CN109860488A - Lithium battery diaphragm coating paste and preparation method thereof and diaphragm containing the slurry - Google Patents
Lithium battery diaphragm coating paste and preparation method thereof and diaphragm containing the slurry Download PDFInfo
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- CN109860488A CN109860488A CN201910064457.1A CN201910064457A CN109860488A CN 109860488 A CN109860488 A CN 109860488A CN 201910064457 A CN201910064457 A CN 201910064457A CN 109860488 A CN109860488 A CN 109860488A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to technical field of lithium batteries more particularly to a kind of lithium battery diaphragm coating pastes, adhesive solution, inorganic oxide, thickener and dispersing agent including adsorbable metal ion；The adhesive solution of the adsorbable metal ion is by will be obtained on strand that metal ion chelation agent is grafted to bonding agent under the action of ultraviolet light using ultraviolet light cross-linking agent.Compared with the prior art, slurry of the invention has efficient metal ion chelating capacity, which can effectively adsorb metal ion in electrolyte for lithium battery diaphragm coating.In addition, the present invention also provides a kind of preparation method of lithium ion battery coating paste and a kind of diaphragms coated with the coating paste.
Description
Technical field
The invention belongs to technical field of lithium batteries more particularly to a kind of lithium battery diaphragm coating paste and preparation method thereof
And the diaphragm containing the slurry.
Background technique
Lithium battery has high energy density and cycle life, is the preferred battery of power device and high capacity electronic product
One of.But after recycling at ambient and elevated temperatures, the metal ion of lithium battery anode dissolution can enter electrolyte and pass through lithium electricity
Pond diaphragm diffuses to cathode of lithium battery, and deposits on graphite cathode surface, and metal deposit hinders lithium ion in graphite
Deintercalation, so that the Reversible Cycle capacity of graphite electrode be made to decay.
Currently, it is following several to inhibit metal ion to have the dysgenic main method of lithium battery:
1) chemical property of positive electrode is improved by coating amorphous layer of nanomaterial.For example, patent
CN201811246578 discloses a kind of fluorapatite cladding nickel-cobalt lithium manganate cathode material method, so that material compact texture is sent out
It is raw to change, reach the performance and structure for improving encapsulated material, improve the capacity retention ratio of nickel-cobalt lithium manganate cathode material, drops
The capacity attenuation rate of low circulation electric discharge；Patent CN201811135072 discloses a kind of titanium phosphate lithium cladding lithium-rich manganese-based anode material
The preparation method of material makes titanium phosphate lithium cladding lithium-rich manganese-based anode material composite material have excellent cyclical stability；Patent
CN201811089226 discloses a kind of preparation method of graphene-coated lithium iron phosphate positive electrode, wraps on LiFePO4 surface
One layer of graphene is covered, the precipitation of metal ion is effectively prevent, and provides the superior electric conductivity of positive electrode.
2) structural stability of positive electrode, Lai Tigao chemical property are improved by doped nano-material.For example, specially
Sharp CN201810954002 discloses a kind of nickelic tertiary cathode material and preparation method, and preparation method is by ternary precursor
Powder and lithium-containing compound, alkali metal element (such as Na, Li), nonmetalloid (B, P, Si) heat preservation a period of time, so that alkali
Metallic element is uniformly spread with nonmetalloid ion to material internal, obtains codoping modified nickelic ternary material.It is modified
Nickelic ternary material in Ni2+With Li+Mixing degree is low, interlamellar spacing increase, stable structure, and have excellent electrochemical activity, times
Rate performance and cyclical stability stable structure, and there is excellent electrochemical activity, high rate performance and cyclical stability.
3) prevent metal ion in the deposition of cathode by using the electrolyte with adsorption of metal ions function instead.As specially
Sharp CN201810942662 discloses a kind of preparation method of suspending stabilized type colloidal electrolyte of high-cooling property, to electrolyte Shangguan
It can roll into a ball and be modified, allow to complexation of metal ions, to ensure that the cyclical stability of battery.
Although the above various schemes can inhibit to a certain extent metal ion to lithium battery adverse effect, technique
All more complicated, cost is also higher.
Summary of the invention
It is an object of the present invention to: in view of the deficiencies of the prior art, and a kind of lithium battery diaphragm is provided and is starched with coating
Material, has efficient metal ion chelating capacity, which can effectively adsorb golden in electrolyte for lithium battery diaphragm coating
Belong to ion.
To achieve the goals above, the invention adopts the following technical scheme:
A kind of lithium battery diaphragm coating paste, adhesive solution, inorganic oxide including adsorbable metal ion, increasing
Thick dose and dispersing agent；The adhesive solution of the adsorbable metal ion is by utilizing ultraviolet light cross-linking agent by metal ion chela
It is obtained on the strand that mixture is grafted to bonding agent under the action of ultraviolet light.
As a kind of improvement of lithium battery diaphragm coating paste of the present invention, the adsorbable metal ion glues
The mass ratio for connecing agent solution, the inorganic oxide, the thickener and the dispersing agent is 100:(5~10): (1~10):
(0.05~0.1).
As a kind of improvement of lithium battery diaphragm coating paste of the present invention, the bonding agent is styrene-fourth
Diene polymer, Kynoar-hexafluoropropene, polyacrylic acid, polymethylacrylic acid, polyacrylate, gathers Kynoar
Methyl methacrylate, sodium carboxymethylcellulose, butadiene-acrylonitrile polymer, polyvinylpyrrolidone, gathers polyacrylonitrile
At least one of acrylicstyrene and dimethyl siloxane.
As a kind of improvement of lithium battery diaphragm coating paste of the present invention, the metal ion chelation agent is hydroxyl
Any one in ethyl-3-acetic acid ethylenediamine, ethylenediamine tetra-acetic acid and aminotriacetic acid.
As a kind of improvement of lithium battery diaphragm coating paste of the present invention, the ultraviolet light cross-linking agent is hexichol
Ketone or benzyl phenyl ketone.
As a kind of improvement of lithium battery diaphragm coating paste of the present invention, the inorganic oxide is oxidation
Calcium, zinc oxide, magnesia, titanium dioxide, silica, zirconium dioxide, stannic oxide, ceria, aluminum oxide and vigorous
At least one of nurse stone.
As a kind of improvement of lithium battery diaphragm coating paste of the present invention, the thickener is carboxymethyl cellulose
Plain sodium or POLYPROPYLENE GLYCOL.
As a kind of improvement of lithium battery diaphragm coating paste of the present invention, the dispersing agent be polyethylene glycol,
Any one in polyvinylpyrrolidone and polyacrylamide.
Compared with the prior art, coating paste of the invention contains the adhesive solution of adsorbable metal ion, therein
Metal-chelator has the coating paste of adsorption function to metal ion, can occur with the metal ion of dissolution further anti-
It answers, reduces deposition of the metal ion in cathode of dissolution, and then reduce the stability of SEI film, guarantee battery safety for a long time
It uses.And the present invention also further adds inorganic oxide, on the one hand can increase adsorption capacity, on the other hand can guarantee
The good chemical stability of battery diaphragm, lithium ion permeability, thermal stability and mechanical strength.
The second object of the present invention is: providing a kind of preparation method of lithium battery diaphragm coating paste, including following
Preparation method:
S1, bonding agent and deionized water are pressed (1~2): 9 mass ratio disperses, and obtains bonding agent aqueous dispersions；
S2, by metal ion chelation agent, ultraviolet light cross-linking agent and step S1 obtain bonding agent aqueous dispersions by (0.2~
0.8): (0.5~1): 100 mass ratio mixing, stir evenly obtain bonding agent, metal-chelator, ultraviolet light cross-linking agent it is mixed
Close solution；
The step S2 mixed solution obtained is added in ultraviolet reactor by S3, is carried out in the atmosphere of protection gas purple
Outer light irradiation, obtains the adhesive solution of adsorbable metal ion；
S4 is dispersed inorganic oxide and deionized water by the mass ratio of 1:9, adjusts pH, is obtained uniform inorganic
Oxidate dispersion solution；
S5, the inorganic oxide point that the adhesive solution of the step S3 adsorbable metal ion obtained, step S4 are obtained
Dispersion liquid, dispersing agent and thickener press 100:(50~100): (1~10): the mass ratio mixing of (0.05~0.1) obtains adsorbable
The lithium ion battery separator coating paste of metal ion.
Compared with the prior art, preparation method of the invention and operating condition are relatively simple, without putting into a large amount of fund
And manpower, it is suitable for batch production.
The third object of the present invention is: providing a kind of lithium battery diaphragm, an at least surface for the diaphragm is coated with one
Layer with a thickness of 1~5um lithium battery diaphragm coating paste.
Compared with the prior art, it is coated with the coating paste with adsorption function on diaphragm of the invention, can and dissolve out
Metal ion further reaction occurs, reduce deposition of the metal ion in cathode of dissolution, and then reduce the stabilization of SEI film
Property, guarantee that battery is used safely for a long time.
Specific embodiment
The present invention is described in further detail With reference to embodiment, but embodiments of the present invention are not
It is limited to this.
Comparative example 1
A kind of lithium battery diaphragm coating paste, it is fine comprising Kynoar-hexafluoropropene, aluminum oxide and carboxymethyl
Tie up plain sodium.
The preparation method of above-mentioned lithium battery diaphragm coating paste, the specific steps are as follows:
Kynoar-hexafluoropropene and sodium carboxymethylcellulose are add to deionized water, stir 2h at 50 DEG C,
Wherein, the mass ratio of Kynoar-hexafluoropropene and sodium carboxymethylcellulose is 95:5, is agglomerated into the suspended dispersed of bulky grain
Liquid；It is subsequently added into aluminum oxide particle and is stirred 1h, aluminum oxide is with Kynoar-hexafluoropropene mass ratio
50:50 obtains the mixed slurry of inorganic particulate and bonding agent.
Embodiment 1
A kind of lithium battery diaphragm coating paste, Kynoar solution, boehmite comprising adsorbable metal ion are divided
Powder polyethylene glycol and sodium cellulose glycolate, four mass ratioes are 100:6:5:0.05；Wherein, adsorbable metal ion is poly-
Vinylidene mixed solution is by being grafted to hydroxyethylethylene diamine tri-acetic acid under the action of ultraviolet light using benzophenone
It is obtained on the strand of Kynoar.
The preparation method of above-mentioned lithium battery diaphragm coating paste, the specific steps are as follows:
S1 in deionized water by Kynoar 1:10 in mass ratio dispersion stirs 0.5~2h, obtains polyvinylidene fluoride
Alkene aqueous dispersions；
S2 obtains metal ion chelation agent hydroxyethylethylene diamine tri-acetic acid, ultraviolet light cross-linking agent benzophenone and step S1
The Kynoar aqueous dispersions 0.5:1:100 in mass ratio mixing obtained, stirs 0.5~2h, obtains Kynoar, ethoxy
The mixed solution of ethylenediamine triacetic acid, benzophenone；
S3, the step S2 mixed solution obtained is added in ultraviolet reactor, is carried out in the atmosphere of nitrogen ultraviolet
Light irradiation, irradiation distance 20cm irradiate 0.5~1h, obtain the Kynoar solution of adsorbable metal ion；
Boehmite 1:9 in mass ratio is add to deionized water by S4, with 10wt% hydrochloric acid adjust dispersion liquid pH to 1~
3, obtain uniform boehmite dispersion；
S5, the boehmite water that the Kynoar solution of the step S3 adsorbable metal ion obtained, step S4 are obtained
Dispersion liquid, polyethylene glycol and sodium cellulose glycolate 100:60:5:0.05 in mass ratio mixing, 2~3h of stirring obtain adsorbable
The coating paste of metal ion.
Embodiment 2
A kind of lithium battery diaphragm coating paste, the polymethyl methacrylate solution comprising adsorbable metal ion, two
Titanium oxide, dispersing agent polyethylene glycol and sodium cellulose glycolate, four mass ratioes are 100:8:4:0.05；Wherein, adsorbable gold
Belong to ion polymethyl methacrylate mixed solution be by using benzophenone by ethylenediamine tetra-acetic acid ultraviolet light work
It is grafted on the strand of polymethyl methacrylate and obtains under.
The preparation method of above-mentioned lithium battery diaphragm coating paste, the specific steps are as follows:
S1 in deionized water by polymethyl methacrylate 1:9 in mass ratio dispersion stirs 0.5~2h, obtains poly- first
Base methyl acrylate aqueous dispersions；
S2 obtains metal ion chelation agent ethylenediamine tetra-acetic acid, ultraviolet light cross-linking agent benzophenone and step S1 poly-
Methyl methacrylate aqueous dispersions 0.5:1:100 in mass ratio mixing, stirring 0.5-2h, acquisition polymethyl methacrylate,
The mixed solution of ethylenediamine tetra-acetic acid, benzophenone；
S3, the step S2 mixed solution obtained is added in ultraviolet reactor, is carried out in the atmosphere of nitrogen ultraviolet
Light irradiation, irradiation distance 20cm irradiate 0.5-1h, obtain the polymethyl methacrylate solution of adsorbable metal ion；
Titanium dioxide 1:9 in mass ratio is add to deionized water by S4, adjusts dispersion liquid pH to 1 with 10wt% hydrochloric acid
~3, obtain uniform titanium oxide dispersion；
S5, two that the polymethyl methacrylate solution of the step S3 adsorbable metal ion obtained, step S4 are obtained
Titanium oxide dispersion liquid, dispersing agent and thickener 100:80:4:0.05 in mass ratio mixing, stirring 2-3h obtain adsorbable metal from
The coating paste of son.
Embodiment 3
A kind of lithium battery diaphragm coating paste, the Kynoar comprising adsorbable metal ion-hexafluoropropene solution,
Silica, dispersing agent polyethylene glycol and sodium cellulose glycolate, four mass ratioes are 100:9:4:0.05；Wherein, adsorbable
The Kynoar of metal ion-hexafluoropropene mixed solution is by utilizing benzophenone by aminotriacetic acid in ultraviolet light
It is grafted on Kynoar-hexafluoropropene strand and obtains under effect.
The preparation method of above-mentioned lithium battery diaphragm coating paste, the specific steps are as follows:
S1 in deionized water by Kynoar-hexafluoropropene 1:9 in mass ratio dispersion stirs 0.5~2h, obtains
Biasfluoroethylene-hexafluoropropylene aqueous dispersions；
S2, the inclined fluorine that metal ion chelation agent aminotriacetic acid, ultraviolet light cross-linking agent benzophenone and step S1 are obtained
Ethylene-hexafluoropropene aqueous dispersions 0.5:1:100 in mass ratio mixing, 0.5~2h of stirring, acquisition biasfluoroethylene-hexafluoropropylene,
The mixed solution of aminotriacetic acid, benzophenone；
S3, the step S2 mixed solution obtained is added in ultraviolet reactor, is carried out in the atmosphere of nitrogen ultraviolet
Light irradiation, irradiation distance 20cm irradiate 0.5~1h, obtain Kynoar-hexafluoropropene solution of adsorbable metal ion；
Silica 1:9 in mass ratio is add to deionized water by S4, adjusts dispersion liquid pH to 1 with 10wt% hydrochloric acid
~3, obtain uniform silica dispersions；
S5, two that the biasfluoroethylene-hexafluoropropylene solution of the step S3 adsorbable metal ion obtained, step S4 are obtained
Silica dispersion liquid, dispersing agent and thickener 100:90:4:0.05 in mass ratio mixing, stirring 2-3h obtain adsorbable metal from
The coating paste of son.
Embodiment 4
A kind of lithium battery diaphragm coating paste, the styrene-butadiene solution comprising adsorbable metal ion,
Aluminum oxide, dispersing agent polyethylene glycol and sodium cellulose glycolate, four mass ratioes are 100:9:4:0.06；Wherein, it can inhale
The styrene-butadiene mixed solution of attached metal ion is by utilizing benzophenone by aminotriacetic acid in ultraviolet light
Under the action of be grafted on the strand of styrene-butadiene and obtain.
The preparation method of above-mentioned lithium battery diaphragm coating paste, the specific steps are as follows:
S1 in deionized water by styrene-butadiene 1:9 in mass ratio dispersion stirs 0.5~2h, obtains
Styrene-butadiene aqueous dispersions；
S2, the benzene second that metal ion chelation agent aminotriacetic acid, ultraviolet light cross-linking agent benzophenone and step S1 are obtained
Alkene-butadiene polymer aqueous dispersions 0.5:1:100 in mass ratio mixing, stirs 0.5~2h, it is poly- to obtain styrene-butadiene
Close the mixed solution of object, aminotriacetic acid, benzophenone；
Step S2 acquisition mixed solution is added in ultraviolet reactor, ultraviolet light is carried out in the atmosphere of nitrogen by S3
Irradiation, irradiation distance 20cm irradiate 0.5-1h, obtain the styrene-butadiene solution of adsorbable metal ion；
Aluminum oxide 1:9 in mass ratio is add to deionized water by S4, is adjusted dispersion liquid pH with 10wt% hydrochloric acid and is arrived
1~3, obtain uniform aluminum oxide dispersion liquid；
Step S3 is obtained the styrene-butadiene solution of adsorbable metal ion by S5, step S4 obtains three oxygen
Change two aluminium dispersion liquids, dispersing agent and thickener 100:90:4:0.06 in mass ratio mixing, 2~3h of stirring obtains adsorbable metal
The coating paste of ion.
Embodiment 5
A kind of lithium battery diaphragm coating paste, polyacrylonitrile, ceria, dispersing agent comprising adsorbable metal ion
Polyethylene glycol and sodium cellulose glycolate, four mass ratioes are 100:10:5:0.07；Wherein, poly- the third of adsorbable metal ion
Alkene nitrile mixed solution is point by the way that aminotriacetic acid to be grafted to polyacrylonitrile using benzyl phenyl ketone under the action of ultraviolet light
It is obtained in subchain.
The preparation method of above-mentioned lithium battery diaphragm coating paste, the specific steps are as follows:
S1 in deionized water by polyacrylonitrile 1:9 in mass ratio dispersion stirs 0.5~2h, obtains polyacrylonitrile moisture
Dispersion liquid；
S2, poly- third that metal ion chelation agent aminotriacetic acid, ultraviolet light cross-linking agent benzyl phenyl ketone and step S1 are obtained
Alkene nitrile aqueous dispersions 0.5:1:100 in mass ratio mixing, stirs 0.5~2h, obtains polyacrylonitrile, aminotriacetic acid, hexichol second
The mixed solution of ketone；
S3, the step S2 mixed solution obtained is added in ultraviolet reactor, is carried out in the atmosphere of nitrogen ultraviolet
Light irradiation, irradiation distance 20cm irradiate 0.5-1h, obtain the polyacrylonitrile solution of adsorbable metal ion；
Ceria 1:9 in mass ratio is add to deionized water by S4, adjusts dispersion liquid pH to 1 with 10wt% hydrochloric acid
~3, obtain uniform ceria dispersion liquid；
S5, the ceria point that the polyacrylonitrile solution of the step S3 adsorbable metal ion obtained, step S4 are obtained
Dispersion liquid, dispersing agent and thickener 100:100:5:0.07 in mass ratio mixing, 2~3h of stirring obtain the painting of adsorbable metal ion
Layer slurry.
Embodiment 6
A kind of lithium battery diaphragm coating paste, polyacrylonitrile, zinc oxide, polyethylene pyrrole comprising adsorbable metal ion
Pyrrolidone and POLYPROPYLENE GLYCOL, four mass ratioes are 100:5:4:0.08；Wherein, the polyacrylonitrile mixing of adsorbable metal ion is molten
Liquid is by will be obtained on strand that aminotriacetic acid is grafted to polyacrylonitrile under the action of ultraviolet light using benzyl phenyl ketone.
The preparation method of above-mentioned lithium battery diaphragm coating paste, the specific steps are as follows:
S1 in deionized water by polyacrylonitrile 1:9 in mass ratio dispersion stirs 0.5~2h, obtains polyacrylonitrile moisture
Dispersion liquid；
S2, poly- third that metal ion chelation agent aminotriacetic acid, ultraviolet light cross-linking agent benzyl phenyl ketone and step S1 are obtained
Alkene nitrile aqueous dispersions 0.5:1:100 in mass ratio mixing, stirs 0.5~2h, obtains polyacrylonitrile, aminotriacetic acid, hexichol second
The mixed solution of ketone；
S3, the step S2 mixed solution obtained is added in ultraviolet reactor, is carried out in the atmosphere of nitrogen ultraviolet
Light irradiation, irradiation distance 20cm irradiate 0.5-1h, obtain the polyacrylonitrile solution of adsorbable metal ion；
Zinc oxide 1:9 in mass ratio is add to deionized water by S4, with 10wt% hydrochloric acid adjust dispersion liquid pH to 1~
3, obtain uniform zinc oxide fluid dispersion；
S5 disperses the polyacrylonitrile solution of the step S3 adsorbable metal ion obtained, step the S4 zinc oxide obtained
Liquid, dispersing agent and thickener 100:50:4:0.08 in mass ratio mixing, 2~3h of stirring obtain the coating of adsorbable metal ion
Slurry.
Embodiment 7
A kind of lithium battery diaphragm coating paste, polyacrylic acid-styrene comprising adsorbable metal ion and adsorbable
Dimethyl siloxane, magnesia, polyvinylpyrrolidone and the POLYPROPYLENE GLYCOL of metal ion, four mass ratioes are 100:5:4:
0.09；Wherein, the polyacrylic acid of adsorbable metal ion-styrene mixed solution is by utilizing benzyl phenyl ketone by three second of amino
Acid is grafted on polyacrylic acid-styrene strand under the action of ultraviolet light and obtains, the dimethyl of adsorbable metal ion
Siloxanes mixed solution is by the way that aminotriacetic acid is grafted to dimethyl silica under the action of ultraviolet light using benzyl phenyl ketone
It is obtained on the strand of alkane.
The preparation method of above-mentioned lithium battery diaphragm coating paste, the specific steps are as follows:
S1 disperses polyacrylic acid-styrene, dimethyl siloxane and deionized water 0.5:0.5:9 in mass ratio,
0.5~2h is stirred, polyacrylic acid-styrene, dimethyl siloxane mix moisture dispersion liquid are obtained；
S2, poly- third that metal ion chelation agent aminotriacetic acid, ultraviolet light cross-linking agent benzyl phenyl ketone and step S1 are obtained
Olefin(e) acid-styrene, dimethyl siloxane mix moisture dispersion liquid 0.5:1:100 in mass ratio mixing, stir 0.5~2h, are gathered
Acrylicstyrene, dimethyl siloxane, aminotriacetic acid, benzyl phenyl ketone mixed solution；
S3, the step S2 mixed solution obtained is added in ultraviolet reactor, is carried out in the atmosphere of nitrogen ultraviolet
Light irradiation, irradiation distance 20cm irradiate 0.5-1h, obtain polyacrylic acid-styrene solution of adsorbable metal ion and can inhale
The dimethyl siloxane solution of attached metal ion；
Magnesia 1:9 in mass ratio is add to deionized water by S4, with 10wt% hydrochloric acid adjust dispersion liquid pH to 1~
3, obtain uniform magnesium oxide dispersion liquid；
S5, by polyacrylic acid-styrene solution of the step S3 adsorbable metal ion obtained and adsorbable metal ion
Dimethyl siloxane solution, step S4 obtain magnesium oxide dispersion liquid, dispersing agent and thickener 100:50:4 in mass ratio:
0.09 mixing, 2~3h of stirring obtain the coating paste of adsorbable metal ion.
Embodiment 8
A kind of lithium battery diaphragm coating paste, the butadiene-acrylonitrile polymer comprising adsorbable metal ion, oxidation
Calcium, polyacrylamide and sodium carboxymethylcellulose, four mass ratioes are 100:5:4:0.1；Wherein, the fourth of adsorbable metal ion
Butadiene-acrylonitrile mixed with polymers solution is by being grafted to aminotriacetic acid under the action of ultraviolet light using benzyl phenyl ketone
It is obtained on the strand of butadiene-acrylonitrile polymer.
The preparation method of above-mentioned lithium battery diaphragm coating paste, the specific steps are as follows:
S1 in deionized water by butadiene-acrylonitrile polymer 1:9 in mass ratio dispersion stirs 0.5~2h, obtains
Butadiene-acrylonitrile polymer aqueous dispersions；
S2, the fourth two that metal ion chelation agent aminotriacetic acid, ultraviolet light cross-linking agent benzyl phenyl ketone and step S1 are obtained
Alkene-acrylonitrile polymer aqueous dispersions 0.5:1:100 in mass ratio mixing, stirs 0.5~2h, it is poly- to obtain butadiene-acrylonitrile
Close the mixed solution of object, aminotriacetic acid, benzyl phenyl ketone；
S3, the step S2 mixed solution obtained is added in ultraviolet reactor, is carried out in the atmosphere of nitrogen ultraviolet
Light irradiation, irradiation distance 20cm irradiate 0.5-1h, obtain the butadiene-acrylonitrile polymer solution of adsorbable metal ion；
Calcium oxide 1:9 in mass ratio is add to deionized water by S4, with 10wt% hydrochloric acid adjust dispersion liquid pH to 1~
3, obtain uniform calcium oxide dispersion liquid；
S5 obtains the butadiene-acrylonitrile polymer solution of the step S3 adsorbable metal ion obtained, step S4
Calcium oxide dispersion liquid, dispersing agent and thickener 100:50:4:0.1 in mass ratio mixing, 2~3h of stirring obtain adsorbable metal from
The coating paste of son.
Embodiment 9
A kind of lithium battery diaphragm coating paste, Kynoar solution, zirconium dioxide comprising adsorbable metal ion,
Dispersing agent polyethylene glycol and sodium cellulose glycolate, four mass ratioes are 100:6:5:0.05；Wherein, adsorbable metal ion
Kynoar mixed solution is by being grafted hydroxyethylethylene diamine tri-acetic acid under the action of ultraviolet light using benzophenone
It is obtained on to the strand of Kynoar.
The preparation method of above-mentioned lithium battery diaphragm coating paste, the specific steps are as follows:
S1 in deionized water by polymethylacrylic acid 1:10 in mass ratio dispersion stirs 0.5~2h, obtains poly- methyl
Acrylic acid aqueous dispersions；
S2 obtains metal ion chelation agent hydroxyethylethylene diamine tri-acetic acid, ultraviolet light cross-linking agent benzophenone and step S1
The polymethylacrylic acid aqueous dispersions 0.5:1:100 in mass ratio mixing obtained, stirs 0.5-2h, obtains polymethylacrylic acid, hydroxyl
The mixed solution of ethyl-3-acetic acid ethylenediamine, benzophenone；
Step S2 acquisition mixed solution is added in ultraviolet reactor, ultraviolet light is carried out in the atmosphere of nitrogen by S3
Irradiation, irradiation distance 20cm irradiate 0.5~1h, obtain the polymethyl acid solution of adsorbable metal ion；
Zirconium dioxide 1:9 in mass ratio is add to deionized water by S4, adjusts dispersion liquid pH to 1 with 10wt% hydrochloric acid
~3, obtain uniform zirconium dioxide dispersion liquid；
S5, the titanium dioxide that the polymethyl acid solution of the step S3 adsorbable metal ion obtained, step S4 are obtained
Zirconium dispersion liquid, polyethylene glycol and sodium cellulose glycolate 100:60:5:0.05 in mass ratio mixing, stirring 2-3h obtain adsorbable
The coating paste of metal ion.
Embodiment 10
A kind of lithium battery diaphragm coating paste, polyvinylpyrrolidonesolution solution, dioxy comprising adsorbable metal ion
Change tin, dispersing agent polyethylene glycol and sodium cellulose glycolate, four mass ratioes are 100:7:5:0.05；Wherein, adsorbable metal
The polyvinylpyrrolidone mixed solution of ion is by utilizing benzophenone by hydroxyethylethylene diamine tri-acetic acid in ultraviolet light
It is grafted on the strand of polyvinylpyrrolidone and obtains under effect.
The preparation method of above-mentioned lithium battery diaphragm coating paste, the specific steps are as follows:
S1 in deionized water by polyvinylpyrrolidone 1:10 in mass ratio dispersion stirs 0.5~2h, obtains poly- second
Alkene pyrrolidone aqueous dispersions；
S2 obtains metal ion chelation agent hydroxyethylethylene diamine tri-acetic acid, ultraviolet light cross-linking agent benzophenone and step S1
The polyvinylpyrrolidone aqueous dispersions 0.5:1:100 in mass ratio mixing obtained, stirs 0.5-2h, obtains polyvinylpyrrolidine
Ketone, hydroxyethylethylene diamine tri-acetic acid, benzophenone mixed solution；
Step S2 acquisition mixed solution is added in ultraviolet reactor, ultraviolet light is carried out in the atmosphere of nitrogen by S3
Irradiation, irradiation distance 20cm irradiate 0.5~1h, obtain the polyvinylpyrrolidonesolution solution of adsorbable metal ion；
Stannic oxide 1:9 in mass ratio is add to deionized water by S4, adjusts dispersion liquid pH to 1 with 10wt% hydrochloric acid
~3, obtain uniform stannic oxide dispersion liquid；
S5, the dioxy that the polyvinylpyrrolidonesolution solution of the step S3 adsorbable metal ion obtained, step S4 are obtained
Change tin dispersion liquid, polyethylene glycol and sodium cellulose glycolate 100:70:5:0.05 in mass ratio mixing, stirring 2-3h acquisition can inhale
The coating paste of attached metal ion.
Embodiment 11
A kind of lithium battery diaphragm coating paste, the polyvinylpyrrolidonesolution solution comprising adsorbable metal ion, oxidation
Calcium and titanium dioxide, dispersing agent polyethylene glycol and sodium cellulose glycolate, four mass ratioes are 100:8:6:0.05；Wherein, may be used
The polyvinylpyrrolidone mixed solution of adsorbing metal ions is by the way that hydroxyethylethylene diamine tri-acetic acid is existed using benzophenone
It is grafted on the strand of polyvinylpyrrolidone and obtains under the action of ultraviolet light.
The preparation method of above-mentioned lithium battery diaphragm coating paste, the specific steps are as follows:
S1 in deionized water by polyvinylpyrrolidone 1:10 in mass ratio dispersion stirs 0.5~2h, obtains poly- second
Alkene pyrrolidone aqueous dispersions；
S2 obtains metal ion chelation agent hydroxyethylethylene diamine tri-acetic acid, ultraviolet light cross-linking agent benzophenone and step S1
The polyvinylpyrrolidone aqueous dispersions 0.5:1:100 in mass ratio mixing obtained, stirs 0.5-2h, obtains polyvinylpyrrolidine
Ketone, hydroxyethylethylene diamine tri-acetic acid, benzophenone mixed solution；
Step S2 acquisition mixed solution is added in ultraviolet reactor, ultraviolet light is carried out in the atmosphere of nitrogen by S3
Irradiation, irradiation distance 20cm irradiate 0.5~1h, obtain the polyvinylpyrrolidonesolution solution of adsorbable metal ion；
S4 mixes calcium oxide, titanium dioxide and deionized water 0.5:0.5:9 in mass ratio, with 10wt% hydrochloric acid
Dispersion liquid pH to 1~3 is adjusted, uniform calcium oxide, titanium oxide dispersion are obtained；
S5, the oxidation that the polyvinylpyrrolidonesolution solution of the step S3 adsorbable metal ion obtained, step S4 are obtained
Calcium, titanium oxide dispersion, polyethylene glycol and sodium cellulose glycolate 100:80:6:0.05 in mass ratio mixing, stir 2-3h
Obtain the coating paste of adsorbable metal ion.
Embodiment 12
A kind of lithium battery diaphragm coating paste, the polyvinylpyrrolidonesolution solution comprising adsorbable metal ion, oxidation
Zinc and zirconium dioxide, dispersing agent polyethylene glycol and sodium cellulose glycolate, four mass ratioes are 100:10:8:0.05；Wherein, may be used
The polyvinylpyrrolidone mixed solution of adsorbing metal ions is by the way that hydroxyethylethylene diamine tri-acetic acid is existed using benzophenone
It is grafted on the strand of polyvinylpyrrolidone and obtains under the action of ultraviolet light.
The preparation method of above-mentioned lithium battery diaphragm coating paste, the specific steps are as follows:
S1 in deionized water by polyvinylpyrrolidone 1:10 in mass ratio dispersion stirs 0.5~2h, obtains poly- second
Alkene pyrrolidone aqueous dispersions；
S2 obtains metal ion chelation agent hydroxyethylethylene diamine tri-acetic acid, ultraviolet light cross-linking agent benzophenone and step S1
The polyvinylpyrrolidone aqueous dispersions 0.5:1:100 in mass ratio mixing obtained, stirs 0.5-2h, obtains polyvinylpyrrolidine
Ketone, hydroxyethylethylene diamine tri-acetic acid, benzophenone mixed solution；
S3, the step S2 mixed solution obtained is added in ultraviolet reactor, is carried out in the atmosphere of nitrogen ultraviolet
Light irradiation, irradiation distance 20cm irradiate 0.5~1h, obtain the polyvinylpyrrolidonesolution solution of adsorbable metal ion；
S4 mixes zinc oxide, zirconium dioxide and deionized water 0.5:0.5:9 in mass ratio, is adjusted with 10wt% hydrochloric acid
Dispersion liquid pH to 1~3 obtains uniform zinc oxide and zirconium dioxide dispersion liquid；
S5, the oxidation that the polyvinylpyrrolidonesolution solution of the step S3 adsorbable metal ion obtained, step S4 are obtained
Zinc and zirconium dioxide dispersion liquid, polyethylene glycol and sodium cellulose glycolate 100:100:8:0.05 in mass ratio mixing, stir 2-
3h obtains the coating paste of adsorbable metal ion.
Embodiment 13
A kind of lithium battery diaphragm coating paste, the polyvinylpyrrolidonesolution solution comprising adsorbable metal ion, oxidation
Magnesium and boehmite, dispersing agent polyethylene glycol and sodium cellulose glycolate, four mass ratioes are 100:5:3:0.05；Wherein, it can inhale
The polyvinylpyrrolidone mixed solution of attached metal ion is by utilizing benzophenone by ethylenediamine tetra-acetic acid in ultraviolet light
It is grafted on the strand of polyvinylpyrrolidone and obtains under effect.
The preparation method of above-mentioned lithium battery diaphragm coating paste, the specific steps are as follows:
S1 in deionized water by polyvinylpyrrolidone 1:10 in mass ratio dispersion stirs 0.5~2h, obtains poly- second
Alkene pyrrolidone aqueous dispersions；
S2 obtains metal ion chelation agent ethylenediamine tetra-acetic acid, ultraviolet light cross-linking agent benzophenone and step S1 poly-
Vinylpyrrolidone aqueous dispersions 0.5:1:100 in mass ratio mixing, stirs 0.5-2h, obtains polyvinylpyrrolidone, second two
The mixed solution of amine tetraacethyl, benzophenone；
S3, the step S2 mixed solution obtained is added in ultraviolet reactor, is carried out in the atmosphere of nitrogen ultraviolet
Light irradiation, irradiation distance 20cm irradiate 0.5~1h, obtain the polyvinylpyrrolidonesolution solution of adsorbable metal ion；
S4 mixes magnesia, boehmite and deionized water 0.5:0.5:9 in mass ratio, is adjusted and is divided with 10wt% hydrochloric acid
Dispersion liquid pH to 1~3 obtains uniform magnesia, boehmite dispersion；
S5, the oxidation that the polyvinylpyrrolidonesolution solution of the step S3 adsorbable metal ion obtained, step S4 are obtained
Magnesium, boehmite dispersion, polyethylene glycol and sodium cellulose glycolate 100:50:3:0.05 in mass ratio mixing, stirring 2-3h are obtained
Obtain the coating paste of adsorbable metal ion.
Embodiment 14
A kind of lithium battery diaphragm coating paste, polyvinylpyrrolidonesolution solution, dioxy comprising adsorbable metal ion
Change cerium and aluminum oxide, dispersing agent polyethylene glycol and sodium cellulose glycolate, four mass ratioes are 100:7:5:0.05；Its
In, the polyvinylpyrrolidone mixed solution of adsorbable metal ion is by utilizing benzophenone by three second of hydroxyethyl ethylenediamine
It is obtained on the strand that acid is grafted to polyvinylpyrrolidone under the action of ultraviolet light.
The preparation method of above-mentioned lithium battery diaphragm coating paste, the specific steps are as follows:
S1 in deionized water by polyvinylpyrrolidone 1:10 in mass ratio dispersion stirs 0.5~2h, obtains poly- second
Alkene pyrrolidone aqueous dispersions；
S2 obtains metal ion chelation agent hydroxyethylethylene diamine tri-acetic acid, ultraviolet light cross-linking agent benzophenone and step S1
The polyvinylpyrrolidone aqueous dispersions 0.5:1:100 in mass ratio mixing obtained, stirs 0.5-2h, obtains polyvinylpyrrolidine
Ketone, hydroxyethylethylene diamine tri-acetic acid, benzophenone mixed solution；
Step S2 acquisition mixed solution is added in ultraviolet reactor, ultraviolet light is carried out in the atmosphere of nitrogen by S3
Irradiation, irradiation distance 20cm irradiate 0.5~1h, obtain the polyvinylpyrrolidonesolution solution of adsorbable metal ion；
S4, by ceria, aluminum oxide and deionization, whose 0.5:0.5:9 in mass ratio is mixed, with 10wt% hydrochloric acid
Dispersion liquid pH to 1~3 is adjusted, uniform ceria, aluminum oxide dispersion liquid are obtained；
S5, the dioxy that the polyvinylpyrrolidonesolution solution of the step S3 adsorbable metal ion obtained, step S4 are obtained
Change cerium, aluminum oxide dispersion liquid, polyethylene glycol and sodium cellulose glycolate 100:70:5:0.05 in mass ratio mixing, stirring
2-3h obtains the coating paste of adsorbable metal ion.
Embodiment 15
A kind of lithium battery diaphragm coating paste, dimethyl siloxane, stannic oxide comprising adsorbable metal ion divide
Powder polyethylene glycol and sodium cellulose glycolate, four mass ratioes are 100:6:5:0.05；Wherein, the two of adsorbable metal ion
Methylsiloxane mixed solution is by the way that ethylenediamine tetra-acetic acid is grafted to diformazan under the action of ultraviolet light using benzophenone
It is obtained on the strand of radical siloxane.
The preparation method of above-mentioned lithium battery diaphragm coating paste, the specific steps are as follows:
S1 in deionized water by dimethyl siloxane 1:10 in mass ratio dispersion stirs 0.5~2h, obtains dimethyl
Aqueous silicone dispersion；
S2, two that metal ion chelation agent ethylenediamine tetra-acetic acid, ultraviolet light cross-linking agent benzophenone and step S1 are obtained
Methylsiloxane aqueous dispersions 0.5:1:100 in mass ratio mixing, stirs 0.5-2h, obtains dimethyl siloxane, ethylenediamine tetraacetic
The mixed solution of acetic acid, benzophenone；
Step S2 acquisition mixed solution is added in ultraviolet reactor, ultraviolet light is carried out in the atmosphere of nitrogen by S3
Irradiation, irradiation distance 20cm irradiate 0.5~1h, obtain the dimethyl siloxane solution of adsorbable metal ion；
Stannic oxide 1:9 in mass ratio is add to deionized water by S4, adjusts dispersion liquid pH to 1 with 10wt% hydrochloric acid
~3, obtain uniform zirconium dioxide dispersion liquid；
S5, the titanium dioxide that the dimethyl siloxane solution of the step S3 adsorbable metal ion obtained, step S4 are obtained
Tin dispersion liquid, polyethylene glycol and sodium cellulose glycolate 100:60:5:0.05 in mass ratio mixing, stirring 2-3h obtain adsorbable
The coating paste of metal ion.
The film that 1~15 gained coating paste of embodiment blade coating to polytetrafluoroethylene (PTFE) film surface forms 1~5um thickness is applied
Layer sufficiently infiltrates LiPF6Electrolyte is assembled into LiFePO4/ graphite lithium battery tests its cyclicity using electrochemical workstation
Can, test result is shown in Table 1.
1 test result of table
By the test data of table 1 it is found that with without adsorbable metal ion adhesive solution coating paste (comparative example
1) compare, lithium battery diaphragm of the invention with coating paste (embodiment 1~15) be coated on diaphragm and be used for battery when, have compared with
High capacity retention ratio, that is to say, that lithium battery diaphragm coating paste of the invention can improve the cycle performance of battery, this is
Because slurry of the invention has adsorption function to metal ion, further reaction can occur with the metal ion of dissolution, subtract
The metal ion dissolved out less cathode deposition, and then reduce SEI film stability, guarantee battery use safely for a long time.
According to the disclosure and teachings of the above specification, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula is changed and is modified.Therefore, the invention is not limited to above-mentioned specific embodiment, all those skilled in the art exist
Made any conspicuous improvement, replacement or modification all belong to the scope of protection of the present invention on the basis of the present invention.This
Outside, although using some specific terms in this specification, these terms are merely for convenience of description, not to the present invention
Constitute any restrictions.
Claims (10)
1. a kind of lithium battery diaphragm coating paste, it is characterised in that: adhesive solution including adsorbable metal ion, inorganic
Oxide, thickener and dispersing agent；The adhesive solution of the adsorbable metal ion is by utilizing ultraviolet light cross-linking agent will
It is obtained on the strand that metal ion chelation agent is grafted to bonding agent under the action of ultraviolet light.
2. lithium battery diaphragm coating paste according to claim 1, it is characterised in that: the adsorbable metal ion
Adhesive solution, the inorganic oxide, the thickener and the dispersing agent mass ratio be 100:(5~10): (1~
10): (0.05~0.1).
3. lithium battery diaphragm coating paste according to claim 1, it is characterised in that: the bonding agent is styrene-
Butadiene polymer, Kynoar, Kynoar-hexafluoropropene, polyacrylic acid, polymethylacrylic acid, polyacrylate,
Polymethyl methacrylate, polyacrylonitrile, sodium carboxymethylcellulose, butadiene-acrylonitrile polymer, polyvinylpyrrolidone,
Polyacrylic acid-at least one of styrene and dimethyl siloxane.
4. lithium battery diaphragm coating paste according to claim 1, it is characterised in that: the metal ion chelation agent is
Any one in hydroxyethylethylene diamine tri-acetic acid, ethylenediamine tetra-acetic acid and aminotriacetic acid.
5. lithium battery diaphragm coating paste according to claim 1, it is characterised in that: the ultraviolet light cross-linking agent is two
Benzophenone or benzyl phenyl ketone.
6. lithium battery diaphragm coating paste according to claim 1, it is characterised in that: the inorganic oxide is oxidation
Calcium, zinc oxide, magnesia, titanium dioxide, silica, zirconium dioxide, stannic oxide, ceria, aluminum oxide and vigorous
At least one of nurse stone.
7. lithium battery diaphragm coating paste according to claim 1, it is characterised in that: the thickener is that carboxymethyl is fine
Tie up plain sodium or POLYPROPYLENE GLYCOL.
8. lithium battery diaphragm coating paste according to claim 1, it is characterised in that: the dispersing agent is poly- second two
Any one in alcohol, polyvinylpyrrolidone and polyacrylamide.
9. a kind of preparation method of lithium battery diaphragm coating paste according to any one of claims 1 to 8, which is characterized in that
Including following preparation method:
S1, bonding agent and deionized water are pressed (1~2): 9 mass ratio disperses, and obtains bonding agent aqueous dispersions；
S2, the bonding agent aqueous dispersions that metal ion chelation agent, ultraviolet light cross-linking agent and step S1 are obtained press (0.2~0.8):
(0.5~1): 100 mass ratio mixing stirs evenly that obtain bonding agent, metal-chelator, the mixing of ultraviolet light cross-linking agent molten
Liquid；
The step S2 mixed solution obtained is added in ultraviolet reactor by S3, carries out ultraviolet light in the atmosphere of protection gas
Irradiation, obtains the adhesive solution of adsorbable metal ion；
S4 is dispersed inorganic oxide and deionized water by the mass ratio of 1:9, is adjusted pH, is obtained uniform inorganic oxide
Object dispersion liquid；
S5, the inorganic oxide dispersion liquid that the adhesive solution of the step S3 adsorbable metal ion obtained, step S4 are obtained,
Dispersing agent and thickener press 100:(50~100): (1~10): the mass ratio mixing of (0.05~0.1) obtains adsorbable metal
The lithium ion battery separator coating paste of ion.
10. a kind of lithium battery diaphragm, it is characterised in that: it is 1~5um's that an at least surface for the diaphragm, which is coated with a layer thickness,
Lithium battery diaphragm coating paste as described in claim 1~8.
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Application publication date: 20190607 |