the lithium ion battery for using polyolefin film, there are security risks.The nano materials such as coating alumina on polyolefin film, can
Prepare coating film.In this coating film diaphragm, organic material makes diaphragm have flexibility, meets the requirement of battery assembly.?
Under high temperature, organic component can be melted in coating film, blocked diaphragm hole, slowed down or prevent cell reaction, to ensure battery
Safety.Inorganic material is distributed in diaphragm outer layer in coating film, plays the effect of rigid backbone, ensures the safety of lithium ion battery
Property.Coating film is generally made of basement membrane, adhesive, inorganic nano material.
From the point of view of adhesive, current coating film using PVDF resin [Hennige V., et al. US 7790321,
2010. 7. 9.], polymethyl methacrylate (PMMA) [Zhao Jinbao etc., Chinese invention patent, 103035866 A of CN,
2013.4.10.], butadiene-styrene rubber (SBR) [Park J. H., et al. J. Power Sources, 2010,195
(24): 8306-8310.], silica solution [Lee J. R., et al. J. Power Sources, 2012,216:42-
47.] and Kynoar-hexafluoropropene (PVDF-HFP) [Jeong H. S., et al. Electrochim. Acta,
The binders such as 2012,86:317-322.].[Sohn J. Y., et al., the J. Solid State such as Sohn
Electrochem., 2012,16,551-556.] by polymethyl methacrylate (PMMA), Kynoar-hexafluoropropene
(PVDF-HFP) and nanometer Al2O3Mixture be coated in PE film on, prepare the coating film of PVDF-HFP/PMMA.
Adsorption theory thinks, bonding be two kinds of materials intermolecular contacts and interfacial force caused by.Bonding force it is main come
Source is intermolecular force, including hydrogen bond and Van der Waals force.It referred to as soaks, to obtain good when adhesive is continuously contacted with adherend
Good bond effect requires the surface tension of adhesive to be less than the surface tension of adherend.
Jeong etc. [Jeong H. S., et al. Electrochim. Acta, 2012,86:317-322.]
The study found that performance of the ratio regular meeting of Kynoar-hexafluoropropene (PVDF-HFP) binder and coating membrane granule to diaphragm
There is significant impact.The content for improving binder in coat can reduce falling off for coat particle, improve diaphragm mechanical performance.
But, membrane surface property can be changed by the coat particle that binder coats, the wetability to electrolyte is reduced, to battery
High rate during charging-discharging is unfavorable.Song etc. [Song J., et al. Electrochim. Acta, 2012,85:
524-530.] it finds, on the duct that nanometer coated particle is easily deposited in basement membrane under the action of binder, reduce the hole of diaphragm
Rate increases the resistance of lithium ion cross-film diffusion.
From the point of view of applying coating, the inorganic material studied includes nanometer Al2O3、ZrO2、SiO2、TiO2、MgO、CaO、
CaCO3、BaSO4, zeolite, boehmite, clay etc..[Takemura D., the et al. J. Power such as Takemura
Sources, 2005,146 (1/2): 779-783.] investigate Al2O3Influence of the partial size to membrane properties.They have found, apply
Cover Al2O3The high temperature resistance of diaphragm can be improved.Choi etc. [Choi E. S., et al. J. Mater. Chem.,
2011, (38): 14747-14754.] use partial size 40nm SiO2PE microporous barrier is coated, coating film is prepared.With special duct
Inorganic material be also used for replace nanometer Al2O3As coating agent, it is used to prepare coating film.In this coating film, solvation
Lithium ion can be passed through from inorganic particle gap, and " green channel " provided along inorganic particle directly transmits.
From the point of view of basement membrane, since the reactivity of polyolefin-based film surface is little, glued between the coating and basement membrane on coating film
It ties not close.In long-term charge and discharge process, the coat of coating film is easy to fall off.Untreated polyolefin compound is (as gathered
Ethylene, polypropylene) it is difficult to be bonded.
Since during long-term charge and discharge cycles, coating film is easy to appear picking phenomenon.In order to improve this phenomenon,
[Chen H., the et al. Plasma activation and atomic layer deposition of TiO such as Chen2
on polypropylene membranes for improved performances of lithium-ion
Batteries, J. Membr. Sci., 2014,458,217-224.] first with the table of plasma technique processing PP film
Then face is coated with TiO2, coating film is made.Studies have shown that corona treatment can be obtained in PP film generates polar group on surface
Group, is conducive to TiO2Dispersion on the diaphragm surface makes the diaphragm imbibition rate with higher of preparation and ionic conductivity, lower
Percent thermal shrinkage.The lithium ion battery discharge capacity with higher and multiplying power discharging property assembled with this diaphragm.
Although by above-mentioned study on the modification there is problem in the application of battery system in coating film.For example, coating film meeting
Increase the internal resistance of cell, discharge capacity of the cell is made to be difficult to bring into play.Picking influences the security performance of battery.Applying coating with just
Pole, cathode, electrolyte matching there are still clearly disadvantageous.
In order to solve the problems, such as that coating film is applied, the compound of the key containing P-O is added in the present invention in coat.By
It can react, be formed and the valuable key connection of basement membrane in the compound of the key containing P-O and the polyolefin base membrane of corona treatment
Coat significantly improves the binding force between coating film floating coat and basement membrane, reduces the internal resistance of cell, reduces picking phenomenon.Due to containing
The compound of P-O key permits by force the wetability of electrolyte compared with wetability of the coating agents such as the coating alumina of forefathers to electrolyte
More, strong to the affinity of electrolyte, imbibition ability is strong.It is good with the matching of anode, cathode, electrolyte, hence it is evident that improve coating film
Performance.
Summary of the invention
The technical solution adopted in the present invention comprises the steps of:
In a kettle, according to volume ratio (0.1~10): acetone and dimethylformamide are mixed to prepare mixed solution by 1 ratio.
Be added mixed solution weight 0.33~2% weight coating agent, 1~50 min of supersonic oscillations, be made be uniformly mixed it is suspended
Liquid.The polymethyl methacrylate of 0.33~2% weight of mixed solution weight is added in suspension.Supersonic oscillations 10~
50min.8~12 h are stirred at 50~90 DEG C, and solution in reaction kettle is made to be changed into thick liquid.It will tile through overshoot basement membrane
It opens, thick liquid is coated in the surface of the basement membrane Jing Guo radiation treatment, it is true at any temperature of 50~110 DEG C of temperature ranges
The polymer film of polymer/metallic salt is made in empty drying or forced air drying.
The coating agent is tripolyphosphate zinc, aluminium triphosphate or tripolyphosphate boron of the partial size in the μ m of 1nm~5.
It is described through overshoot basement membrane be under chlorine, fluorine gas, hydrogen fluoride, formaldehyde or formic acid atmosphere, by glow discharge,
The basement membrane of corona discharge or RF low-temperature plasma electric discharge or jet stream discharge of plasma in low temperature processing 1s~10min.
The polymethyl methacrylate is polymethyl methacrylate of the average molecular weight in 40~1,700,000 ranges.
The vacuum drying is the heat drying carried out in 0.00001~0.1atm range pressure.
The basement membrane is monofilm or multilayer film containing polypropylene or polyethylene layer.
The multilayer film is the diaphragm that the number of plies is formed in the monofilm of 2~20 ranges.
Cost of material of the invention is lower, and preparation process is simple, easy to operate, and time-consuming is few, and the coating film of preparation is applied to
The internal resistance of cell can be obviously reduced in battery system, be significantly improved, change with the matching of the materials such as anode, cathode, electrolyte
It has been apt to the cycle performance of battery, has laid a good foundation for industrialization.
Detailed description of the invention
Fig. 1 is the basement membrane of the coating film of the embodiment of the present invention 1 and the infared spectrum of coating bed boundary.
Fig. 2 is impedance spectra of the button cell in different circulations of the preparation of the embodiment of the present invention 1.
Specific embodiment
The present invention is further detailed below with reference to embodiment.Embodiment is only to further supplement of the invention
And explanation, rather than the limitation to invention.
Embodiment 1
In a kettle, according to volume ratio 1:1 mixing acetone and dimethylformamide, mixed solution is obtained.Mixed solution is added
Uniformly mixed suspension is made in 1.25% weight of weight and the tripolyphosphate zinc of partial size 20nm, 15 min of supersonic oscillations.
1.25% weight of mixed solution weight and the polymethyl methacrylate of average molecular weight 800,000, ultrasound are added in suspension
Wave vibrates 25min.9 h are stirred at 70 DEG C, and solution in reaction kettle is made to be changed into thick liquid.By polypropylene monofilm (thickness
Be 20 μm) tiling after, it is each to two surfaces of monofilm under RF low-temperature plasma discharging condition under formic acid atmosphere
60s is handled, thick liquid is coated on two surfaces of treated monofilm, coating overall thickness is 12 μm, in 60 DEG C
And be dried in vacuo under conditions of 0.09atm, the polymer film of polymer/metallic salt is made.
Li will be formed1.05Ni0.5Co0.2Mn0.3O2Tertiary cathode material, acetylene black and the PVDF binder of type are according to 85:10:
5 weight ratio weighs, and using N-Methyl pyrrolidone as grinding aid, uniform sizing material is made in ball milling mixing 3h.Uniform sizing material is coated
In aluminum foil current collector, positive plate is made after drying.Lithium metal, the coating film of preparation, positive plate, battery case and electrolyte are set
In the glove box full of argon atmosphere, it is assembled into CR2025 type button cell.To preparation on new Weir battery test system
Button cell carry out charge and discharge and cycle performance test.Test temperature is room temperature (25 ± 1 DEG C).The section of charge and discharge is 2.5
~4.3V.Charge and discharge cycles experiment carries out under 1C multiplying power electric current.Charge-discharge test shows putting for the circulation of sample the 1st of preparation
Capacitance is 179mAh/g.
Embodiment 2
In a kettle, according to volume ratio 0.1:1 mixing acetone and dimethylformamide, mixed solution is obtained.It is molten that mixing is added
Uniformly mixed suspension is made in 0.33% weight of liquid weight and the tripolyphosphate zinc of partial size 1nm, supersonic oscillations 1min.?
0.33% weight of mixed solution weight and the polymethyl methacrylate of average molecular weight 400,000, ultrasonic wave are added in suspension
Vibrate 10min.8 h are stirred at 50 DEG C, and solution in reaction kettle is made to be changed into thick liquid.After polyethylene monolayer film is tiled,
Under fluorine gas atmosphere, to a surface treatment 1s of monofilm under the conditions of jet stream discharge of plasma in low temperature, by thick liquid
It on surface coated in treated monofilm, is dried in vacuo under conditions of 50 DEG C and 0.00028atm, polymerization gold is made
Belong to the polymer film of salt.
Embodiment 3
In a kettle, according to volume ratio 10:1 mixing acetone and dimethylformamide, mixed solution is made.Mixed solution is added
Uniformly mixed suspension is made in 2% weight and 1 μm of partial size of aluminium triphosphate of weight, supersonic oscillations 30min.Suspended
2% weight of mixed solution weight and the polymethyl methacrylate of average molecular weight 1,700,000, supersonic oscillations are added in liquid
50min.In 90 DEG C of 12 h of stirring, solution in reaction kettle is made to be changed into thick liquid.After the tiling of PP/PE/PP multilayer film, in chlorine
Under gas atmosphere, 10min is handled to a PP layer surface of multilayer film under RF low-temperature plasma discharging condition, by viscous fluid
Body is coated on the surface of treated multilayer film, is dried in vacuo under conditions of 110 DEG C and 0.055 atm, and polymerization is made
The polymer film of metal salt.
Embodiment 4
In a kettle, according to volume ratio 1:1 mixing acetone and dimethylformamide, mixed solution is obtained.Mixed solution is added
Uniformly mixed suspension is made in 2% weight of weight and the tripolyphosphate zinc of partial size 50nm, 50 min of supersonic oscillations.Outstanding
1% weight of mixed solution weight and the polymethyl methacrylate of average molecular weight 900,000, supersonic oscillations are added in turbid
20min.In 60 DEG C of 10 h of stirring, solution in reaction kettle is made to be changed into thick liquid.After the tiling of PP/PE multilayer film, it is being fluorinated
Under nitrogen atmosphere, discharge treatment 1min is carried out to the surface of the PE layer of multilayer film under the conditions of jet stream low temperature plasma, it will be sticky
Liquid is coated on the surface of treated multilayer film, is dried in vacuo under conditions of 110 DEG C and 0.01atm, and polymerization is made
The polymer film of metal salt.
Embodiment 5
In a kettle, according to volume ratio 0.1:1 mixing acetone and dimethylformamide, mixed solution is obtained.It is molten that mixing is added
Uniformly mixed suspension is made in 0.5% weight and 5 μm of partial size of tripolyphosphate boron of liquid weight, 50 min of supersonic oscillations.
1.4% weight of mixed solution weight and the polymethyl methacrylate of average molecular weight 1,000,000, ultrasound are added in suspension
Wave vibrates 15min.In 90 DEG C of 9 h of stirring, solution in reaction kettle is made to be changed into thick liquid.By the PP/PP multilayer of polypropylene screen
After film tiling, in the case where being fluorinated nitrogen atmosphere, to a surface treatment 50s of multilayer film under corona discharge conditions, by thick liquid
On surface coated in treated multilayer film, in 70 DEG C of forced air dryings, the polymer film of polymer/metallic salt is made.
Embodiment 6
In a kettle, according to volume ratio 10:1 mixing acetone and dimethylformamide, mixed solution is obtained.Mixed solution is added
1.67% weight of weight and the aluminium triphosphate of grain diameter 60nm, 1 min of supersonic oscillations, be made be uniformly mixed it is suspended
Liquid.2% weight of mixed solution weight and the polymethyl methacrylate of average molecular weight 400,000, ultrasound are added in suspension
Wave vibrates 30min.In 50 DEG C of stirring 8h, solution in reaction kettle is made to be changed into thick liquid.After the tiling of polypropylene screen monofilm,
Under formaldehyde atmosphere, to a surface treatment 10min of monofilm under corona discharge conditions, thick liquid is coated in and is passed through
It on the surface of the monofilm of processing, is dried in vacuo under conditions of 50 DEG C and 0.00095 atm, the polymerization of polymer/metallic salt is made
Object film.
Embodiment 7
In a kettle, according to volume ratio 5:1 mixing acetone and dimethylformamide, mixed solution is obtained.Mixed solution is added
0.67% weight of weight and the tripolyphosphate zinc of grain diameter 100nm, 30 min of supersonic oscillations are made uniformly mixed and hang
Turbid.2% weight of mixed solution weight and the polymethyl methacrylate of average molecular weight 900,000 are added in suspension, surpasses
Sonication 50min.In 75 DEG C of 12 h of stirring, solution in reaction kettle is made to be changed into thick liquid.PP/PE multilayer film is tiled
Afterwards, under formic acid atmosphere, 10 min is respectively handled to two surfaces of multilayer film under the conditions of glow discharge, thick liquid is coated
It on two surfaces of treated multilayer film, is dried in vacuo under conditions of 100 DEG C and 0.0002atm, polymerization gold is made
Belong to the polymer film of salt.
Claims (7)
1. a kind of preparation method of the polymer film of polymer/metallic salt, it is characterised in that preparation step is as follows: in a kettle, pressing
According to volume ratio (0.1~10): 1 ratio mixes acetone and dimethylformamide, and mixed solution is made；Mixed solution weight is added
0.33~2% weight coating agent, uniformly mixed suspension is made in 1~50 min of supersonic oscillations；Add in suspension
Enter the polymethyl methacrylate of 0.33~2% weight of mixed solution weight；10~50min of supersonic oscillations；At 50~90 DEG C
8~12 h of lower stirring, make solution in reaction kettle be changed into thick liquid；It will be opened by the tiling of radiation treatment basement membrane, viscous fluid
Body is coated in the surface of treated basement membrane, and vacuum drying or air blast are dry at any temperature of 50~110 DEG C of temperature ranges
It is dry, coating film is made；The coating agent is polyphosphoric acids zinc, aluminium triphosphate or tripolyphosphate boron.
2. a kind of preparation method of the polymer film of polymer/metallic salt according to claim 1, it is characterised in that described
Coating agent is tripolyphosphate zinc, aluminium triphosphate or tripolyphosphate boron of the partial size in the μ m of 1nm~5.
3. a kind of preparation method of the polymer film of polymer/metallic salt according to claim 1, it is characterised in that the warp
Overshoot basement membrane be under chlorine, fluorine gas, hydrogen fluoride, formaldehyde or formic acid atmosphere, it is low by glow discharge, corona discharge, radio frequency
The basement membrane of isothermal plasma electric discharge or jet stream discharge of plasma in low temperature processing 1s~10min.
4. a kind of preparation method of the polymer film of polymer/metallic salt according to claim 1, it is characterised in that described
Polymethyl methacrylate is polymethyl methacrylate of the average molecular weight in 40~1,700,000 ranges.
5. a kind of preparation method of the polymer film of polymer/metallic salt according to claim 1, it is characterised in that described
Vacuum drying is the heat drying carried out in 0.00001~0.1atm range pressure.
6. a kind of preparation method of the polymer film of polymer/metallic salt according to claim 1, it is characterised in that described
Basement membrane is monofilm or multilayer film containing polypropylene or polyethylene layer.
7. a kind of preparation method of the polymer film of polymer/metallic salt according to claim 6, it is characterised in that described
Multilayer film is the diaphragm that the number of plies is formed in the monofilm of 2~20 ranges.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102479932A (en) * | 2010-11-23 | 2012-05-30 | 清华大学 | Using method of lithium ion battery modifying agent, lithium ion battery diaphragm, and battery |
| CN102969473A (en) * | 2012-12-04 | 2013-03-13 | 宁德时代新能源科技有限公司 | Organic/inorganic composite porous thin film and electrochemical energy storing device using same |
| CN103311539A (en) * | 2013-05-17 | 2013-09-18 | 深圳市慧通天下科技股份有限公司 | High-voltage high-energy-density lithium ion battery |
| CN104112833A (en) * | 2014-06-06 | 2014-10-22 | 珠海光宇电池有限公司 | Lithium ion battery separating membrane, preparing method thereof and applications of the separating membrane |
| CN105990035A (en) * | 2016-01-27 | 2016-10-05 | 安徽旭峰电容器有限公司 | Ultrathin low-impedance supercapacitor-used separator material |
| CN107438912A (en) * | 2015-04-02 | 2017-12-05 | Sk新技术株式会社 | Secondary lithium batteries composite diaphragm and its manufacture method |
-
2018
- 2018-07-10 CN CN201810751797.7A patent/CN109021275A/en not_active Withdrawn
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102479932A (en) * | 2010-11-23 | 2012-05-30 | 清华大学 | Using method of lithium ion battery modifying agent, lithium ion battery diaphragm, and battery |
| CN102969473A (en) * | 2012-12-04 | 2013-03-13 | 宁德时代新能源科技有限公司 | Organic/inorganic composite porous thin film and electrochemical energy storing device using same |
| CN103311539A (en) * | 2013-05-17 | 2013-09-18 | 深圳市慧通天下科技股份有限公司 | High-voltage high-energy-density lithium ion battery |
| CN104112833A (en) * | 2014-06-06 | 2014-10-22 | 珠海光宇电池有限公司 | Lithium ion battery separating membrane, preparing method thereof and applications of the separating membrane |
| CN107438912A (en) * | 2015-04-02 | 2017-12-05 | Sk新技术株式会社 | Secondary lithium batteries composite diaphragm and its manufacture method |
| CN105990035A (en) * | 2016-01-27 | 2016-10-05 | 安徽旭峰电容器有限公司 | Ultrathin low-impedance supercapacitor-used separator material |
Non-Patent Citations (3)
| Title |
|---|
| LAURENT PUECH ET AL.: ""Elaboration and characterization of a free standing LiSICON membrane for aqueous lithium–air battery"", 《JOURNAL OF POWER SOURCES》 * |
| 周连江等: "《无机盐工业手册 下》", 30 June 1996, 化学工业出版社 * |
| 李广宇等: "《胶粘与密封新技术》", 31 January 2006, 国防工业出版社 * |
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Application publication date: 20181218 |