CN104861847B - Aqueous coating material of organo-mineral complexing and preparation method thereof - Google Patents
Aqueous coating material of organo-mineral complexing and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to aqueous coating material of a kind of organo-mineral complexing and preparation method thereof, the composition and weight/mass percentage composition of the coating material are：Inorganic nano-particle aqueous liquid dispersion 10~60%, cellulose aquagel dispersion liquid 2~30%, surfactant 0.2~4%, deionized water surplus；Cellulose base hydrogel prepared by the present invention has heat endurance good, has preferable bond effect under low-solid content, and solid content can reach more than 10cp in its viscosity less than 10% time；Bonded firmly with substrate polyolefin film with the aqueous coating of above-mentioned cellulose base hydrogel and inorganic nanoparticles after compound, be conducive to barrier film large-scale production, and improve the performances such as the heat endurance, mechanical property, wetability of barrier film；Traditional organic solvent system is instead of, the characteristics of with safety and environmental friendliness.The present invention is to significant in terms of raising lithium ion battery separator battery safety, mechanical performance and chemical property.
Description
Technical field
The present invention relates to aqueous coating material of a kind of organo-mineral complexing and preparation method thereof.
Background technology
Microporous membrane is widely used, under the conditions of with certain porosity, good mechanical properties etc. can as lithium from
Sub- battery diaphragm.Barrier film is its important composition part, plays a part of isolation both positive and negative polarity, allows lithium ion by lithium ion
The security of battery is most important.
The diaphragm material of lithium ion battery is largely to have TPO now, and such as polyethylene, polypropylene or both are combined
Material etc., they have preferable distribution of pores, mechanical performance, chemical-resistance.But there is heat endurance in polyolefine material
The shortcomings of difference, electrolyte wetability are poor, in order to further improve lithium ion battery security performance and chemical property, it is necessary to
Further improve heat endurance, mechanical performance and the lyophily of barrier film.
The present invention prepares a kind of novel cellulose based aquagel dispersion, and this and inorganic nanoparticles are combined into system
For the aqueous coating material for going out a kind of organo-mineral complexing, with the aqueous coating material modified micropore film of this organo-mineral complexing
Afterwards, the thermal stability and mechanical performance of substrate microporous membrane are enhanced, has to the security of lithium ion battery and significantly carries
It is high.
The present invention compared with prior art, with substantive distinguishing features prominent as follows and marked improvement：First, present invention system
Standby cellulose base hydrogel has heat endurance good, has preferable bond effect under low-solid content；Secondly as cellulose
Based aquagel has good water retention, and this is conducive to improving holding effect of the barrier film to electrolyte；3rd, increase substantially
The heat endurance and mechanical strength of substrate microporous membrane；4th, with this cellulose base hydrogel dispersion and inorganic nano
Aqueous coating and substrate film bonding after grain is compound is firm, is conducive to barrier film large-scale production, and it is steady to improve the heat of barrier film
Qualitative, mechanical property, wetability and ionic conductivity；Finally, the gel of preparation be aqueous phase system, instead of traditional modification every
The organic solvent systems such as PVDF or PVDF-HFP that film is used, the characteristics of with safety and environmental friendliness.The present invention is to improving
It is significant in terms of lithium ion battery separator battery safety, chemical property and service life.
The content of the invention
One of the object of the invention is to provide a kind of organo-mineral complexing aqueous coating material, and this coating material is used
A kind of hydrogel dispersion of cellulose base, the gel dispersion system instead of traditional organic phase system, with low-solid content
The characteristics of high bond effect, make the production of battery more environmentally friendly.
The second object of the present invention is the preparation method for providing the coating material.
To achieve the above object, present invention synthetic cellulose based aquagel first, then by cellulose base hydrogel and nothing
Machine nano-particles reinforcement, synthetic cellulose based aquagel, first by cellulose be initially dissolved in acetone, butanone, 2- butanone one
Plant or two or more mixtures, wherein cellulose is NC Nitroncellulose, single cellulose acetate, cellulose diacetate or three
One kind in cellulose acetate, molecular weight cellulose is that hydroxyl accounts for mass percent for 3%-10% in 5000-50000, cellulose,
Acetyl group weight/mass percentage composition 75-82%, the mol ratio of cellulose and organic many isocyanide esters is 1-5, and cellulose is anti-with prepolymer
It is 65-85 DEG C to answer temperature, and the reaction time is 1-2.5 hours；
Above-mentioned cellulose organic solution and isocyanide ester functional prepolymer are subjected to graft reaction, wherein cellulose with it is organic
The mol ratio of many isocyanide esters is 1-5, and reaction temperature is 65-85 DEG C, and the reaction time is 1-2.5 hours, and catalysts are two
One kind in butyl tin dilaurate, dibutyl tin dilaurate；Reaction adds triethylamine after terminating or ethylenediamine is carried out
Neutralize, degree of neutralization is 0.8-1.0；Then deionized water emulsification is added, vacuum distillation steams organic solvent formation cellulose aqueous
Gel aqueous dispersion liquid.
The present invention one kind be used for the aqueous coating material of organo-mineral complexing, it is characterised in that the composition of the coating material and
Weight/mass percentage composition is：
Inorganic nano-particle aqueous liquid dispersion 10~60%
Cellulose aquagel dispersion liquid 2~30%
Surfactant 0.2~4%
Deionized water surplus；
Described cellulose aquagel dispersion liquid is cellulose organic solution and isocyanide ester functional prepolymer in the aqueous solution
Three-dimensional reticular fiber hydrogel dispersion, the grafting rate of the polymer formed formed by middle carry out graft polymerization reaction
For 10~50%, its solid content is：2~10%；Described isocyanide ester functional prepolymer is by hydrophilic chain extender and organic polyisocyanate
The isocyanide ester functional prepolymer that nitrile acid esters is obtained through prepolymerization.
Above-mentioned cellulose aquagel average particle size particle size is in 50~800nm.
Above-mentioned cellulose is NC Nitroncellulose, single cellulose acetate, cellulose diacetate or Triafol T, fiber
The plain equal relative molecular weight of weight is 5000~50000, and it is 3%~10%, acetyl group quality hundred that hydroxyl, which accounts for mass percent, in cellulose
Divide content 75~82%.
Above-mentioned organic many isocyanide esters are：IPDI, toluene di-isocyanate(TDI), diphenyl methane two
One kind in isocyanates, methyl diphenylene diisocyanate and hexamethylene diisocyanate.
The solid content of above-mentioned inorganic nano-particle aqueous liquid dispersion is 10~60%, and inorganic nano-particle therein is：Two
In silicon oxide particle, alundum (Al2O3) particle, TiO 2 particles, zirconium dioxide particle, Ti -Si zeolite, Si-Al molecular sieve
At least one, particle diameter is 50~100nm.
Above-mentioned surfactant is polyvinylpyrrolidone PVP, polyethylene glycol, PEO-PPOX-poly-
At least one of oxirane triblock copolymer P123, polyethers F127, polysorbate, sldium lauryl sulfate.
Above-mentioned hydrophilic chain extender is dihydromethyl propionic acid, diaminobenzoic acid, 1,4- butanediol -2- sodium sulfonates or poly- second
Glycol.
A kind of method for preparing the aqueous coating material of above-mentioned organo-mineral complexing, it is characterised in that the specific step of this method
Suddenly it is：
A. organic many isonitrile esters of gallic acid and hydrophilic chain extender are pressed 1：（0.2~0.8）Mixed in molar ratio after, 45~65
Prepolymerization is carried out at a temperature of DEG C, the pre-polymerization time is 0.5~1.5 hour, obtains isocyanide ester functional prepolymer；
B. isocyanide ester functional prepolymer obtained by the acetone or butanone solution of cellulose and step a is subjected to graft reaction,
The mol ratio of wherein cellulose and isocyanide ester functional prepolymer is 1：（1~5）, reaction temperature is 65~85 DEG C, reaction time
For 1~2.5 hour, catalysts were dibutyltin dilaurate or dibutyl tin dilaurate；Reaction is added after terminating
Triethylamine or ethylenediamine are neutralized, degree of neutralization（Degree of neutralization refers to that the degree neutralization reactions here that neutralization reaction is carried out are carboxylics
The neutralization of base and amino, degree of neutralization 0.8 refers to that amino reacts away 80% carboxyl）For 0.8-1.0；Then deionized water is added
Emulsification, vacuum distillation steams organic solvent formation cellulose aquagel dispersion liquid；
C. inorganic nano-particle is disperseed to be configured to inorganic nano-particle aqueous liquid dispersion in deionized water；
D. inorganic nano-particle aqueous liquid dispersion, rapid b gained cellulose aquagels dispersion liquid, surface obtained by step c are lived
Property agent, deionized water is well mixed forms the aqueous coating material of organo-mineral complexing.
The aqueous coating material of the organo-mineral complexing of the present invention is applied using dip coating, rolling method, spraying process or the tape casting
Cloth is in the one or both sides of microporous membrane, then at 40-70 DEG C, dries 1-10min, obtains coating modified microporous barrier, its
One-sided coatings thickness is 1-4 μm；Microporous membrane used is that cellophane, non-woven fabrics, polyethylene porous film, polypropylene are more
Hole film, polypropylene, polyethylene/polypropylene composite materials porous membrane.
The present invention compared with prior art, with substantive distinguishing features prominent as follows and marked improvement：
1st, cellulose base hydrogel prepared by the present invention has heat endurance good, has under low-solid content and preferably bonds effect
Really, solid content can reach more than 10cp in its viscosity less than 10% time；
2nd, the aqueous coating and substrate polyolefin film with above-mentioned cellulose base hydrogel and inorganic nanoparticles after compound
Bonding is firm, is conducive to barrier film large-scale production, and improve the performances such as the heat endurance, mechanical property, wetability of barrier film；
3rd, the cellulose base hydrogel prepared is aqueous phase system, traditional organic solvent system is instead of, with safe, green
The characteristics of color, environmental protection.The present invention is to improving lithium ion battery separator battery safety, mechanical performance and chemical property etc.
Aspect is significant.
Embodiment
The present invention is further illustrated with reference to embodiments.
The wherein involved for example organic polyisocyanate nitrile acid esters of the medicine for preparing cellulose base hydrogel dispersion, hydrophilic chain extension
Agent, NC Nitroncellulose, single cellulose acetate, cellulose diacetate or Triafol T are adopted to such as Aladdin, Sigma, lark
Wei Deng Reagent Companies.
Wherein described surfactant is polyvinylpyrrolidone PVP, polyethylene glycol, PEO-polycyclic oxygen third
At least one of alkane-PEO triblock copolymer P123, polyethers F127, polysorbate, sldium lauryl sulfate adopt to
Such as Aladdin, Sigma, lark prestige Reagent Company.
Wherein involved inorganic nanoparticles aqueous liquid dispersion such as titanium dioxide TiO2, silica SiO2, three oxidations
Two aluminium Al2O3, zirconium dioxide ZrO2 colloidal sols use commercial prod.Such as ashland Nyacol Nanotec Solution of the U.S.
ZrO2 dispersion liquids, the SiO2 dispersion liquids of Shanghai Chemical Co., Ltd. of Hang Seng, the limited public affairs of this promise New Chemical Material of Dalian science and technology
The Al2O3 dispersion liquids of department, the TiO of Wuhan Hong Xinkang Fine Chemical Co., Ltd2Dispersion liquid.
Wherein involved Ti -Si zeolite is according to document Preparation of Colloidal Suspensions of
Discrete TS-1 Crystal. Chemistry of materials, 1997, 9(1):It 210-217. is made.
Wherein involved Si-Al molecular sieve is according to document Comparing synthesis routes to nano-
crystalline zeolite ZSM-5. Microporous and mesoporous materials, 2003, 57(1):
83-92. is made.
Individually below by cellulose base hydrogel dispersion prepare with aqueous organo-mineral complexing coating example 1-5 come
Illustrate：
Embodiment 1
The cellulose base hydrogel dispersion of the modification lithium-ion battery barrier film of the present embodiment, includes following raw material：
IPDI 5g, dihydromethyl propionic acid 1.21g, NC Nitroncellulose 2g is dissolved in 65g acetone, dibutyl tin
Cinnamic acid tin catalyst 0.02g, deionized water 60g, diethylamino 0.8g,
The specific solution of the modification lithium-ion battery barrier film cellulose base hydrogel dispersion of this example includes
Following steps：
1) take 5g IPDIs as in the solution for having dissolved 1.21g dihydromethyl propionic acids, be warming up to 45
DEG C, it is uniformly mixed, prepolymerization time is 30 minutes, prepolymerization temperature is 45 DEG C,
2）Then 2g NC Nitroncelluloses are dissolved in 65g acetone soln, add dibutyl tin dilaurate 0.02g and mix
Close, then the mixed solution of cellulose and catalyst added into reaction 1.5 hours in prepolymer,
3）After the completion of question response, room temperature is cooled to, diethylamino quality is first added and is sufficiently mixed for 0.8g, add deionization
Water quality 60g is emulsified, and vacuum distillation obtains hydrogel dispersion C1,
Modified microporous membrane is prepared with following material in the present embodiment：
The cellulose aquagel dispersion C1 15% of above-mentioned preparation
Aqueous silica dispersion liquid 50%
Surfactant is PVP 0.2%
Deionized water 34.8%
Substrate film is polyethylene film,
Coating method is dip-coating method, and preparation process is as follows：By cellulose aquagel dispersion C1 deionized waters
Solid content 3.75% is diluted to, substrate film is immersed in the different aqueous gel dispersion liquids of four kinds of the above 2 minutes, is combined
Film, is put into 70 DEG C of oven dryings 10 minutes.Film longitudinal phase tensile strength 120.3MPa is measured than original substrate PE films
100MPa adds more than 14%, is about 5% in 150 DEG C of lower diaphragm plate shrinkage factors, and pure PE films are 94%.
Embodiment 2
The cellulose base hydrogel dispersion of the present embodiment, includes the raw material of following weight：Toluene di-isocyanate(TDI) 5g,
Diaminobenzoic acid 2.41g, single cellulose acetate 2g are dissolved in 70g acetone, dibutyl tin dilaurate catalyst 0.02g,
Deionized water 60g, diethylamino 0.8g
The specific solution of the modification lithium-ion battery barrier film cellulose base hydrogel dispersion of this example includes
Following steps：
1) take 5g toluene di-isocyanate(TDI)s as in the solution for having dissolved 2.41g diaminobenzoic acids, be warming up to 45 DEG C,
It is uniformly mixed, prepolymerization time is 30 minutes, prepolymerization temperature is 45 DEG C,
2）The mono- cellulose acetates of 2g are dissolved in 70g acetone soln, add dibutyl tin dilaurate 0.02g mixing,
The mixed solution of cellulose and catalyst is added in prepolymer again and reacted 1.5 hours,
3）After the completion of question response, room temperature is cooled to, diethylamino 0.8g is first added and is sufficiently mixed, add deionized water quality
60g is emulsified, and vacuum distillation obtains hydrogel dispersion C2
The microporous membrane that this example is modified is prepared with following material：
The cellulose aquagel dispersion C2 10% of above-mentioned preparation
Aluminum oxide nanoparticles aqueous liquid dispersion 50%
Surfactant is P123 0.5%
Deionized water 39.5%
Substrate film is PET film,
Coating method is dip-coating method, and preparation process is as follows：First cellulose aquagel dispersion C2 and three is aoxidized
Two aluminum nanoparticles aqueous liquid dispersions and deionized water are mixed 1 hour, and substrate film is immersed in into coating after being uniformly dispersed
2 minutes in liquid, then lifting obtains laminated film, is put into 70 DEG C of oven dryings 10 minutes.Measure film longitudinal phase tensile strength
210.3MPa, does not shrink substantially in 150 DEG C of lower diaphragm plates.
Embodiment 3
The cellulose base hydrogel dispersion of the present embodiment, includes the raw material of following weight：The isocyanide of diphenyl methane two
Acid esters 5g, BDO -2- sodium sulfonate 1.53g, cellulose diacetate 2g are dissolved in 70g butanone, dibutyl tin cinnamic acid
Tin catalyst 0.02g, deionized water 60g, diethylamino 0.8g
The specific solution of the modification lithium-ion battery barrier film cellulose base hydrogel dispersion of this example includes
Following steps：
1) 5g methyl diphenylene diisocyanates are taken as the solution for having dissolved 1.53g1,4- butanediol -2- sodium sulfonates
In, 45 DEG C are warming up to, is uniformly mixed, after being well mixed, in 45 DEG C of prepolymerizations 30 minutes,
2）2g cellulose diacetates are dissolved in 70g butanone solution, add dibutyl tin dilaurate 0.02g mixing,
The mixed solution of cellulose and catalyst is added in prepolymer again and reacted 1.5 hours
3）After the completion of question response, room temperature is cooled to, diethylamino quality is first added and is sufficiently mixed for 0.8g, add deionization
Water quality 60g is emulsified, and vacuum distillation obtains hydrogel dispersion C3
Modified microporous membrane is prepared with following material in the present embodiment：
The cellulose aquagel dispersion C3 10% of above-mentioned preparation
Titania nanoparticles aqueous liquid dispersion 50%
Surfactant is polyethylene glycol 4%
Deionized water 36%
Substrate film is non-woven fabrics,
Coating method is dip-coating method, and preparation process is as follows：First by cellulose aquagel dispersion C3 and titanium dioxide
Titanium nano particle aqueous liquid dispersion and deionized water are mixed 1 hour, and substrate film is immersed in into coating fluid after being uniformly dispersed
In 2 minutes, then lifting obtains laminated film, is put into 70 DEG C of oven dryings 5 minutes.Measure film basic in 150 DEG C of lower diaphragm plates
Do not shrink.
Embodiment 4
The cellulose base hydrogel dispersion of the present embodiment, includes the raw material of following weight：Cyclohexyl isocyanate 5g,
Polyethylene glycol 1.21g, Triafol T 2g is dissolved in 70g butanone, dibutyl tin cinnamic acid alkene catalyst 0.02g, go from
Sub- water 50g, diethylamino 0.8g
The specific solution of the modification lithium-ion battery barrier film cellulose base hydrogel dispersion of this example includes
Following steps：
1) take 5g cyclohexyl isocyanates as in the solution for having dissolved 1.21g polyethylene glycol, being warming up to 55 DEG C, stir
It is well mixed, prepolymerization 45 minutes under the conditions of 55 DEG C,
2）2g Triafol Ts are dissolved in 70g butanone solution, add dibutyl tin cinnamic acid 0.02g mixing, then
The mixed solution of cellulose and catalyst is added in prepolymer and reacted 2 hours,
3）After the completion of question response, room temperature is cooled to, diethylamino quality is first added and is sufficiently mixed for 0.8g, add deionization
Water quality 50g is emulsified, and vacuum distillation obtains dispersion C4
Modified microporous membrane is prepared with following material in the present embodiment：
The cellulose aquagel dispersion C4 30% of above-mentioned preparation
Titania nanoparticles aqueous liquid dispersion 10%
Surfactant is polyethers F127 5%
Deionized water 55%
Substrate film is polypropylene,
Coating method is dip-coating method, and preparation process is as follows：First by cellulose aquagel dispersion C4 with dioxy
Change titanium nano particle aqueous liquid dispersion and deionized water is mixed 1 hour, using lifting coating method coating after being uniformly dispersed
In polypropylene diaphragm both sides, 70 DEG C of oven dryings are placed into 5 minutes.Film longitudinal phase tensile strength 157.3MPa is measured than original
The increase of base polypropylene film is obvious, is 16.5% in 150 DEG C of lower diaphragm plate shrinkage factors, and pure PP films are 85%.
Embodiment 5
The cellulose base hydrogel dispersion of the present embodiment, includes the raw material of following weight：The isocyanic acid of hexa-methylene two
Ester 5g, dihydromethyl propionic acid 2.41g, NC Nitroncellulose 2g is dissolved in 70g acetone, dibutyl tin dilaurate catalyst
0.02g, deionized water 60g, diethylamino 0.8g
The specific solution of the modification lithium-ion battery barrier film cellulose base hydrogel dispersion of this example includes
Following steps：
1) take 5g hexamethylene diisocyanates as in the solution for having dissolved 2.41g dihydromethyl propionic acids, be warming up to 45
DEG C, it is uniformly mixed, prepolymerization time is 30 minutes, prepolymerization temperature is 45 DEG C,
2）2g NC Nitroncelluloses are dissolved in 70g acetone soln, add dibutyl tin dilaurate 0.02g mixing, then
The mixed solution of cellulose and catalyst is added in prepolymer and reacted 1.5 hours,
3）After the completion of question response, room temperature is cooled to, diethylamino 0.8g is first added and is sufficiently mixed, add deionized water quality
60g is emulsified, and vacuum distillation obtains hydrogel dispersion C5
Modified microporous membrane is prepared with following material in the present embodiment：
The cellulose aquagel dispersion C5 12.7% of above-mentioned preparation
Zirconium dioxide nanoparticles aqueous liquid dispersion 60%
Surfactant is polysorbate 0.3%
Deionized water 17%
Substrate polyethylene polypropylene polyethylene multilayer film,
Coating method is dip-coating method, and preparation process is as follows：First by cellulose aquagel dispersion C1, C2, C3, C4
In one kind mixed 1 hour with zirconium dioxide nanoparticles aqueous liquid dispersion and deionized water, in barrier film both sides using carrying
Coating method coating is drawn, 70 DEG C of oven dryings are placed into 5 minutes.Film is measured not shrink substantially in 150 DEG C of lower diaphragm plates.
Claims (4)
1. a kind of aqueous coating material of organo-mineral complexing is in the application of lithium battery diaphragm, it is characterised in that the group of the coating material
Into and weight/mass percentage composition be：
Inorganic nano-particle aqueous liquid dispersion 10~60%；
Cellulose aquagel dispersion liquid 2~30%；
Surfactant 0.2~4%；
Deionized water surplus；
The cellulose aquagel dispersion liquid is that cellulose organic solution is carried out in aqueous with isocyanate functional prepolymer's thing
Three-dimensional reticular fiber hydrogel dispersion formed by graft polymerization reaction, the grafting rate of the polymer formed for 10~
50%, its solid content is：2~10%；Described isocyanate functional prepolymer's thing is by hydrophilic chain extender and organic multiple isocyanate
The isocyanate functional prepolymer's thing obtained through prepolymerization.
2. the aqueous coating material of organo-mineral complexing according to claim 1 exists in the application of lithium battery diaphragm, its feature
It is NC Nitroncellulose, single cellulose acetate, cellulose diacetate or Triafol T in described cellulose, cellulose weight is equal
Relative molecular weight is 5000~50000, and it is 3~10%, acetyl group weight/mass percentage composition 75 that hydroxyl, which accounts for mass percent, in cellulose
~82%.
3. the aqueous coating material of organo-mineral complexing according to claim 1 exists in the application of lithium battery diaphragm, its feature
In：The solid content of inorganic nano-particle aqueous liquid dispersion is 10~60%, and inorganic nano-particle therein is：Alundum (Al2O3) grain
At least one of son, TiO 2 particles, zirconium dioxide particle, Ti -Si zeolite, Si-Al molecular sieve, particle diameter be 50~
100nm。
4. the aqueous coating material of organo-mineral complexing according to claim 1 exists in the application of lithium battery diaphragm, its feature
In surfactant be polyvinylpyrrolidone, polyethylene glycol, PEO-PPOX-PEO three block
At least one of copolymer, polyethers F127, polysorbate, sldium lauryl sulfate.
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| CN110797494B (en) * | 2019-11-08 | 2020-08-04 | 华南理工大学 | Diaphragm functional coating material for lithium ion battery and preparation method thereof |
| CN115011053B (en) * | 2022-06-21 | 2023-08-01 | 中国科学院苏州纳米技术与纳米仿生研究所 | High-reflection fractal structure hydrogel, and preparation method and application thereof |
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