CN103515564B - A kind of composite diaphragm and preparation method thereof - Google Patents
A kind of composite diaphragm and preparation method thereof Download PDFInfo
- Publication number
- CN103515564B CN103515564B CN201310482147.4A CN201310482147A CN103515564B CN 103515564 B CN103515564 B CN 103515564B CN 201310482147 A CN201310482147 A CN 201310482147A CN 103515564 B CN103515564 B CN 103515564B
- Authority
- CN
- China
- Prior art keywords
- inorganic particulate
- polymer particle
- particle
- preparation
- inorganic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
Supporting layer and organic/inorganic particle the invention discloses a kind of composite diaphragm, including stacking are blended coat；The coat includes being evenly mixed in polymer particle and inorganic particulate in adhesive, the coating layer surface and it is internal there is microcellular structure, porosity ranges are 20% 80%, and average pore size is 0.01 μm 10 μm；The polymer particle includes that polytetrafluoroethylene (PTFE), Kynoar, Kynoar hexafluoropropylene copolymer, polyimides, polypropylene be fine, one or more in aramid fiber resin, the particle size range of the polymer particle is 0.01 μm~10 μm, and the inorganic particulate includes SiO2、Al2O3、CaO、TiO2、MgO、ZnO、SnO2、ZrO2In any one or it is various, the particle size range of the inorganic particulate is 0.01 μm~10 μm, and the mass ratio of the polymer particle and inorganic particulate is 1: 10~10: 1.Method the invention also discloses this composite diaphragm is prepared.The present invention has thermal safety good and strong to the absorption holding capacity of electrolyte；The advantage of low cost and low stain can be realized simultaneously.
Description
Technical field
The present invention relates to lithium battery diaphragm, more particularly, to a kind of composite diaphragm high of security performance under high temperature and its preparation
Method.
Background technology
Barrier film as one of big material of lithium battery four, although and the electrochemical reaction that is not involved in battery, but lithium is electric
Significant components in pond, while membrane technique is also one of key technology of the lithium battery development of restriction China and application.The appearance of battery
The key performances such as amount, cycle performance and charging and discharging currents density all have direct relation with barrier film, and the improvement of membrane properties is right
The combination property for improving lithium battery plays an important role.
At present, the lithium battery diaphragm of commercialization is with polyolefin（PP、PE）Based on single thin film or plural layers.Polyolefin
Material has intensity and preferable chemical stability higher, and used as a kind of thermoplastic, porous polyolefin is being higher than
Self-closing function with shrinkage porosity under conditions of glass transition temperature, impedance is substantially risen, is limited by the electric current of battery
System, can to a certain extent prevent the phenomenons such as the blast that causes due to overheat, be a kind of relatively reliable lithium battery diaphragm material
Material.But, the fusing point of polyolefin-based separator is general below 180 DEG C, deforms under high temperature serious.When battery temperature outside or
Internal factor effect is lower to be raised, and barrier film can deform contraction, it is likely that cause battery short circuit, cause the generation of accident.Especially
The electrokinetic cell of high power discharge, internal temperature of battery is higher during use, and it is preferably thermally safe that this requires that barrier film has
Property.
The content of the invention
There is potential safety hazard at high temperature to overcome existing polyalkene diaphragm, it is an object of the invention to provide one
Safe composite diaphragm and preparation method thereof under kind high temperature.
The present invention is achieved through the following technical measures, a kind of composite diaphragm, including stacking supporting layer and organic/nothing
Machine particle is blended coat；The coat includes the polymer particle and inorganic particulate that are evenly mixed in adhesive, described
Coating layer surface and inside have microcellular structure, and porosity ranges are 20%-80%, and average pore size is 0.01 μm -10 μm；It is described poly-
Polymer particle includes polytetrafluoroethylene (PTFE), Kynoar, Kynoar-hexafluoropropylene copolymer, polyimides, polypropylene
One or more in fine, aramid fiber resin, the particle size range of the polymer particle is 0.01 μm~10 μm, the inorganic grain
Attached bag includes SiO2、Al2O3、CaO、TiO2、MgO、ZnO、SnO2、ZrO2In any one or it is various, the inorganic particulate
Particle size range is 0.01 μm~10 μm, and the mass ratio of the polymer particle and inorganic particulate is 1: 10~10: 1.
Used as a kind of preferred embodiment, the supporting layer is polyethylene porous film, polypropylene porous membrane or polypropylene/poly-
Ethylene/polypropylene composite porous film, at 8 μm~100 μm, porosity ranges are 30%~80% to the thickness range of supporting layer, are put down
Equal aperture is 0.01 μm~10 μm.
Used as a kind of preferred embodiment, the thickness range of the supporting layer is 8 μm~25 μm, porosity ranges are 30%~
50%, average pore size is 100nm~150nm.
Used as a kind of preferred embodiment, the polymer particle is that Kynoar or Kynoar-hexafluoropropene are common
Polymers, the particle size range of the polymer particle is 0.1 μm~2 μm.
Used as a kind of preferred embodiment, the inorganic particulate is SiO2Or Al2O3, the particle size range of the inorganic particulate is 0.1
μm~3 μm.
Used as a kind of preferred embodiment, the thickness of the coat is 1 μm~10 μm.
Used as a kind of preferred embodiment, the thickness of the coat is 1 μm~4 μm.
The invention also discloses a kind of preparation method of composite diaphragm, comprise the following steps：
1）, using deionized water as solvent, Aqueous Adhesives, surfactant, dispersant, thickener etc. is high in normal temperature
Speed stirring lower dissolving, wiring solution-forming；Above-mentioned polymer particle and inorganic particulate is added, high-speed stirred is uniform, is made into aqueous
Slurry；The mass percent of each material is in slurry：0.1%~2% water soluble polymer thickener, 0.01%~2% it is aqueous
Dispersant, 0.01%~2% surfactant, 0.1%~5% Aqueous Adhesives, 5%~50% polymer particle and inorganic grain
Son, 50%~83% deionized water；
2）, using micro- gravure roller coating, water paste prepared by the first step is coated on supporting layer barrier film, application rate is
5~100m/min；
3）, by coat film obtained in the previous step by 50~100 DEG C of oven for drying, obtain final composite membrane.
As a kind of preferred embodiment, the polymer particle and inorganic particulate mass percent in the slurry is 15%~
45%。
Used as a kind of preferred embodiment, the Aqueous Adhesives are polyvinyl alcohol, polyethylene glycol oxide, acrylic compounds water solubility
At least one in glue, styrene-butadiene latex；The surfactant is fluorocarbon surfactant, silane surface active agent, polyalcohol
At least one in class surfactant；The dispersant is polyoxyethylene dioleate, poly- TEG monostearate, gathers
TEG monoleate, polyoxypropylene mannitol dioleate, polyoxypropylene stearate, polyoxyethylene fatty acid, alkyl
At least one in benzene sulfonate, polyoxyethylene alkylether, polyvinylpyrrolidone；The thickener is carboxymethyl cellulose
At least one in element, sodium carboxymethylcellulose, polyvinyl alcohol；The speed of the high-speed stirred is 2000~5000r/min；Every
The application rate of film is 10~70m/min, and oven temperature is 50~80 DEG C, and drying time is 3~120s.
The present invention is added with resistant to elevated temperatures inorganic particulate in coat, improves the thermal safety of barrier film；Composite membrane exists
Placed 1 hour at a high temperature of 135 DEG C, percent thermal shrinkage is less than 3%.Meanwhile, inorganic particulate improves infiltration of the electrolyte to barrier film
Property, it is easy to the absorption of electrolyte；Organic filler, can be swelling in the electrolytic solution, has good absorption and keeps the ability of electrolyte,
With electrical conductivity higher, so that lithium battery has good service life cycle；Meanwhile, battery plus-negative plate is glued well
Knot laminating, improves battery core hardness and body holding capacity.Coating sizing-agent solvent for use is water, organic without acetone, DMF, NMP etc.
Solvent, will not pollute to environment, will not endanger the health of workman.As the product of industrialized production, using water as molten
Agent significantly reduces production cost, makes product more competitive.
The present invention has the thermal safety for improving conventional polyolefins barrier film poor and poor to the absorption holding capacity of electrolyte
Shortcoming；The advantage of low cost and low stain is realized simultaneously.
Brief description of the drawings
Fig. 1 illustrates for the cross section of the embodiment of the present invention；
Fig. 2 schemes for the modified layer composite membrane apparent form SEM of the embodiment of the present invention；
Fig. 3 is the electrolyte retention curve map of the embodiment of the present invention.
Specific embodiment
With reference to embodiment and compare accompanying drawing the present invention is described in further detail.
With reference to Fig. 1, a kind of composite diaphragm, including the supporting layer 1 and organic/inorganic particle of stacking are blended coat 2, its system
Preparation Method comprises the following steps：
1）, using deionized water as solvent, Aqueous Adhesives, surfactant, dispersant, thickener etc. is high in normal temperature
Speed stirring lower dissolving, wiring solution-forming；Polymer particle and inorganic particulate are added, high-speed stirred is uniform, is made into water paste；Slurry
The mass percent of each material is in material：0.1%~2% water soluble polymer thickener, 0.01%~2% aqueous dispersion,
0.01%~2% surfactant, 0.1%~5% Aqueous Adhesives, 5%~50% polymer particle and inorganic particulate, 50%
~83% deionized water；
2）, using micro- gravure roller coating, water paste prepared by the first step is coated on supporting layer barrier film, application rate is
5~100m/min；
3）, by coat film obtained in the previous step by 50~100 DEG C of oven for drying, obtain final composite membrane.
The coating processes selection in each embodiment of lower example：Micro- gravure roller coating is used, application rate is 40m/min；Coating basement membrane
It is the 16 μ dry method microporous polypropylene membranes of Shenzhen Senior Material Technology Co., Ltd., porosity is 42%；Entered using three-level baking oven
Row drying, oven temperatures at different levels are respectively 50~57 DEG C, 55~63 DEG C, 63~70 DEG C.The thickness of coat is 3 μ, is coated with caudacoria
Thickness be 19 μ.
Hereinafter the formula and technique again in detail in several embodiments to slurry are illustrated.
Embodiment 1
Weight proportion organic/inorganic stuff and other stuff in slurry: deionized water=100: 200, PVDF-HFP: Al2O3=20∶80。
First in adhesive PVA and tackifier CMC addition deionized waters, at normal temperatures with 300r/min stirring 20min until completely
Dissolving, the weight proportion of wherein PVA and CMC is respectively PVA: organic/inorganic stuff and other stuff=4.5: 100, CMC: organic/inorganic
Stuff and other stuff=1.5: 100.Then fluorocarbon surfactant, aqueous dispersion polyoxypropylene are sequentially added in above-mentioned solution sweet
Dew alcohol dioleate and organic/inorganic stuff and other stuff powder, continue to stir 10min with 300r/min, finally high in 5000r/min
The lower stirring 5min of speed, slurry preparation is completed.Wherein fluorocarbon surfactant: organic/inorganic stuff and other stuff=0.2: 100, polyoxy third
Alkene mannitol dioleate: organic/inorganic stuff and other stuff=0.6: 100.PVDF-HFP weight average molecular weight is about 370,000, and particle diameter is
100~300nm, Al2O3D50=1.0 μm of powder.
Embodiment 2
Weight proportion organic/inorganic stuff and other stuff in slurry: deionized water=100: 200, PVDF-HFP: Al2O3=38∶62。
First in adhesive PVA and tackifier CMC addition deionized waters, at normal temperatures with 300r/min stirring 20min until completely
Dissolving, the weight proportion of wherein PVA and CMC is respectively PVA: organic/inorganic stuff and other stuff=4.5: 100, CMC: organic/inorganic
Stuff and other stuff=1.5: 100.Then fluorocarbon surfactant, aqueous dispersion polyoxypropylene are sequentially added in above-mentioned solution sweet
Dew alcohol dioleate and organic/inorganic stuff and other stuff powder, continue to stir 10min with 300r/min, finally high in 5000r/min
The lower stirring 5min of speed, slurry preparation is completed.Wherein fluorocarbon surfactant: organic/inorganic stuff and other stuff=0.2: 100, polyoxy third
Alkene mannitol dioleate: organic/inorganic stuff and other stuff=0.6: 100.PVDF-HFP weight average molecular weight is about 370,000, and particle diameter is
100~300nm, Al2O3D50=1.0 μm of powder.
Embodiment 3
Weight proportion organic/inorganic stuff and other stuff in slurry: deionized water=100: 200, PVDF-HFP: Al2O3=47∶53。
First in adhesive PVA and tackifier CMC addition deionized waters, at normal temperatures with 300r/min stirring 20min until completely
Dissolving, the weight proportion of wherein PVA and CMC is respectively PVA: organic/inorganic stuff and other stuff=4.5: 100, CMC: organic/inorganic
Stuff and other stuff=1.5: 100.Then fluorocarbon surfactant, aqueous dispersion polyoxypropylene are sequentially added in above-mentioned solution sweet
Dew alcohol dioleate and organic/inorganic stuff and other stuff powder, continue to stir 10min with 300r/min, finally high in 5000r/min
The lower stirring 5min of speed, slurry preparation is completed.Wherein fluorocarbon surfactant: organic/inorganic stuff and other stuff=0.2: 100, polyoxy third
Alkene mannitol dioleate: organic/inorganic stuff and other stuff=0.6: 100.PVDF-HFP weight average molecular weight is about 370,000, and particle diameter is
100~300nm, Al2O3D50=1.0 μm of powder.
Embodiment 4
Weight proportion organic/inorganic stuff and other stuff in slurry: deionized water=100: 200, PVDF-HFP: Al2O3=20∶80。
First in adhesive PVA and tackifier CMC addition deionized waters, at normal temperatures with 300r/min stirring 20min until completely
Dissolving, the weight proportion of wherein PVA and CMC is respectively PVA: organic/inorganic stuff and other stuff=4.5: 100, CMC: organic/inorganic
Stuff and other stuff=1.5: 100.Then fluorocarbon surfactant, polyethylene of dispersing agent pyrrolidones are sequentially added in above-mentioned solution
（PVP）With organic/inorganic stuff and other stuff powder, continue to stir 10min with 300r/min, finally stirred under 5000r/min high speeds
5min is mixed, slurry preparation is completed.Wherein fluorocarbon surfactant: organic/inorganic stuff and other stuff=0.2: 100, PVP: organic/nothing
Machine stuff and other stuff=0.6: 100.PVDF-HFP weight average molecular weight is about 370,000, and particle diameter is 100~300nm, Al2O3Powder D50=
1.0μm。
Embodiment 5
Weight proportion organic/inorganic stuff and other stuff in slurry: deionized water=100: 200, PVDF-HFP: Al2O3=20∶80。
During acrylic compounds adhesive and tackifier CMC are added deionized water first, at normal temperatures with 300r/min stirring 20min until
It is completely dissolved, the weight proportion of wherein adhesive and CMC is respectively acrylic compounds adhesive: organic/inorganic stuff and other stuff=4.5:
100, CMC: organic/inorganic stuff and other stuff=1.5: 100.Then fluorocarbon surfactant, dispersion are sequentially added in above-mentioned solution
Agent polyvinylpyrrolidone（PVP）With organic/inorganic stuff and other stuff powder, continue to stir 10min with 300r/min, finally exist
5000r/min is lower at a high speed to stir 5min, and slurry preparation is completed.Wherein fluorocarbon surfactant: organic/inorganic stuff and other stuff=0.2
: 100, PVP: organic/inorganic stuff and other stuff=0.6: 100.PVDF-HFP weight average molecular weight is about 370,000, and particle diameter is 100~
300nm, Al2O3D50=1.0 μm of powder.
The following is the formula and technique of the slurry in several comparative examples for illustrating effect of the present invention.
Comparative example 1
Weight proportion Al in slurry2O3: deionized water=100: 200.Adhesive PVA and tackifier CMC is added first is gone
In ionized water, at normal temperatures with 300r/min stirring 20min until being completely dissolved, the weight proportion of wherein PVA and CMC is respectively
PVA∶Al2O3=4.5: 100, CMC: Al2O3=1.5∶100.Then polyethylene of dispersing agent pyrrolidines is sequentially added in above-mentioned solution
Ketone（PVP）And Al2O3, continue to stir 10min with 300r/min, finally stir 5min, slurry preparation under 5000r/min high speeds
Complete.Wherein PVP: Al2O3=0.6: 100, Al2O3D50=1.0 μm of powder.
Comparative example 2
Weight proportion PVDF-HFP in slurry: deionized water=100: 500.First acrylic compounds adhesive and tackifier
CMC is added in deionized water, stirs 20min with 300r/min until being completely dissolved at normal temperatures, wherein acrylic compounds adhesive
Weight proportion with CMC is respectively adhesive: PVDF-HFP=5: 100, CMC: PVDF-HFP=1: 100.Then in above-mentioned solution
In sequentially add fluorocarbon surfactant, polyethylene of dispersing agent pyrrolidones（PVP）With PVDF-HFP powder, continue with 300r/
Min stirs 10min, and 5min is finally stirred under 5000r/min high speeds, and slurry preparation is completed.Wherein fluorocarbon surfactant:
PVDF-HFP=0.1: 100, PVP: PVDF-HFP=0.3: 100.PVDF-HFP weight average molecular weight is about 370,000, and particle diameter is 100~
300nm。
Comparative example 3
This comparative example is the 16 μ microporous polypropylene membranes of Shenzhen Senior Material Technology Co., Ltd., porosity 42%, surface
Any coating is not coated with, other any surfaces is not done yet and is modified.
Table 1 is the barrier film prepared according to embodiment 1~5 and the method for comparative example 1~3.As can be seen from the table embodiment 1,
4th, 5 and comparative example 1 have preferable heat resistance, the heat resistance influence of a small amount of PVDF-HFP on barrier film is little in this explanation figure layer.
But as the increase barrier film heat resistance of PVDF-HFP ratios decreases, such as embodiment 2 and 3.Simultaneously from the data in table I
Also know, the ability for adding appropriate PVDF-HFP effectively to improve barrier film Electolyte-absorptive in the coating.
Table 1：
Fig. 3 is the embodiment of the present invention 5 and the barrier film of the method for comparative example 1 preparation to electrolyte retention correlation curve.Tool
Body examination method for testing：All it is the barrier film of 100mm × 100mm above two size, 1h is soaked in the electrolytic solution；Surface is dried in taking-up
Electrolyte, weighs the amount of Electolyte-absorptive；Then allow its exposure in atmosphere, the electrolyte for once retaining was recorded every 10 minutes
Quality；Finally make the amount and the graph of a relation for exposing the time in atmosphere for retaining electrolyte.Fig. 2 changes for the embodiment of the present invention
Property after layer composite membrane apparent form SEM figure.
Be can be seen that under suitable organic-inorganic particle proportion from the data of test, stuff and other stuff containing organic/inorganic is applied
The barrier film of layer can both possess the excellent heat resistance of ceramic coated film, while the also good absorption of polymer-coated film keeps electricity
Solution liquid energy power.
Above is being set forth composite diaphragm of the present invention and preparation method thereof, it is used to help understand the present invention, but this
The implementation method of invention is simultaneously not restricted to the described embodiments, it is any without departing from the change made under the principle of the invention, modify, replace
Generation, combination, simplification, should be equivalent substitute mode, be included within protection scope of the present invention.
Claims (6)
1. supporting layer and organic/inorganic the particle blending of a kind of preparation method of composite diaphragm, the composite diaphragm, including stacking
Coat；The coat includes the polymer particle and inorganic particulate that are evenly mixed in adhesive, the coating layer surface
And it is internal with microcellular structure, porosity ranges are 20%-80%, and average pore size is 0.01 μm -10 μm；The polymer particle
It is 1: 10~10: 1 with the mass ratio of inorganic particulate；The polymer particle is Kynoar or Kynoar-hexafluoro
Propylene copolymer；The particle size range of the polymer particle is 0.1 μm~2 μm；The inorganic particulate is SiO2 or Al2O3, institute
The particle size range for stating inorganic particulate is 0.1 μm~3 μm；The thickness of the coat is 1 μm~10 μm；It is characterized in that preparation side
Method comprises the following steps：
1), using deionized water as solvent, Aqueous Adhesives, surfactant, dispersant, thickener in normal temperature high-speed stirred
Lower dissolving, wiring solution-forming；Mentioned kind, particle diameter and mass ratio being pressed again and adding polymer particle and inorganic particulate, high-speed stirred is equal
It is even, it is made into water paste；The mass percent of each material is in slurry：0.1%~2% water soluble polymer thickener,
0.01%~2% aqueous dispersion, 0.01%~2% surfactant, 0.1%~5% Aqueous Adhesives, 5%~
50% polymer particle and inorganic particulate, 50%~83% deionized water；
2), using micro- gravure roller coating, water paste prepared by the first step is coated into porosity for 42%, 16 μ dry method polypropylene
On microporous barrier, application rate is 40m/min；
3), coat film obtained in the previous step is dried by three-level baking oven, oven temperatures at different levels are respectively 50~57 DEG C,
55~63 DEG C, 63~70 DEG C；The thickness of coat is 3 μ, and the thickness for being coated with caudacoria is 19 μ, obtains final composite membrane.
2. preparation method according to claim 1, it is characterised in that：The supporting layer is polyethylene porous film, poly- third
Alkene porous membrane or polypropylene, polyethylene/polypropylene composite materials porous membrane, the thickness range of supporting layer 8 μm~100 μm, hole
Gap rate scope is 30%~80%, and average pore size is 0.01 μm~10 μm.
3. preparation method according to claim 2, it is characterised in that：The thickness range of the supporting layer is 8 μm~25 μm,
Porosity ranges are 30%~50%, and average pore size is 100nm~150nm.
4. preparation method according to claim 1, it is characterised in that：The thickness of the coat is 1 μm~4 μm.
5. preparation method according to claim 1, it is characterised in that：The polymer particle and inorganic particulate are in the slurry
Mass percent be 15%~45%.
6. preparation method according to claim 1, it is characterised in that：The Aqueous Adhesives are polyvinyl alcohol, polyoxygenated
At least one in ethene, acrylic compounds water-soluble glue, styrene-butadiene latex；The surfactant is fluorocarbon surfactant, silicon
At least one in alkane surfactant, polyol surfactant；The dispersant is polyoxyethylene dioleate, poly- four
Ethylene glycol monostearate, poly- TEG monoleate, polyoxypropylene mannitol dioleate, polyoxypropylene stearate,
At least one in polyoxyethylene fatty acid, alkylbenzenesulfonate, polyoxyethylene alkylether, polyvinylpyrrolidone；It is described
Thickener is at least one in carboxymethylcellulose calcium, sodium carboxymethylcellulose, polyvinyl alcohol；The speed of the high-speed stirred is
2000~5000r/min；The application rate of barrier film is 10~70m/min, and the oven for drying time is 3~120s.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310482147.4A CN103515564B (en) | 2013-10-15 | 2013-10-15 | A kind of composite diaphragm and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310482147.4A CN103515564B (en) | 2013-10-15 | 2013-10-15 | A kind of composite diaphragm and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103515564A CN103515564A (en) | 2014-01-15 |
| CN103515564B true CN103515564B (en) | 2017-06-30 |
Family
ID=49897936
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310482147.4A Active CN103515564B (en) | 2013-10-15 | 2013-10-15 | A kind of composite diaphragm and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103515564B (en) |
Families Citing this family (46)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104979516B (en) * | 2014-04-10 | 2018-08-03 | 宁德时代新能源科技股份有限公司 | Electrochemical device and method for producing electrochemical device separation film |
| CN104064710A (en) * | 2014-06-20 | 2014-09-24 | 青岛中科华联新材料有限公司 | Production technology of high-porosity lithium battery membrane by adopting ceramic coating |
| CN104269506A (en) * | 2014-10-24 | 2015-01-07 | 深圳市星源材质科技股份有限公司 | Method and device for preparing composite diaphragm of lithium battery in multilayer co-extrusion coating way |
| CN104332578A (en) * | 2014-11-20 | 2015-02-04 | 深圳市星源材质科技股份有限公司 | Adhesive composite diaphragm and manufacturing method thereof |
| CN104466059A (en) * | 2014-11-27 | 2015-03-25 | 百顺松涛（天津）动力电池科技发展有限公司 | Lithium-ion battery separator and reparation method thereof |
| EP3866244A1 (en) * | 2014-12-05 | 2021-08-18 | Celgard, LLC | Improved coated separators for lithium batteries and related methods |
| CN105633326B (en) * | 2015-06-03 | 2019-07-12 | 北京星和众工设备技术股份有限公司 | Aromatic polyamide composite diaphragm |
| CN105070867A (en) * | 2015-07-17 | 2015-11-18 | 普天新能源（深圳）有限公司 | Composite diaphragm and preparation method thereof and lithium ion battery |
| CN104979515B (en) * | 2015-07-29 | 2017-05-10 | 沧州明珠隔膜科技有限公司 | Aramid fiber polymer coated lithium ion battery membrane and preparation method thereof |
| CN104993089B (en) * | 2015-07-29 | 2018-03-16 | 沧州明珠隔膜科技有限公司 | A kind of lithium ion battery separator of aramid fiber coating and preparation method thereof |
| CN105140454B (en) * | 2015-09-11 | 2017-04-05 | 江西师范大学 | PI‑ZrO2PTFE ternary nanos are combined many curved hole membrane materials and its preparation method and application |
| CN105449141A (en) * | 2015-12-24 | 2016-03-30 | 深圳中兴创新材料技术有限公司 | Preparation method of battery diaphragm and battery membrane |
| CN106147225A (en) * | 2016-07-07 | 2016-11-23 | 无锡市宝来电池有限公司 | A kind of high-performance corrosion resistant battery diaphragm composite |
| CN106207056A (en) * | 2016-07-15 | 2016-12-07 | 无锡市宝来电池有限公司 | A kind of corrosion resistant composite battery separator film material compositions |
| CN106997940A (en) * | 2017-04-29 | 2017-08-01 | 合肥国轩高科动力能源有限公司 | A kind of water paste coated for lithium ion battery separator and preparation method thereof |
| CN108977748B (en) * | 2017-06-01 | 2021-11-19 | 佛山市顺德区美的电热电器制造有限公司 | Non-stick coating, preparation method thereof, pot and cooking equipment |
| CN107170942B (en) * | 2017-06-01 | 2020-06-05 | 青岛中科华联新材料股份有限公司 | High-temperature-resistant aramid fiber lithium ion battery composite diaphragm and preparation method thereof |
| CN107634168A (en) * | 2017-08-25 | 2018-01-26 | 佛山市盈博莱科技股份有限公司 | The coating slurry of lithium ion battery separator, lithium ion battery separator and preparation method thereof |
| CN107611320B (en) * | 2017-09-08 | 2021-06-29 | 上海凯矜新材料科技有限公司 | Aqueous slurry for lithium battery coating diaphragm, lithium battery coating diaphragm and preparation method thereof |
| CN107845759B (en) * | 2017-11-01 | 2021-01-29 | 安徽安凯汽车股份有限公司 | Preparation process of new energy battery composite fiber diaphragm |
| CN107964677A (en) * | 2017-11-28 | 2018-04-27 | 宁波市鄞州龙腾工具厂 | A kind of high rigidity tow arm |
| KR102280606B1 (en) * | 2018-01-05 | 2021-07-22 | 주식회사 엘지에너지솔루션 | Separator Comprising CMC, Particle-Type Binder, and Soluble-Type Binder |
| CN108400271B (en) * | 2018-02-12 | 2020-11-27 | 重庆云天化纽米科技股份有限公司 | Preparation method of water-based PVDF slurry with stable system for lithium ion battery diaphragm |
| CN108400365B (en) * | 2018-03-01 | 2021-11-12 | 南京瑞贻电子科技有限公司 | Zinc-bromine flow battery |
| CN110323391B (en) * | 2018-03-30 | 2022-01-07 | 比亚迪股份有限公司 | Polymer diaphragm and preparation method thereof, dispersion, lithium ion battery and preparation method thereof |
| CN108717964B (en) * | 2018-06-04 | 2021-05-14 | 珠海恩捷新材料科技有限公司 | Lithium ion battery diaphragm slurry, preparation method thereof and lithium ion battery diaphragm |
| CN108878749A (en) * | 2018-06-29 | 2018-11-23 | 珠海光宇电池有限公司 | A kind of diaphragm and preparation method thereof and lithium-sulfur cell using the diaphragm |
| CN109181523A (en) * | 2018-07-17 | 2019-01-11 | 河北金力新能源科技股份有限公司 | Aqueous aramid fiber coating slurry, aqueous aramid fiber/ceramics mixing coating liquid, and its preparation method and application |
| CN109321042A (en) * | 2018-08-08 | 2019-02-12 | 泰州衡川新能源材料科技有限公司 | Lithium battery diaphragm coating aramid fiber composition and preparation method thereof |
| CN109244321B (en) * | 2018-09-18 | 2021-10-01 | 武汉惠强新能源材料科技有限公司 | Heat-resistant water-based coating for lithium battery diaphragm and preparation method and application thereof |
| CN109346650A (en) * | 2018-10-25 | 2019-02-15 | 苏州捷力新能源材料有限公司 | A kind of lithium ion battery separator and preparation method of the mixed painting of ceramics PVDF |
| CN109546056B (en) * | 2018-11-27 | 2021-06-01 | 河北金力新能源科技股份有限公司 | Diaphragm coating liquid and water system nano para-aramid coated diaphragm |
| CN110105089B (en) * | 2019-05-10 | 2021-07-06 | 济南大学 | By using TiO2/SiO2Method for modifying piezoelectric ceramic surface by composite film and application thereof |
| CN110350214B (en) * | 2019-07-11 | 2021-02-02 | 佛山市金辉高科光电材料股份有限公司 | Zinc-air battery diaphragm and preparation method thereof |
| KR102196914B1 (en) * | 2019-08-22 | 2020-12-31 | 지머터리얼즈 주식회사 | Composite separator for lithium secondary battery and method of manufacturing the same |
| CN110660949A (en) * | 2019-10-08 | 2020-01-07 | 宁波中科达新材料有限公司 | Preparation method of inorganic and organic composite coating diaphragm |
| CN110993863B (en) * | 2019-11-11 | 2021-09-21 | 江苏厚生新能源科技有限公司 | High-cohesiveness water-based PVDF slurry, preparation method and application thereof |
| CN110993857A (en) * | 2019-11-20 | 2020-04-10 | 盐山万兴新能源有限公司 | Oily PVDF (polyvinylidene fluoride) coating process for lithium battery diaphragm |
| CN111244365B (en) * | 2020-01-18 | 2020-11-10 | 江苏厚生新能源科技有限公司 | Composite coating diaphragm with consistent aperture and preparation method thereof |
| CN111244364B (en) * | 2020-01-18 | 2020-11-13 | 江苏厚生新能源科技有限公司 | PVDF (polyvinylidene fluoride) coated diaphragm, preparation method thereof and lithium ion battery |
| CN111883726A (en) * | 2020-08-28 | 2020-11-03 | 芜湖天弋能源科技有限公司 | Lithium ion battery diaphragm slurry and preparation method and application thereof |
| KR102582604B1 (en) * | 2020-11-30 | 2023-09-22 | 컨템포러리 엠퍼렉스 테크놀로지 씨오., 리미티드 | Separator, its manufacturing method, and secondary batteries, battery modules, battery packs and devices related thereto |
| CN113178663A (en) * | 2021-04-28 | 2021-07-27 | 惠州亿纬锂能股份有限公司 | Composite diaphragm and preparation method and application thereof |
| CN114284641A (en) * | 2021-11-09 | 2022-04-05 | 江苏卓高新材料科技有限公司 | Composite coating diaphragm, preparation method thereof, battery with composite coating diaphragm and object with composite coating diaphragm |
| CN115101888B (en) * | 2022-06-16 | 2024-03-26 | 广东工业大学 | Multistage Kong Qianwei cloth-based polymer composite membrane and preparation method and application thereof |
| CN116487819A (en) * | 2022-12-28 | 2023-07-25 | 江苏卓高新材料科技有限公司 | Composite diaphragm and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101542777A (en) * | 2007-02-05 | 2009-09-23 | Lg化学株式会社 | Organic/inorganic composite separator having porous active coating layer and electrochemical device containing the same |
| CN102459439A (en) * | 2009-06-17 | 2012-05-16 | Sk新技术 | Microporous polyethylene film with thermally stable hybrid-composite layers |
| CN103003339A (en) * | 2010-06-10 | 2013-03-27 | Sk新技术株式会社 | Microporous composite film with high thermostable organic/inorganic coating layer |
| CN103078077A (en) * | 2013-01-17 | 2013-05-01 | 中国科学院金属研究所 | Lithium ion battery diaphragm with special structure and preparation method thereof |
| CN103180373A (en) * | 2011-04-05 | 2013-06-26 | W-Scope株式会社 | Porous membrane and method for producing same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101369645A (en) * | 2008-09-23 | 2009-02-18 | 天津力神电池股份有限公司 | Method of manufacturing diaphragm used for high security lithium ion secondary battery |
| CN102610773B (en) * | 2012-03-06 | 2017-06-06 | 宁德新能源科技有限公司 | A kind of polymer Li-ion battery and its barrier film |
| CN102916149B (en) * | 2012-09-26 | 2015-10-28 | 东莞市创明电池技术有限公司 | A kind of lithium battery micro-pore septum and preparation technology thereof |
-
2013
- 2013-10-15 CN CN201310482147.4A patent/CN103515564B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101542777A (en) * | 2007-02-05 | 2009-09-23 | Lg化学株式会社 | Organic/inorganic composite separator having porous active coating layer and electrochemical device containing the same |
| CN102459439A (en) * | 2009-06-17 | 2012-05-16 | Sk新技术 | Microporous polyethylene film with thermally stable hybrid-composite layers |
| CN103003339A (en) * | 2010-06-10 | 2013-03-27 | Sk新技术株式会社 | Microporous composite film with high thermostable organic/inorganic coating layer |
| CN103180373A (en) * | 2011-04-05 | 2013-06-26 | W-Scope株式会社 | Porous membrane and method for producing same |
| CN103078077A (en) * | 2013-01-17 | 2013-05-01 | 中国科学院金属研究所 | Lithium ion battery diaphragm with special structure and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103515564A (en) | 2014-01-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103515564B (en) | A kind of composite diaphragm and preparation method thereof | |
| CN103746085B (en) | A kind of coating composite diaphragm and preparation method thereof | |
| CN104157819A (en) | Ceramic-gel polymer multilayer composite lithium battery diaphragm and preparation method thereof | |
| CN102751462B (en) | Power lithium ion battery and composite diaphragm thereof | |
| Li et al. | Research on a gel polymer electrolyte for Li-ion batteries | |
| CN106159173B (en) | Polymer composite membrane and preparation method thereof, polymer composite membrane prepared by method, gel electrolyte and lithium ion battery | |
| KR100877161B1 (en) | A multi-porous separator for secondary battery with enhanced heat stability and high power output | |
| CN104124427B (en) | Electrode, electrochemical device comprising electrode, and manufacture method of electrode | |
| JP5282181B1 (en) | Non-aqueous secondary battery separator and non-aqueous secondary battery | |
| CN104157818A (en) | Lithium battery diaphragm compounded from aqueous polymer and inorganic nanoparticles and preparation method thereof | |
| EP2077594A1 (en) | Composite separator films for lithium-ion batteries | |
| JP2023030093A (en) | Polylactam-coated separator membrane for lithium-ion secondary battery and related coating formulation | |
| CN104272501A (en) | Porous separator coated with organic/inorganic complex using aqueous coating solution, method for manufacturing same, and electrochemical device using same | |
| CN106654119A (en) | Mixed coating diaphragm and preparation method and application thereof | |
| KR20230113649A (en) | Improved coated separators for lithium batteries and related methods | |
| CN105140450A (en) | Lithium ion battery composite separator, preparation method thereof, and lithium ion battery | |
| CN105932203A (en) | Porous lithium ion battery separator with interpenetrating polymer network structure, and preparation method and application for porous lithium ion battery separator | |
| CN103531736A (en) | High-heat-resistance lithium-ion battery diaphragm and preparation method thereof | |
| JPWO2013058369A1 (en) | Non-aqueous secondary battery separator and non-aqueous secondary battery | |
| CN105206777B (en) | Lithium battery diaphragm of the porous inorganic oxide containing lithium ion conduction and preparation method thereof | |
| JP2021520607A (en) | Coating slurries for manufacturing separators, separators for electrochemical devices and their manufacturing methods | |
| KR102507794B1 (en) | Coating liquid used for lithium ion battery, lithium ion battery diaphragm and lithium ion battery | |
| KR102481773B1 (en) | multilayer separator | |
| US20210328271A1 (en) | Enhanced solid state battery cell | |
| CN104979516A (en) | Electrochemical apparatus, isolation membrane used therein and preparation method of the isolation membrane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| C53 | Correction of patent of invention or patent application | ||
| CB03 | Change of inventor or designer information |
Inventor after: Wu Shuqiu Inventor after: Wang Jingang Inventor after: Chen Xiufeng Inventor after: Chen Liang Inventor after: Yang Jiafu Inventor before: Chen Xiufeng Inventor before: Chen Liang Inventor before: Yang Jiafu Inventor before: Wu Shuqiu Inventor before: Wang Jingang |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: CHEN XIUFENG CHEN LIANG YANG JIAFU WU SHUQIU WANG JINGANG TO: WU SHUQIU WANG JINGANG CHEN XIUFENG CHEN LIANG YANG JIAFU |
|
| SE01 | Entry into force of request for substantive examination | ||
| C53 | Correction of patent of invention or patent application | ||
| CB02 | Change of applicant information |
Address after: 518000 Guangdong province Shenzhen Guangming New District Office of Gongming rural road Applicant after: Shenzhen Senior Technology Material Co., Ltd. Address before: 518000, Guangdong, Shenzhen, Nanshan District Lang Road, Tong Fang information port, block A, building 5 Applicant before: Shenzhen Senior Technology Material Co., Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |