A kind of ceramic-coated separator and preparation method thereof and the application in lithium ion battery
Technical field
The present invention relates to a kind of membrane of lithium ion battery and preparation method thereof, more particularly to a kind of ceramic diaphragm and its system
Preparation Method and the application in lithium ion battery.
Background technology
Lithium ion battery has the advantages that energy density height, long lifespan, power density are big and small, is widely used in
The portable electric appts such as laptop, digital camera, mobile phone, at the same also large-scale application in electric automobile and large-scale
Energy-storage system.But there are the security risk such as battery short circuit, explosion, on fire in use for lithium-ion-power cell.
One of the critical material of membrane as lithium ion battery, directly affects the security and chemical property of battery.
Now widely used commercialized lithium battery diaphragm is all to utilize PE, PP and other polyolefin and their mixture or common
The characteristics of polymers is process, polyolefin is that crystallinity is high, solvent resistance is strong, surface polarity and surface energy are low, so for one
As coating attachment it is difficult, it is necessary to carry out effort in surface treatment and the aspect of modified paint two.Surface treatment can use flame, electricity
Dizzy and chemical treatment, but since membrane thicknesses are typically only several microns to tens microns, to process for treating surface and equipment requirement
It is high, and must paint at once after handling, it is unfavorable for large-scale production.And there are fusing point for this conventional membrane for polymer
The problems such as low, bad mechanical property, overcharge or thermal contraction can occur for (more than 100 DEG C) and easily by lithium branch when temperature raises
Crystalline substance pierces through, so as to cause the safety problem such as battery short circuit, on fire.Further, since the hydrophobic performance of membrane for polymer itself, causes
Its infiltration and retention to electrolyte is poor, limits the big high rate performance of battery, also have impact on lithium ion battery in electronic vapour
Application on car.
By the way that its heat endurance, shrinkage and absorbency can be effectively improved in conventional membrane surface coated ceramic coating,
So as to fulfill the purpose for improving battery security and chemical property.At present, the ceramic coating slurry of document and patent report
Mainly there is two major class of solvent-borne type and water-based system.Solvent-borne type cost of sizing agent is high, and in drying course organic solvent volatilization meeting
Cause environmental pollution.But for water-based system, since traditional lithium ion battery separator is mostly polyolefins non-polar high polymer
Material, it is poor there are wettability with water-based ceramic slurry, cause ceramic particle skewness and ceramic layer and membrane on membrane
The binding agent that matrix is only relied in ceramic coating bonds, and adhesion strength is weaker, thus the membrane is in processing, coiling electrode group and electricity
In the charge and discharge process in pond, it is also easy to produce coating granule and comes off, so as to causes the performance heterogeneities such as the resistance to thermal and electrochemical of membrane, very
To influence battery performance uniformity.This is not mainly due to having polar group, surface energy low in vistanex, for general coating
Be attached with certain difficulty.In addition, the ceramic particle used in ceramic coating is generally nanometer oxide particle, it is easily rolled into a ball
It is poly-, it is difficult in ceramic slurry dispersed.In order to improve the dispersiveness of ceramic powder and improve the cementitiousness of ceramics and membrane,
Chinese patent CN103956450 carries out " grafting " to ceramic particle using anion surfactant and is modified, but the grafting process
Condition it is harsh and cumbersome time-consuming, it is necessary to nitrogen atmosphere protection and be heated to reflux 4~6 it is small when, and be grafted after the completion of, need to centrifuge
Grafting ceramics simultaneously wash repeatedly.Chinese patent CN104466060A disclose a kind of multi-layer co-extruded coating prepare lithium ion it is compound every
The method of film, which is coated with two kinds of functional coatings, although thermal safety and the imbibition of membrane can be improved to a certain extent
Property and environmentally friendly, but do not solve fundamentally water-based bacteria cellulose slurry and aqueous ceramic slurry with it is nonpolar
Polyalkene diaphragm between wettability it is poor, coating is difficult to be evenly distributed, and two kinds of functional coatings and polyalkene diaphragm poor adhesive force
The problems such as.Therefore research fundamentally solve polyolefins basement membrane is Nian Jie with ceramic coating loosely, ceramic coating be easily peeled off it is de-
The problems such as falling has been that situation is compeled.
The content of the invention
The technical problem to be solved in the present invention is overcome the deficiencies of the prior art and provide one kind to improve existing water-based body
Be slurry coating ceramic coating easily come off, the ceramic-coated separator of dusting problems and preparation method thereof.
In order to solve the above technical problems, technical solution proposed by the present invention is:
A kind of ceramic-coated separator, is symmetrical five laminate, including two outermost ceramic coatings, outer layer twice
Chloridized polyolefin coating and intermediate layer matrix membrane.
Above-mentioned ceramic-coated separator, it is preferred that the chloridized polyolefin coating is chlorinated polypropylene coating, chlorination gathers
The mixed coating of vinyl coating or chlorinated polypropylene and haloflex;Described matrix membrane is polyolefins membrane.
Above-mentioned ceramic-coated separator, it is preferred that the polyolefins membrane is PP membranes, PE membranes or PP/PE are compound
Membrane.
Above-mentioned ceramic-coated separator, it is preferred that the thickness of the ceramic coating is 3~15 μm.
The present invention provides a kind of preparation method of above-mentioned ceramic-coated separator, comprises the following steps:
1) 20~40 parts by weight Nano Ceramic Particles are taken, are added in the ethanol and hydrochloric acid solution of pH=3~5, stirring 1~2
Hour, it is then centrifuged for separating, obtains the Nano Ceramic Particles of modification;
2) take 10~20 parts by weight water-soluble resins to add in deionized water to stir evenly, then sequentially add 0.8~1.5
Parts per weight dispersing agent and 0.3~1.0 parts by weight defoamer, it is lasting to stir, add the nanometer of the modification of step 1) preparation
Ceramic particle, ball milling, filtering, vacuum defoamation, obtain ceramic coating slurry;
3) spraying precoating is carried out to matrix membrane using the water-soluble chlorinated polyolefin resin solution of 3wt%~15wt%
Processing, it is then dry at a temperature of 35 DEG C~55 DEG C, form one layer of chloridized polyolefin coating on two surfaces of matrix membrane;
4) chlorination of the ceramic coating slurry coated in matrix membrane prepared by step 2) is gathered using micro- gravure coating technique
On alkene coating, it is 3 μm~15 μm to control thickness of ceramic coating;Coating obtains described after 40 DEG C~55 DEG C drying, winding
Ceramic-coated separator finished product.
Above-mentioned preparation method, it is preferred that in the step 1), Nano Ceramic Particles are nano aluminium oxide, nano-silica
Change one or several kinds of mixtures in titanium, nano zircite, nano-sized iron oxide and nano zine oxide;Nano Ceramic Particles
Particle size is 0.3~1.0 μm.
Above-mentioned preparation method, it is preferred that in the step 2), water-soluble resin is aqueous polyacrylamide acid resin, water-based
One in maleic anhydride modified polyacrylic resin, waterborne polyurethane resin, water-based polystyrene resin and aqueous epoxy resins
Kind is several;Dispersant for amino-organosilanes, carboxyl organosilan, polyvalent alcohol, phenylbenzimidazole sulfonic acid salt, alkyl quaternary ammonium salts,
One or several kinds in alkyl quaternary alkylphosphonium salt and its derivative;Defoamer for polysiloxanes, acrylate copolymer, titanate esters,
One or several kinds in rare-earth coupling agent, soap salt.
Above-mentioned preparation method, it is preferred that in the step 2), when the time of ball milling is 0.5~2 small, the speed of ball milling
For 800~4000rpm/min.
Above-mentioned preparation method, it is preferred that in the step 3), the coated weight of water-soluble chlorinated polyolefin resin solution is
5~50g of water-soluble chlorinated polyolefin resin solution is coated on every square metre of matrix membrane.
The present invention also provides a kind of application of above-mentioned ceramic-coated separator in lithium ion battery.
Compared with prior art, the advantage of the invention is that:
1) ceramic-coated separator of the invention by ceramic coating/chlorinated polyolefin hydrocarbon layers/matrix membrane/chlorinated polyolefin hydrocarbon layers/
The five-layer structure of ceramic coating composition, wherein chlorinated polyolefin hydrocarbon layers play the role of one " forming a connecting link ", since chlorination gathers
Olefin layer carries substantial amounts of polar group-Cl, can not only improve the adhesion strength of base material membrane and ceramic coating, but also chlorination
Polyolefin and polypropylene and polyethylene etc. have similar crystal structure and size, thus have good cohere to base material membrane
Performance, so that cohesive force between raising ceramic coating and base material membrane, plays the role of being difficult to coming off, not dry linting.
2) ceramic-coated separator of the invention by ceramic coating/chlorinated polyolefin hydrocarbon layers/matrix membrane/chlorinated polyolefin hydrocarbon layers/
The five-layer structure of ceramic coating composition, wherein chlorinated polyolefin hydrocarbon layers are due to that containing Cl elements, can play certain fire retardation.
3) Nano Ceramic Particles are carried on a small quantity just through weak acid pretreatment rear surface compensation in preparation method of the invention
Electric charge, due to the like charges effect of repelling each other, thus can effectively prevent Nano Ceramic Particles reunion, playing raising, it is dispersed
Effect.
4) Nano Ceramic Particles are carried on a small quantity by weak acid pretreatment rear surface compensation in the preparation method of the present invention
There is chelating and charge effect between carboxyl, amino and epoxide group in positive charge, with water-soluble resin, can not only promote
Disperseing for modified Nano ceramic particle, also improves the adhesive property of nano ceramic coat.
5) lithium ion battery made of ceramic-coated separator of the invention has extended cycle life, by 200 cycle performances
After test, battery capacity conservation rate is still up to more than 97%.
Brief description of the drawings
Fig. 1 is the structure diagram of the ceramic-coated separator of the present invention.
Fig. 2 is the scanning electron microscopic picture of common PP membranes.
Fig. 3 is the scanning electron microscopic picture of ceramic-coated separator prepared by the embodiment of the present invention 1.
Battery prepared by the ceramic-coated separator and common PP membranes that Fig. 4 is prepared for the embodiment of the present invention 1 is under 3C multiplying powers
Cycle life compare figure.
Marginal data:
1st, ceramic coating;2nd, chloridized polyolefin coating;3rd, matrix membrane.
Embodiment
For the ease of understanding the present invention, the present invention is made below in conjunction with Figure of description and preferred embodiment more complete
Face, meticulously describe, but protection scope of the present invention is not limited to embodiment in detail below.
Unless otherwise defined, all technical terms used hereinafter and the normally understood implication of those skilled in the art
It is identical.Technical term used herein is intended merely to the purpose of description specific embodiment, is not intended to the limitation present invention
Protection domain.
Except there is a special instruction, the various reagents used in the present invention, raw material be can be commercially commodity or
Person can pass through product made from known method.
Embodiment 1:
A kind of ceramic-coated separator, as shown in Figure 1, be symmetrical five laminate, including two outermost ceramics apply
Layer 1, twice the chlorinated polypropylene coating 2 of outer layer and the matrix membrane 3 in intermediate layer;Matrix membrane 3 is PP membranes;Ceramic coating 1
Thickness be 10 μm.
The preparation method of above-mentioned ceramic-coated separator, including operating procedure in detail below:
1) nano alumina particles that 30g particle sizes are 500nm are added to the ethanol and mixed in hydrochloric acid of 150g pH=4
In solution, when stirring 1 is small, it is then centrifuged for separating, obtains the nano alumina particles of modification.
2) the water-soluble maleic anhydride modified polyacrylic resins (solid content 40%) of 20g are taken, 50g deionized waters is added and stirs
Mix uniformly, then sequentially add 0.8g amino-organosilanes and 0.5g acrylate copolymers, lasting stirring, then adds 30g
By the nano alumina particles of modification, using 2000rpm/min speed ball milling 2 it is small when, then filtering, vacuum defoamation,
It can obtain ceramic coating slurry.
3) surface spraying precoating processing is carried out to PP membranes using the water-soluble chlorinated polypropylene solution of 10wt%
(dosage is that the membrane coated weight of unit square metre area is 15g), is then dried with 40 DEG C of hot-airs.
4) the ceramic coating slurry dual coating that step 2) is prepared is being passed through by step 3) place using micro- gravure coating technique
On the PP membranes managed, it is 10 μm to control thickness of ceramic coating;After coating 55 DEG C drying, winding, you can obtain ceramic coating every
Film finished product.
The material property of ceramic-coated separator manufactured in the present embodiment and common PP membranes is tested, as a result such as table 1.From table 1
In as can be seen that ceramic-coated separator manufactured in the present embodiment heat resistance and being folded without breaking intensity obviously higher than common PP
Membrane, its horizontal and vertical hot audience ratings of baking 30min is respectively less than 5% at a high temperature of 140 DEG C, illustrates the ceramic-coated separator
With good high high-temp stability.From table 1 it can also be seen that ceramic-coated separator manufactured in the present embodiment air permeability and
Internal resistance is consistent substantially with common PP membranes.
The comparison of 1 ceramic-coated separator of table and the material property of common PP membranes
Common PP membranes and ceramic-coated separator manufactured in the present embodiment are done into scanning electron microscope respectively, its stereoscan photograph
Respectively as shown in Fig. 2 and Fig. 3.As can be seen that the table of ceramic-coated separator manufactured in the present embodiment from the comparison of Fig. 2 and Fig. 3
Face is smooth, and nano alumina particles are evenly distributed, and is formd between nano alumina particles than more uniform gap structure, carries
The high heat-shrinkable of ceramic-coated separator.
Positive plate is prepared by positive electrode of LiFePO4, Delanium is that negative material prepares negative plate, respectively will this
Ceramic-coated separator and common PP membranes prepared by embodiment is wound with positive and negative electrode pole piece, is added electrolyte, is assembled into
Lithium ion battery, and its relevant chemical property is tested respectively.As shown in figure 4, it is ceramics manufactured in the present embodiment
The cycle life of battery prepared by coated separator and common PP membranes under 3C multiplying powers compares figure.Figure 4, it is seen that passing through
Cross after 100 circulations, battery capacity circulation conservation rate and the ceramic-coated separator system of the present embodiment prepared by common PP membranes
Standby battery capacity circulation conservation rate is not much different.But after 200 circulations, the battery prepared with common PP membranes holds
The conservation rate of amount is 88.74%;And the present embodiment membrane coated separator prepare battery through capacity retention ratio still 97% with
On.It can be seen from the above that nano aluminium oxide ceramic-coated separator manufactured in the present embodiment will to the guarantor's fluidity and wettability of electrolyte
Higher than common PP membranes.In addition, the chlorinated polypropylene coating of ceramic-coated separator manufactured in the present embodiment and answering for nano ceramics
Conjunction sandwich construction improves the interface stability between membrane and positive and negative electrode, so as to improve the cycle life of battery.
Embodiment 2:
A kind of ceramic-coated separator, as shown in Figure 1, be symmetrical five laminate, including two outermost ceramics apply
Layer 1, twice the chlorinated polyethylene ene coatings 2 of outer layer and the matrix membrane 3 in intermediate layer;Matrix membrane 3 is PE membranes;Ceramic coating 1
Thickness be 5 μm.
The preparation method of above-mentioned ceramic-coated separator, including operating procedure in detail below:
1) nano alumina particles that 35g particle sizes are 500nm are taken to add the ethanol and mixed in hydrochloric acid of 140g pH=3
In solution, when stirring 1.5 is small, it is then centrifuged for separating, obtains the nano alumina particles of modification.
2) 20g water-soluble polypropylenes acid resin (solid content 35%) is taken, 35g deionized waters is added and stirs evenly, then
1.2g polyvalent alcohols and 0.8g polysiloxanes are sequentially added, lasting stirring, then adds nano oxygens of the 35g Jing Guo modification
Change aluminum particulate, using 3000rpm/min speed ball milling 2 it is small when, then filtering, vacuum defoamation, you can obtain ceramic coating slurry.
3) surface spraying precoating processing is carried out to PP membranes using the water-soluble chlorinated polyethylene resin solution of 8wt%
(dosage is that the membrane coated weight of unit square metre area is 20g), is then dried with 35 DEG C of hot-airs.
4) the slurry dual coating that step 2) is prepared is being passed through by the processed PP of step 3) using micro- gravure coating technique
On membrane, it is 5 μm to control coating layer thickness;50 DEG C of drying, winding after coating, you can obtain ceramic-coated separator finished product.
The ceramic-coated separator of the present embodiment is assembled into battery together with battery positive and negative plate, measures its service life, is passed through
After 200 cycle performance tests, the conservation rate of battery capacity is still up to 97%.
Embodiment 3:
A kind of ceramic-coated separator, as shown in Figure 1, be symmetrical five laminate, including two outermost ceramics apply
Layer 1, twice the chlorinated polypropylene coating 2 of outer layer and the matrix membrane 3 in intermediate layer;Matrix membrane 3 is PP membranes;Ceramic coating 1
Thickness be 8 μm.
The preparation method of above-mentioned ceramic-coated separator, including operating procedure in detail below:
1) the nano oxidized iron particle that 40g particle sizes are 400nm is added to the ethanol and mixed in hydrochloric acid of 160g pH=3
In solution, when stirring 2 is small, it is then centrifuged for separating, obtains the nano oxidized iron particle of modification.
2) 30g water soluble polyurethane resins (solid content 35%) are taken, 30g deionized waters is added and stirs evenly, Ran Houyi
Secondary addition 1.2g alkyl quaternary ammonium salts and 0.8g rare-earth coupling agents, lasting stirring, then adds nano oxygens of the 40g Jing Guo modification
Change iron particle, using 2500rpm/min speed ball milling 1 it is small when, then filter, vacuum defoamation, you can obtain ceramic coating slurry.
3) surface spraying precoating processing is carried out to PP membranes using the water-soluble chlorinated polypropylene solution of 9wt%
(dosage is that the membrane coated weight of unit square metre area is 18g), is then dried with 40 DEG C of hot-airs.
4) the ceramic coating slurry dual coating that step 2) is prepared is being passed through by step 3) place using micro- gravure coating technique
On the polypropylene diaphragm managed, it is 8 μm to control coating layer thickness;55 DEG C of drying, winding after coating, you can obtain ceramic-coated separator
Finished product.
The ceramic-coated separator of the present embodiment is assembled into battery together with battery positive and negative plate, measures its service life, is passed through
After 200 cycle performance tests, the conservation rate of battery capacity is still up to 97%.
Embodiment 4:
A kind of ceramic-coated separator, as shown in Figure 1, be symmetrical five laminate, including two outermost ceramics apply
Layer 1, twice the chlorinated polyethylene ene coatings 2 of outer layer and the matrix membrane 3 in intermediate layer;Matrix membrane 3 is PE membranes;Ceramic coating 1
Thickness be 10 μm.
The preparation method of above-mentioned ceramic-coated separator, including operating procedure in detail below:
1) nano zirconia particles that 25g particle sizes are 800nm are added to the ethanol and mixed in hydrochloric acid of 100g pH=4
In solution, when stirring 2 is small, it is then centrifuged for separating, obtains the nano zirconia particles of modification.
2) 30g water-soluble polies styrene resin (solid content 35%) is taken, 45g deionized waters is added and stirs evenly, then
1.0g phenylbenzimidazole sulfonic acids salt and 0.8g soap salt are sequentially added, lasting stirring, then adds nano zircites of the 25g Jing Guo modification
Particle, using 3000rpm/min speed ball milling 1 it is small when, then filtering, vacuum defoamation, you can obtain ceramic coating slurry.
3) PE membranes are carried out at surface spraying precoating using the water-soluble chlorinated polyethylene resin solution of 10wt%
Manage (dosage is that the membrane coated weight of unit square metre area is 15g), then dried with 40 DEG C of hot-airs.
4) the slurry dual coating that step 2) is prepared is being passed through by the processed PE of step 3) using micro- gravure coating technique
On membrane, it is 10 μm to control coating layer thickness;45 DEG C of heat drying, windings after coating, you can obtain ceramic-coated separator finished product.
The ceramic-coated separator of the present embodiment is assembled into battery together with battery positive and negative plate, measures its service life, is passed through
After 200 cycle performance tests, the conservation rate of battery capacity is still up to 97%.