CN101789499B - Coating composite for lithium ion battery separator and foam gluing method - Google Patents
Coating composite for lithium ion battery separator and foam gluing method Download PDFInfo
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- CN101789499B CN101789499B CN2010100229366A CN201010022936A CN101789499B CN 101789499 B CN101789499 B CN 101789499B CN 2010100229366 A CN2010100229366 A CN 2010100229366A CN 201010022936 A CN201010022936 A CN 201010022936A CN 101789499 B CN101789499 B CN 101789499B
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a coating composite for a lithium ion battery separator, wherein the coating composite contains porous electro-insulated oxide particles, binding agent, foaming agent or foam stabilizing agent. The invention further relates to a foam gluing method for the lithium ion battery separator, comprising the steps: mechanically foaming and the coating suspension on the surface of a porous flexible substrate, drying, curing and roll compacting to form a film with micro pores, wherein the suspension contains the coating composite according to the invention. Adopting the coating composition according to the invention and the lithium ion battery separator prepared therefrom can achieve the purpose of small pore diameter, even pore distribution and ensuring the charging and discharging uniformity of lithium ion.
Description
Technical field
The present invention relates to the coating composition that a kind of lithium ion battery separator is used, also relate to the foam gluing method of the lithium ion battery separator that uses this coating composition.
Background technology
Since Sony in 1991 was successfully the lithium ion battery commercialization, lithium ion battery had become the main power supply of mobile phone, notebook computer and digital electronic goods.New forms of energy battery technology development in recent years is very fast; Compare with traditional secondary storage batterys such as lead-acid battery, Ni-MH batteries, characteristics such as power lithium-ion battery is big with its energy density and power density, memory-less effect, self discharge is less and cycle life is long become the developing direction of vehicle mounted dynamic battery.
The lithium-ion-power cell barrier film is the important composition material of lithium ion battery, and normally thin cellular insulant material has good ion trafficability characteristic and mechanical strength, and various chemical substances and chemical solvent are had long-time stability.The non-conductive property of the electronics of barrier film can be isolated the both positive and negative polarity of battery, prevents the contact of two electrodes and short circuit; The multi-cellular structure that the while barrier film has has guaranteed that ion flow is smooth and easy.Externally battery causes the internal temperature rising because when being short-circuited the accident fault, inside battery will produce big electric current; Heat fusing will take place and close microcellular structure in barrier film this moment, thereby cut off electric current, stop battery operated; Prevent explosion accident, guarantee battery and personal safety.Therefore, barrier film is one of critical material of electrokinetic cell.
The barrier film that uses at present mainly is made up of typical organic barrier film such as polyethylene, polypropylene, three layers of composite membrane of polypropylene, polyethylene/polypropylene porous organo polysilica compound barrier film.The production method of perforated membrane mainly contains two kinds of methods: phase separation method (wet method) and stretching pore method (dry method).The former at high temperature is separated macromolecular material and solvent, forms porous membrane, as being primary raw material with the high density polyethylene (HDPE), with solvent at high temperature after the melting mixing, cooling, film forming, obtains loose structure after volatile solvent removed.Stretching pore rule is that polymer is extruded from the mould mouth, stretches with high draw ratio (draw speed/extruded velocity), obtains the sheet material after-baking, produces height-oriented sandwich construction.Further stretch then, crystalizing interface is peeled off, form loose structure.
U.S. Pat 2005084761 discloses a kind of barrier film and manufacturing approach thereof that is used for battery; This manufacturing approach comprises; Provide and have a large amount of holes and its surface and inner sheet flexible parent metal with coating; The material of wherein said base material is selected from weaving of polymer and/or natural fiber or non-woven non-conductive fiber, and said coating is the ceramic coating of porous electric insulation.A kind of porous electric insulation ceramics coating of improving in the above-mentioned United States Patent (USP) is provided among the Chinese patent CN101281961A, has improved the coating mix of lithium ion battery separator resistance to elevated temperatures.But in the manufacturing approach of above two kinds of barrier films that provide, the painting method that suspension is coated on the porous flexible substrate surface all adopts the whole bag of tricks commonly known in the art, as through printing, roll-in, the method for scraping slurry, flood, spray and lifting.
Summary of the invention
The objective of the invention is to overcome the pore-size distribution of resulting battery diaphragm in the manufacturing approach of lithium ion battery separator of above-mentioned prior art uneven defective, a kind of foam gluing method that makes barrier film that the lithium-ion-power cell membrane pore size is evenly distributed with coating composition and a kind of this barrier film is provided.
In order to achieve the above object; Technical scheme of the present invention has provided the coating composition that a kind of lithium-ion-power cell barrier film is used; It is characterized in that the weight percent proportioning is: the porous electric insulation oxide particle of the binding agent of 30-50%, 10-30%, the blowing agent of 0.5-2.0%, the foam stabiliser of 1-3% and the water of surplus.
Technical scheme of the present invention also provides a kind of foam gluing method of lithium-ion-power cell barrier film; Step is: suspension is carried out mechanical foaming; Be coated on the surface of porous flexible base material then and oven dry, bake and roll compacting after form film with micropore; It is characterized in that said suspension contains each described coating composition of claim 1-7.
The present invention adopts coating composition provided by the invention; Make the barrier film of making lithium-ion-power cell and when manufacture batteries coiling electrode group, the tack of coating on this barrier film is good, difficult drop-off; And this coating aperture with micropore is less; Even aperture distribution, thus the high resistance to elevated temperatures of this barrier film not only guaranteed, and guaranteed the uniformity that lithium ion battery discharges and recharges; Thereby make the lithium-ion-power cell that adopts this barrier film have good heat-resisting quantity and uniform charge-discharge performance, improved the useful life and the serviceability of the lithium-ion-power cell that adopts this barrier film.
Production method provided by the invention is different from the prior art suspension is coated in known painting method on the porous flexible substrate surface; As through printing, roll-in, the method for scraping slurry, flood, spray and lifting; Adopt the foam coating technology in the weaving, foam coating is to adopt the method for machinery air to be sneaked into a kind of coating new technology that makes it produce foam and put on envers in the dispersion liquid (acrylic acid ester or polyurethane).Fabric after the coating makes the water evaporation on the fabric through after baking typing, and the part air that is present in the bubble is also discharged from the coated fabric tow sides, and stays the microporous membrane that one deck interpenetrates at fabric face.This be with the foam coating technology first Application in the weaving in the lithium ion battery separator applying glue, the coating that foam gluing obtains has a large amount of micropores, and the aperture is less, even aperture distribution, thereby has guaranteed the uniformity that lithium ion battery discharges and recharges.And, adopting foam coating technology provided by the invention, production technology is simple, and is easy to make.
Description of drawings
Fig. 1 is the flow chart of the foam gluing method of a kind of lithium-ion-power cell barrier film provided by the invention.
Embodiment
The coating composition that a kind of lithium-ion-power cell barrier film is used; It is characterized in that the weight percent proportioning is: the porous electric insulation oxide particle of the binding agent of 30-50%, 10-30%, the blowing agent of 0.5-2.0%, the foam stabiliser of 1-3% and the water of surplus.
The diameter of said porous electric insulation oxide particle is the 5-1000 nanometer, is preferably the 10-50 nanometer.
Said porous electric insulation oxide particle can be various electric insulation oxide particles commonly known in the art, is preferably at least a in aluminium, zirconium, titanium and the silicon oxide particles.
Said adhesive can adopt various adhesive commonly known in the art, is preferably at least a in copolymer, oleic series resin binder or the acrylic ester binding agent of Kynoar, polytetrafluoroethylene, polyacrylic acid, polyacrylonitrile, ethylene fluoride and hexafluoroethylene.
Said blowing agent can adopt various blowing agent commonly known in the art; Be preferably various known surfactants; Sodium cetanesulfonate (AS) like anionic; Lauryl sodium sulfate (SDS), neopelex (ABS) etc., the alkylol APEO of nonionic; APES. cocounut oil acyl diethanol amine (washing agent 6501) etc., at least a in novel green surfactant APG (APG), methyl glucamine (APA), natural tea saponin, rosin polyoxyethylene ester (RPGC) and the Gemini type surfactant.
Said foam stabiliser can adopt various foam stabiliser commonly known in the art, is preferably at least a in stearic acid, sulfo-succinamide, lauryl alcohol, n-butanol, octanol and the silicone based foam stabiliser.
A kind of foam gluing method of lithium-ion-power cell barrier film; Step is: suspension is carried out mechanical foaming; Be coated on the surface of porous flexible base material then and oven dry, bake and roll compacting after form film with micropore; Its step is as shown in Figure 1, and said suspension contains coating composition provided by the invention.
Under preferred situation; For porous electric insulation oxide particle can well, be disperseed in suspension uniformly; The coating of barrier film that makes manufacturing is more equably attached on the porous flexible matrix; Said suspension also can contain dispersant, and the weight ratio of porous electric insulation oxide particle total weight is 0.001-0.05 in dispersant and the coating: 1.
Dispersant can adopt various dispersant well-known in the art; The polymer of for example a lot of alcohols, ester class and/or ethers all can be used as dispersant, is preferably at least a in polyethylene glycol (PEG), polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), polyethylene glycol oxide, polyacrylic acid, Sodium Polyacrylate and the polypropylene.
Under preferred situation, for the viscosity that makes suspension in a reasonable range, coating must be measured and suspension is able to control to the infiltration of barrier film base material, said suspension also can contain thickener, the shared part by weight of thickener is 1-3%.
Thickener can adopt various thickener well-known in the art, and for example a lot of cellulose derivatives, alkali thickening acrylic acid ester all can be used as thickener.
The battery diaphragm that the porosity height of porous flexible base material can make has higher porosity, and therefore, under the preferable case, the porosity of said porous flexible base material surpasses 40%, is preferably 40-80%, more preferably 50-70%.In order to make battery diaphragm thinner, the thickness of preferred porous flexible base material is the 5-30 micron, 8-20 micron more preferably, and low membrane thicknesses can reduce the barrier film resistance when using battery and reduce the weight of battery as far as possible.
The porous flexible base material can adopt various non-conductive polymeric material well-known in the art, the for example film of polyester or polyolefine material.Owing to have higher thermal stability such as the polyolefin of polypropylene (PP) or polyethylene (PE), thereby the film that more preferably adopts polyolefine material is as the porous flexible base material.
The method that coating composition is foamed; Can adopt static type and dynamic type the foaming in wherein a kind of; Foam applying device can use the whole bag of tricks commonly known in the art to apply, like scraper type, pulley type, rubber blanket vacuum pumping-type, net belt type, cylinder and slit.
The temperature that is coated in the foam heating, drying with good stability on the porous flexible substrate surface preferably is lower than softening temperature and fusion temperature as the polymeric material of porous flexible base material; And keep foam in the process of oven dry, not break; Therefore this temperature is preferably 90-120 ℃; Time 1-3min, baking temperature 130-160 ℃, time 1-3min.Above-mentioned method with the foam heating, drying can use the whole bag of tricks commonly known in the art to carry out heating, drying, for example hot-air, infrared radiation.
The stability foam coating needs before baking, to carry out roll compacting, makes the structure of foam coating tightr.The roll compacting linear pressure is preferably 45-294N/cm.
Adopt the foam gluing method of barrier film provided by the invention, can obtain thickness is the 10-20 micron, porosity 50-70%, the lithium-ion-power cell barrier film about average pore size 100 nanometers.
Below in conjunction with embodiment the present invention is described further.
Raw material sources:
Acrylic acid ester emulsion is produced by An Deshi chemical industry (middle mountain) Co., Ltd, and model is AT-6806, viscosity＜200 (3
#Rotor, 60 rev/mins), the pH value is 8.0-9.0, solid content 47-49%;
Alumina powder is produced by the bright nanometer in Dalian road company, and model is the LM2-N290 type, and particle diameter is the 10-50 nanometer;
Blowing agent is a lauryl sodium sulfate, and anion surfactant is produced by Nanjing card Neil science and technology limited Company;
Foam stabilizer is a lauryl alcohol, and Co., Ltd produces by the difficult to understand safe chemical industry in Jinan;
Thickener is the alkali thickening acrylic acid ester emulsion, is produced by An Deshi chemical industry (middle mountain) Co., Ltd, and model is AT-288, viscosity＜50 (1
#Rotor, 60 rev/mins), the pH value is 2.5-3.5, solid content 30-31%.
Embodiment 1
The coating composition that a kind of lithium-ion-power cell barrier film is used is grouped into by following one-tenth in weight portion:
30 parts of acrylic acid ester emulsions;
30 parts of alumina powders;
2 parts of blowing agents (lauryl sodium sulfate);
3 parts of foam stabilizers (lauryl alcohol);
35 parts in water.
Step 1, the alkali thickening acrylic acid ester emulsion of acrylic acid ester emulsion, alumina powder, lauryl sodium sulfate, lauryl alcohol and 3 weight portions is mixed in proportion, regulate viscosity to 2000mPas;
Step 2, above-mentioned suspension is foamed, regulate about foam density to 250 grams per liter.Use foam applying device that foam is coated on the porous flexible matrix uniformly;
Step 3, the foam coating that will be coated on the porous flexible base material are dried 3min under 90 ℃ temperature, water capacity is reached about 10%, after the roll compacting of 45N/cm, under 130 ℃, bake 1min again, and rolling gets lithium ion battery separator.
The gained membrane thicknesses is 20 microns, porosity 69.5%, average pore size 99.2 nanometers.
Embodiment 2
The coating composition that a kind of lithium-ion-power cell barrier film is used is grouped into by following one-tenth in weight portion:
50 parts of acrylic acid ester emulsions;
10 parts of alumina powders;
0.5 part of blowing agent (lauryl sodium sulfate);
1 part of foam stabilizer (lauryl alcohol);
38.5 parts in water.
Step 1, the alkali thickening acrylic acid ester emulsion of acrylic acid ester emulsion, alumina powder, lauryl sodium sulfate, lauryl alcohol and 1 weight portion is mixed in proportion, regulate viscosity to 3000mPas;
Step 2, above-mentioned suspension is foamed, regulate about foam density to 200 grams per liter.Use foam applying device that foam is coated on the porous flexible matrix uniformly;
Step 3, the foam coating that will be coated on the porous flexible base material are dried 1min under 120 ℃ temperature, water capacity is reached about 10%, after the roll compacting of 294N/cm, under 160 ℃, bake 3min again, and rolling gets lithium ion battery separator.
The gained membrane thicknesses is 14 microns, porosity 51.3%, average pore size 108.7 nanometers.
Embodiment 3
The coating composition that a kind of lithium-ion-power cell barrier film is used is grouped into by following one-tenth in weight portion:
40 parts of acrylic acid ester emulsions;
20 parts of alumina powders;
1.5 parts of blowing agents (lauryl sodium sulfate);
2 parts of foam stabilizers (lauryl alcohol);
36.5 parts in water.
Step 1, the alkali thickening acrylic acid ester emulsion of acrylic acid ester emulsion, alumina powder, lauryl sodium sulfate, lauryl alcohol and 2 weight portions is mixed in proportion, the viscosity of regulating coating composition is to 2500mPas;
Step 2, above-mentioned suspension is foamed, regulate about foam density to 210 grams per liter.Use foam applying device that foam is coated on the porous flexible matrix uniformly;
Step 3, the foam coating that will be coated on the porous flexible base material are dried 3min under 110 ℃ temperature, water capacity is reached about 10%, after the roll compacting of 150N/cm, under 150 ℃, bake 2min again, and rolling gets lithium ion battery separator.
The gained membrane thicknesses is 17 microns, porosity 61.3%, average pore size 106.5 nanometers.
Embodiment 4
The coating composition that a kind of lithium-ion-power cell barrier film is used is grouped into by following one-tenth in weight portion:
50 parts of acrylic acid ester emulsions;
25 parts of alumina powders;
1.5 parts of blowing agents (lauryl sodium sulfate);
2.5 parts of foam stabilizers (lauryl alcohol);
21 parts in water.
Step 1, the alkali thickening acrylic acid ester emulsion of acrylic acid ester emulsion, alumina powder, lauryl sodium sulfate, lauryl alcohol and 2 weight portions is mixed in proportion, the viscosity of regulating coating composition is to 2900mPas;
Step 2, above-mentioned suspension is foamed, regulate about foam density to 220 grams per liter.Use foam applying device that foam is coated on the porous flexible matrix uniformly;
Step 3, the foam coating that will be coated on the porous flexible base material are dried 2min under 100 ℃ temperature, water capacity is reached about 10%, after the roll compacting of 200N/cm, under 150 ℃, bake 2min again, and rolling gets lithium ion battery separator.
The gained membrane thicknesses is 18 microns, porosity 66.4%, average pore size 105.0 nanometers.
Embodiment 5
The coating composition that a kind of lithium-ion-power cell barrier film is used is grouped into by following one-tenth in weight portion:
50 parts of the copolymers of Kynoar, polytetrafluoroethylene, polyacrylic acid, polyacrylonitrile, ethylene fluoride and hexafluoroethylene;
Diameter is 25 parts of the zirconia powders of 5-1000 nanometer;
1.5 parts of blowing agents (sodium cetanesulfonate of anionic);
2.5 parts of foam stabilizers (stearic acid);
21 parts in water.
Step 1, with the cellulose derivative (polyanion cellulose of above-mentioned raw materials, 2 weight portions; Hebei is engraved safe chemical industry Co., Ltd and is produced) and polyethylene glycol; Wherein, The weight ratio of polyethylene glycol and zirconia powder is: 0.001: 1, to mix according to the above ratio, and the viscosity of regulating coating composition is to 2900mPas;
Step 2, above-mentioned suspension is foamed, regulate about foam density to 220 grams per liter.Use foam applying device that foam is coated on the porous flexible matrix uniformly;
Step 3, the foam coating that will be coated on the porous flexible base material are dried 2min under 100 ℃ temperature, water capacity is reached about 10%, after the roll compacting of 200N/cm, under 150 ℃, bake 2min again, and rolling gets lithium ion battery separator.
The gained membrane thicknesses is 19 microns, porosity 66.9%, average pore size 104.3 nanometers.
Embodiment 6
The coating composition that a kind of lithium-ion-power cell barrier film is used is grouped into by following one-tenth in weight portion:
50 parts of acroleic acid binding agents (Dongguan City dragon Qin Huagong Co., Ltd);
Diameter is 25 parts of the titanium oxide powders of 5-1000 nanometer;
1.5 parts of blowing agents (neopelex of anionic);
2.5 parts of foam stabilizers (sulfo-succinamide);
21 parts in water.
Step 1, with the alkali thickening acrylic acid ester emulsion and the polyvinyl alcohol of above-mentioned raw materials, 2 weight portions, wherein, the weight ratio of polyvinyl alcohol and titanium oxide powder is: 0.05: 1, mix according to the above ratio, the viscosity of regulating coating composition is to 2900mPas;
Step 2, above-mentioned suspension is foamed, regulate about foam density to 220 grams per liter.Use foam applying device that foam is coated on the porous flexible matrix uniformly;
Step 3, the foam coating that will be coated on the porous flexible base material are dried 2min under 100 ℃ temperature, water capacity is reached about 10%, after the roll compacting of 200N/cm, under 150 ℃, bake 2min again, and rolling gets lithium ion battery separator.
The gained membrane thicknesses is 18 microns, porosity 65.5%, average pore size 105.2 nanometers.
Embodiment 7
The coating composition that a kind of lithium-ion-power cell barrier film is used is grouped into by following one-tenth in weight portion:
50 parts of acrylic acid ester emulsions;
Diameter is 25 parts of the silica powders of 5-1000 nanometer;
1.5 parts of blowing agents (the alkylol APEO of nonionic);
2.5 parts of foam stabilizers (n-butanol);
21 parts in water.
Step 1, with the alkali thickening acrylic acid ester emulsion and the polyvinylpyrrolidone of above-mentioned raw materials, 2 weight portions; Wherein, The weight ratio of polyvinylpyrrolidone and silica powder is: 0.05: 1, to mix according to the above ratio, and the viscosity of regulating coating composition is to 2900mPas;
Step 2, above-mentioned suspension is foamed, regulate about foam density to 220 grams per liter.Use foam applying device that foam is coated on the porous flexible matrix uniformly;
Step 3, the foam coating that will be coated on the porous flexible base material are dried 2min under 100 ℃ temperature, water capacity is reached about 10%, after the roll compacting of 200N/cm, under 150 ℃, bake 2min again, and rolling gets lithium ion battery separator.
The gained membrane thicknesses is 17 microns, porosity 66.0%, average pore size 104.8 nanometers.
Embodiment 8
The coating composition that a kind of lithium-ion-power cell barrier film is used is grouped into by following one-tenth in weight portion:
50 parts of acrylic acid ester emulsions;
Diameter is 25 parts of the silica powders of 5-1000 nanometer;
1.5 parts of blowing agents (APES of nonionic);
2.5 parts of foam stabilizers (n-butanol);
21 parts in water.
Step 1, with the alkali thickening acrylic acid ester emulsion and the polyethylene glycol oxide of above-mentioned raw materials, 2 weight portions, wherein, the weight ratio of polyethylene glycol oxide and silica powder is: 0.05: 1, mix according to the above ratio, the viscosity of regulating coating composition is to 2900mPas;
Step 2, above-mentioned suspension is foamed, regulate about foam density to 220 grams per liter.Use foam applying device that foam is coated on the porous flexible matrix uniformly;
Step 3, the foam coating that will be coated on the porous flexible base material are dried 2min under 100 ℃ temperature, water capacity is reached about 10%, after the roll compacting of 200N/cm, under 150 ℃, bake 2min again, and rolling gets lithium ion battery separator.
The gained membrane thicknesses is 18 microns, porosity 67.1%, average pore size 104.0 nanometers.
Embodiment 9
The coating composition that a kind of lithium-ion-power cell barrier film is used is grouped into by following one-tenth in weight portion:
50 parts of the copolymers of acrylic acid ester emulsion and Kynoar, polytetrafluoroethylene, polyacrylic acid, polyacrylonitrile, ethylene fluoride and hexafluoroethylene; Wherein, the weight ratio between the copolymer of acrylic acid ester emulsion and Kynoar, polytetrafluoroethylene, polyacrylic acid, polyacrylonitrile, ethylene fluoride and hexafluoroethylene is 1: 1;
Diameter is 25 parts of the silica powders of 5-1000 nanometer;
1.5 parts of blowing agents (the cocounut oil acyl diethanol amine of nonionic);
2.5 parts of foam stabilizers (octanol);
21 parts in water.
Step 1, with the alkali thickening acrylic acid ester emulsion and the cellulose derivative (polyanion cellulose of above-mentioned raw materials, 2 weight portions; Hebei is engraved safe chemical industry Co., Ltd and is produced) mixture and polyacrylic acid, wherein, the weight ratio of polyacrylic acid and silica powder is: 0.05: 1; Mix according to the above ratio; The viscosity of regulating coating composition is mixed species to 2900mPas, and the weight ratio between acrylic acid ester emulsion and the cellulose derivative is 1: 1;
Step 2, above-mentioned suspension is foamed, regulate about foam density to 220 grams per liter.Use foam applying device that foam is coated on the porous flexible matrix uniformly;
Step 3, the foam coating that will be coated on the porous flexible base material are dried 2min under 100 ℃ temperature, water capacity is reached about 10%, after the roll compacting of 200N/cm, under 150 ℃, bake 2min again, and rolling gets lithium ion battery separator.
The gained membrane thicknesses is 18 microns, porosity 66.5%, average pore size 105.0 nanometers.
Embodiment 10
The coating composition that a kind of lithium-ion-power cell barrier film is used is grouped into by following one-tenth in weight portion:
50 parts of acrylic acid ester emulsions;
Diameter is 25 parts of the silica powders of 5-1000 nanometer;
1.5 parts of blowing agents (novel green surfactant methyl glucamine);
2.5 parts of foam stabilizers (mixture of octanol and sulfo-succinamide), the weight ratio of octanol and sulfo-succinamide is 1: 1;
21 parts in water.
Step 1, with the alkali thickening acrylic acid ester emulsion and the polypropylene of above-mentioned raw materials, 2 weight portions, wherein, the weight ratio of polypropylene and silica powder is: 0.05: 1, mix according to the above ratio, the viscosity of regulating coating composition is to 2900mPas;
Step 2, above-mentioned suspension is foamed, regulate about foam density to 220 grams per liter.Use foam applying device that foam is coated on the porous flexible matrix uniformly;
Step 3, the foam coating that will be coated on the porous flexible base material are dried 2min under 100 ℃ temperature, water capacity is reached about 10%, after the roll compacting of 200N/cm, under 150 ℃, bake 2min again, and rolling gets lithium ion battery separator.
The gained membrane thicknesses is 19 microns, porosity 66.8%, average pore size 104.4 nanometers.
Embodiment 11
The coating composition that a kind of lithium-ion-power cell barrier film is used is grouped into by following one-tenth in weight portion:
50 parts of acrylic acid ester emulsions;
Diameter is 25 parts of the silica powders of 5-1000 nanometer;
1.5 parts of blowing agents (novel green surfactant APG);
2.5 parts of foam stabilizers (silicone based foam stabiliser QBH (polysiloxane polyether copolymer));
21 parts in water.
Step 1, with the alkali thickening acrylic acid ester emulsion and the Sodium Polyacrylate of above-mentioned raw materials, 2 weight portions, wherein, the weight ratio of Sodium Polyacrylate and silica powder is: 0.05: 1, mix according to the above ratio, the viscosity of regulating coating composition is to 2900mPas;
Step 2, above-mentioned suspension is foamed, regulate about foam density to 220 grams per liter.Use foam applying device that foam is coated on the porous flexible matrix uniformly;
Step 3, the foam coating that will be coated on the porous flexible base material are dried 2min under 100 ℃ temperature, water capacity is reached about 10%, after the roll compacting of 200N/cm, under 150 ℃, bake 2min again, and rolling gets lithium ion battery separator.
The gained membrane thicknesses is 19 microns, porosity 66.1%, average pore size 105.3 nanometers.
Embodiment 12
The coating composition that a kind of lithium-ion-power cell barrier film is used is grouped into by following one-tenth in weight portion:
50 parts of acrylic acid ester emulsions;
Diameter is 25 parts of the silica powders of 5-1000 nanometer;
1.5 parts of blowing agents (novel green surfactant natural tea saponin);
2.5 parts of foam stabilizers (octanol);
21 parts in water.
Step 1, with the alkali thickening acrylic acid ester emulsion of above-mentioned raw materials, 2 weight portions and the mixture of Sodium Polyacrylate and polyvinyl alcohol; Wherein, The weight ratio of Sodium Polyacrylate and polyvinyl alcohol is 1: 1; The weight ratio of mixture and silica powder is: 0.05: 1, to mix according to the above ratio, and the viscosity of regulating coating composition is to 2900mPas;
Step 2, above-mentioned suspension is foamed, regulate about foam density to 220 grams per liter.Use foam applying device that foam is coated on the porous flexible matrix uniformly;
Step 3, the foam coating that will be coated on the porous flexible base material are dried 2min under 100 ℃ temperature, water capacity is reached about 10%, after the roll compacting of 200N/cm, under 150 ℃, bake 2min again, and rolling gets lithium ion battery separator.
The gained membrane thicknesses is 18 microns, porosity 65.9%, average pore size 105.7 nanometers.
Embodiment 13
The coating composition that a kind of lithium-ion-power cell barrier film is used is grouped into by following one-tenth in weight portion:
50 parts of acrylic acid ester emulsions;
Diameter is 25 parts of the silica powders of 5-1000 nanometer;
1.5 parts of blowing agents (novel green surfactant rosin polyoxyethylene ester);
2.5 parts of foam stabilizers (octanol);
21 parts in water.
Step 1, with the alkali thickening acrylic acid ester emulsion of above-mentioned raw materials, 2 weight portions and the mixture of Sodium Polyacrylate and polyvinyl alcohol; Wherein, The weight ratio of Sodium Polyacrylate and polyvinyl alcohol is 1: 1; The weight ratio of mixture and silica powder is: 0.05: 1, to mix according to the above ratio, and the viscosity of regulating coating composition is to 2900mPas;
Step 2, above-mentioned suspension is foamed, regulate about foam density to 220 grams per liter.Use foam applying device that foam is coated on the porous flexible matrix uniformly;
Step 3, the foam coating that will be coated on the porous flexible base material are dried 2min under 100 ℃ temperature, water capacity is reached about 10%, after the roll compacting of 200N/cm, under 150 ℃, bake 2min again, and rolling gets lithium ion battery separator.
The gained membrane thicknesses is 18 microns, porosity 66.4%, average pore size 105.4 nanometers.
Embodiment 14
The coating composition that a kind of lithium-ion-power cell barrier film is used is grouped into by following one-tenth in weight portion:
50 parts of acrylic acid ester emulsions;
Diameter is 25 parts of the silica powders of 5-1000 nanometer;
Blowing agent (quaternary ammonium salt Gemini type surfactant C
12-2-C
122Br) 1.5 parts;
2.5 parts of foam stabilizers (octanol);
21 parts in water.
Step 1, with the alkali thickening acrylic acid ester emulsion of above-mentioned raw materials, 2 weight portions and the mixture of Sodium Polyacrylate and polyvinyl alcohol; Wherein, The weight ratio of Sodium Polyacrylate and polyvinyl alcohol is 1: 1; The weight ratio of mixture and silica powder is: 0.05: 1, to mix according to the above ratio, and the viscosity of regulating coating composition is to 2900mPas;
Step 2, above-mentioned suspension is foamed, regulate about foam density to 220 grams per liter.Use foam applying device that foam is coated on the porous flexible matrix uniformly;
Step 3, the foam coating that will be coated on the porous flexible base material are dried 2min under 100 ℃ temperature, water capacity is reached about 10%, after the roll compacting of 200N/cm, under 150 ℃, bake 2min again, and rolling gets lithium ion battery separator.
The gained membrane thicknesses is 17 microns, porosity 67.0%, average pore size 104.3 nanometers.
Embodiment 15
The coating composition that a kind of lithium-ion-power cell barrier film is used is grouped into by following one-tenth in weight portion:
50 parts of acrylic acid ester emulsions;
Diameter is 25 parts of the silica powders of 5-1000 nanometer;
1.5 parts of blowing agents (mixture of the alkylol APEO of the sodium cetanesulfonate of anionic and nonionic, the weight ratio of the alkylol APEO of the sodium cetanesulfonate of anionic and nonionic is 1: 1);
2.5 parts of foam stabilizers (octanol);
21 parts in water.
Step 1, with the alkali thickening acrylic acid ester emulsion of above-mentioned raw materials, 2 weight portions and the mixture of Sodium Polyacrylate and polyvinyl alcohol; Wherein, The weight ratio of Sodium Polyacrylate and polyvinyl alcohol is 1: 1; The weight ratio of mixture and silica powder is: 0.05: 1, to mix according to the above ratio, and the viscosity of regulating coating composition is to 2900mPas;
Step 2, above-mentioned suspension is foamed, regulate about foam density to 220 grams per liter.Use foam applying device that foam is coated on the porous flexible matrix uniformly;
Step 3, the foam coating that will be coated on the porous flexible base material are dried 2min under 100 ℃ temperature, water capacity is reached about 10%, after the roll compacting of 200N/cm, under 150 ℃, bake 2min again, and rolling gets lithium ion battery separator.
The gained membrane thicknesses is 17 microns, porosity 66.5%, average pore size 104.5 nanometers.
The conventional coating of usefulness and two kinds of methods of foam coating are carried out the surfactant foam applying glue to polyethylene (PE) film of 8 micron thickness respectively, and the membrane properties contrast table that obtains at last is as follows:
| The conventional coating | Foam coating | |
| Membrane thicknesses/micron | 18 | 18 |
| Porosity/% | 50.3 | 66.4 |
| Average pore size/nanometer | 113.6 | 105.0 |
Claims (15)
1. the coating composition that the lithium-ion-power cell barrier film is used is characterized in that, the weight percent proportioning is:
The porous electric insulation oxide particle of the binding agent of 30-50%, 10-30%, the blowing agent of 0.5-2.0%, the foam stabiliser of 1-3% and the water of surplus.
2. the coating composition that a kind of lithium-ion-power cell barrier film according to claim 1 is used is characterized in that the diameter of said porous electric insulation oxide particle is the 5-1000 nanometer.
3. the coating composition that a kind of lithium-ion-power cell barrier film according to claim 1 is used is characterized in that the diameter of said porous electric insulation oxide particle is the 10-50 nanometer.
4. the coating composition that a kind of lithium-ion-power cell barrier film according to claim 1 is used; It is characterized in that said porous electric insulation oxide particle is at least a in al oxide granule, Zirconium oxide particle, titanium oxide particle or the silicon oxide particles.
5. the coating composition that a kind of lithium-ion-power cell barrier film according to claim 1 is used is characterized in that, said adhesive is at least a in oleic series resin binder or the acrylic ester binding agent.
6. the coating composition that a kind of lithium-ion-power cell barrier film according to claim 1 is used is characterized in that said blowing agent is a surfactant.
7. the coating composition that a kind of lithium-ion-power cell barrier film according to claim 6 is used is characterized in that said surfactant is the sodium cetanesulfonate of anionic; Lauryl sodium sulfate, neopelex, the alkylol APEO of nonionic; APES, cocounut oil acyl diethanol amine, APG; Methyl glucamine, natural tea saponin, at least a in rosin polyoxyethylene ester or the Gemini type surfactant.
8. the coating composition that a kind of lithium-ion-power cell barrier film according to claim 1 is used; It is characterized in that said foam stabiliser is at least a in stearic acid, sulfo-succinamide, lauryl alcohol, n-butanol, octanol and the silicone based foam stabiliser.
9. the foam gluing method of a lithium-ion-power cell barrier film; Step is: suspension is carried out mechanical foaming; Be coated on the surface of porous flexible base material then and oven dry, bake and roll compacting after form barrier film with micropore; It is characterized in that said suspension is each described coating composition of claim 1-7.
10. the foam gluing method of a kind of lithium-ion-power cell barrier film according to claim 9; It is characterized in that; Said suspension also contains dispersant; And the weight ratio of porous electric insulation oxide particle total weight is 0.001-0.05 in said dispersant and the said coating composition: 1, and said dispersant is at least a in polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol oxide, polyacrylic acid, Sodium Polyacrylate and the polypropylene.
11. the foam gluing method of a kind of lithium-ion-power cell barrier film according to claim 9; It is characterized in that; Said suspension also contains thickener; And said thickener is coating composition total weight 1-3%, and thickener is at least a in cellulose derivative, the alkali thickening acrylic acid ester.
12. the foam gluing method of a kind of lithium-ion-power cell barrier film according to claim 9 is characterized in that, said porous flexible base material is the film of polyester or polyolefine material, and porosity is 40-80%, and thickness is the 5-30 micron.
13. the foam gluing method of a kind of lithium-ion-power cell barrier film according to claim 9; It is characterized in that; The method that suspension is carried out mechanical foaming is wherein a kind of in static type and the dynamic type foaming, and foam applying device is at least a in scraper type, pulley type, rubber blanket vacuum pumping-type, net belt type, cylinder and the slit.
14. the foam gluing method of a kind of lithium-ion-power cell barrier film according to claim 9 is characterized in that, the temperature of said oven dry is 90-120 ℃, and the time is 1-3min, and the said temperature that bakes is 130-160 ℃, and the time is 1-3min.
15. the foam gluing method of a kind of lithium-ion-power cell barrier film according to claim 9 is characterized in that, the roll compacting linear pressure of said roll compacting is 45-294N/cm.
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