CN103928649B - A kind of modification nonwoven cloth lithium ion battery separator and preparation method thereof - Google Patents
A kind of modification nonwoven cloth lithium ion battery separator and preparation method thereof Download PDFInfo
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- CN103928649B CN103928649B CN201410144003.2A CN201410144003A CN103928649B CN 103928649 B CN103928649 B CN 103928649B CN 201410144003 A CN201410144003 A CN 201410144003A CN 103928649 B CN103928649 B CN 103928649B
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- 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
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
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- 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
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
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- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
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- 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
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- 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
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
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- 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
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/426—Fluorocarbon polymers
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- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
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- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/429—Natural polymers
- H01M50/4295—Natural cotton, cellulose or wood
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- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
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- 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
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- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/443—Particulate material
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- 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
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
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- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/491—Porosity
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The present invention relates to a kind of modification nonwoven cloth lithium ion battery separator, described barrier film includes modification nonwoven cloth base material and compound filler thereof, described modification nonwoven cloth base material includes low melting material and materials with high melting point, described low melting material processes through fusion-crystallization, the weight of materials with high melting point is the 85 99.9% of base material gross weight, and surplus is low melting material；Filler compound on described modification nonwoven cloth base material, including organic polymer, and the first packing material and/or the second packing material.The invention still further relates to this battery diaphragm preparation method, in turn include the following steps: make non-woven fabrics fiber layer；Make modification nonwoven cloth base material；Prepare filler slurry；Fill；Remove solvent；Post processing.The method is simple to operate, low cost, and the product moisture content prepared is low, chemical stability good, mechanical strength is high, improves the yield rate of battery, service life and safety.
Description
Technical field
The present invention relates to a kind of modification nonwoven cloth lithium ion battery separator, also relate to the preparation side of this battery diaphragm
Method.
Background technology
The polyethylene of commercial applications, polypropylene diaphragm are relatively specific for the digital class battery such as mobile phone, camera at present.But should
It is not enough to there is some in class barrier film: on the one hand, owing to polyolefin melt temperature is less than 165 DEG C, battery too high at external temperature or
The when of being accidentally impacted, barrier film may be melt brokenly, causes battery short circuit, thus causes cells burst to explode；On the other hand,
Polyolefin parent's electrolyte ability, keeps electrolyte scarce capacity, causes the performance such as battery cycle life, high current charge-discharge
Difference.This type of barrier film deficiency in terms of security performance and electrical property, limits its use at power energy-storage battery.
In order to improve barrier film security performance and imbibition liquid-keeping property, patent CN102629679A provides a kind of three layers of nanometer
Fiber lithium ion composite diaphragm, this barrier film Heat stability is good, porosity are high, and imbibition ability is good, and improve it by hot pressing is compound
Mechanical strength.But being formed three-layer composite structure by then passing through electrostatic spinning spraying, the peel strength of this barrier film is low, causes its boundary
Face impedance is big, and the internal resistance of cell prepared is bigger than normal, is unfavorable for power energy-storage battery high current charge-discharge, and its aperture is bigger than normal,
In cell fabrication processes, high pressure resistant insulation is poor, and battery internal short-circuit rate is up to 10%.
Patent CN1679185 provides a kind of ceramic diaphragm being applicable to high power lithium ion cell.This barrier film is at nonwoven
Coated ceramic coating on the matrix of cloth, has oxide particle that element is Al, Zr, Si and possesses the nothing of ionic conduction function
Machine material.The great advantage of this barrier film is that ionic conductivity is high, fusing point higher than 250 DEG C, Heat stability is good, electrochemical stability
Good, prepared battery shows excellence on high rate during charging-discharging.But the inorganic material of this diaphragm coating layer is exposed outside
Surface, easily absorbs water, and the water absorption preparing barrier film is high, and the common baking process in cell fabrication processes is difficult to remove this moisture
Totally, once taking more barrier film moisture to battery system, moisture can react with electrolyte, causes battery air-blowing, and internal resistance increases
Greatly so that battery performance is deteriorated, and as big in the capacitance loss of battery, cycle life is poor.It addition, the inorganic painting of its fragility
The layer poor adhesive force to flexible parent metal, causes its mechanically actuated in processing cell process poor, and bending easily occurs in barrier film
The problems such as space, crack and damage, thus cause battery short circuit.Such as battery swell problem to be solved, it is being prepared as the mistake of battery
Journey needs longer baking time or higher temperature except water, then increase its brittle inorganic coating damage and the possibility come off
Property.And this barrier film intensity is poor, it is impossible to meeting the processing request of High-Speed Automatic winding, the dust of resistance to pole piece penetration ability is poor, short
Road rate is higher.
Above-mentioned barrier film is optimized in different performances, but we from above-mentioned analysis it appeared that the most still have bigger
Improvement space.Because power energy-storage battery is required to be high power capacity and the battery of high-power discharge and recharge, its in security performance and
Electrical property aspect proposes the highest requirement to barrier film, and therefore barrier film should be provided simultaneously with good heat stability and electrochemistry
Stability, high lithium-ion-conducting, excellent imbibition liquid-keeping property, moisture is low, be prone to the performances such as battery processing.
Summary of the invention
In order to solve the problems such as existing lithium ion battery separator is hygroscopic, poor heat resistance, intensity are the highest, thus improve lithium from
Sub-battery and safety, the invention provides a kind of modification nonwoven cloth lithium ion battery separator, and the present invention is also simultaneously
A kind of preparation method of this battery diaphragm is provided.
For solving the problems referred to above, the technical solution adopted in the present invention is as follows:
A kind of modification nonwoven cloth lithium ion battery separator, described barrier film includes modification nonwoven cloth base material and compound filling thereof
Agent:
Described filler is filled in the hole of modification nonwoven cloth base material, is now filled with in the hole of non-woven fabrics base material
Fill agent；The most described filler extends whole modification nonwoven cloth base material bag in the hole of modification nonwoven cloth base material outward
Covering, the thickness of described barrier film is 1-10 times of modification nonwoven cloth base material thickness, and the thickness of the most described barrier film is modified
1-2 times of non-woven fabrics base material thickness, now, the structure of described modification nonwoven cloth lithium ion battery separator be centre be one layer of nonwoven
Measuring fiber layer, is filled with filler in the hole of non-woven fabrics base material, and the surface of non-woven fabrics base material is also filled agent and is coated with；
Described modification nonwoven cloth base material: hole that uniform pore size be 1-50000nm is distributed on base material, it is ensured that nonwoven
The thickness of cloth modification composite membrane and the uniformity of aperture structure；Based on factors such as capillary tube imbibition principle and surface tension of liquids,
Substrate porosity is 30-95%, and porosity is more than 30%, and the barrier film prepared has more preferable imbibition liquid-keeping property, it is ensured that lithium
Ion conducts unobstructed in barrier film so that the obtained internal resistance of cell is little, the beneficially high-power discharge and recharge of battery, but porosity is big
In 95%, the intensity that can cause non-woven fabrics base material is not enough, and the diaphragm cell poor in processability prepared, yield rate is low.
Modification nonwoven cloth base material includes low melting material and materials with high melting point, and described low melting material is at fusion-crystallization
Reason, materials with high melting point is the 85-99.9% of modification nonwoven cloth base material gross weight, and remaining is low melting material；Described high-melting-point material
Material is polyester that fusing point is >=200 DEG C, one or more in polyolefin, nitrile polymer, aromatic polyimide, polyethers mix
Make, wherein polyester include but not limited to polyethylene terephthalate (PET), PTT (PPT),
Polybutylene terephthalate (PBT) (PBT), poly-phthalic acid ethyl material；Polyolefin fibrids includes but not limited to gather
(4-methylpentene) material；Cellulose family includes but not limited to polyvinyl formal-nanocrystal cellulose, sky wire material；
Polynitriles class includes but not limited to polyacrylonitrile (PAN) material；Polyimide includes but not limited to aromatic polyimide material；
Polyethers includes but not limited to polyether-ether-ketone, polyether sulfone, polyphenylene oxide, polyphenyl thioether material.Described low melting material is that fusing point is
One or more in the polyolefin of 50-199 DEG C, polyvinyl alcohol, polystyrene, heat bonding polyester, fluorine-based polymer.
Select and there is the base material that low melting material and materials with high melting point prepare so that base material has bimodal fusing point, necessarily
Heat and mechanical pressure under time, the low melting material that weight portion is few starts to soften melted, and changes original fiber morphology, weight
It is newly formed the uniform structure of surfacing, and the many high-melting-point material of main part of weight portion is not changed in because of its high-temperature stability.
After heat pressure discharges, the molten low melting point thing before melted gradually cools and solidifies or recrystallization, and materials with high melting point is tight
Be combined with each other, improve intensity and the surface smoothness of whole base material, its hot strength is up to 60MPa, and puncture strength can
Reach 3N.Low melting material accounts for the 0.1-15% of substrate weight, and materials with high melting point accounts for the 85-99.9% of substrate weight.Low melting point
Material content is more than 15%, and the base material high-temperature hot shrinkage prepared is the poorest, and barrier film the most easily shrinks thus causes
Battery plus-negative plate contact short circuit explodes；Low melting material content is less than 0.1%, and the membrane surface roughness prepared is the biggest, thickness
Uniformity is the poorest, and its mechanical strength is the poorest simultaneously, and the puncture short of resistance to insulating properties test percent of pass is the lowest.
In the present invention, preferred fusion-crystallization processes and refers to low melting material on its fusing point at a temperature of 0-10 DEG C
Heating makes it melt, and then cooling is allowed to cool the process of crystallization.Described melted temperature is to use the fusing point of low melting material
On 0-10 DEG C so that the few low melting material of weight portion softens melted, and changes original fiber morphology, re-forms surface
The structure of even uniform, and the many high-melting-point material of main part of weight portion is not changed in because of its high-temperature stability, when stop heating,
When temperature reduces, high-melting-point substances is closely combined with each other by the crystallisation by cooling of the molten low melting point thing of thawing, improves whole
The intensity of individual base material.
Filler on described modification nonwoven cloth base material, including organic polymer, the first packing material and/or second is filled
Material, wherein:
Described organic polymer be the one in fluorine-based polymer, rubber, esters polymer, cellulose, starch etc. or
Two or more combinations, described fluorine-based polymer include but not limited to Kynoar, Kynoar-hexafluoropropene, poly-four
Fluorothene, polyvinylidene fluoride-trichloro ethylene；Described rubber includes but not limited to butadiene-styrene rubber, carboxylic styrene-butadiene rubber, butyronitrile rubber
Glue, silicone rubber；Described esters polymer includes but not limited to polymethyl methacrylate, polyethyl methacrylate, poly-methyl
Butyl acrylate, polyacrylic acid glycerol ester, polyacrylic acid glycol ester, polyethylene vinyl acetate, polyvinyl acetate；Institute
State cellulose and include but not limited to cellulose acetate, cellulose acetate-butyrate, cellulose-acetate propionate, cyanethyl cellulose, carboxylic
Methylcellulose and mixture thereof；Described starch includes but not limited to cyanoethyl pullulan, amylopectin etc..
Selected organic polymer possesses close electrolyte ability, to guarantee the imbibition liquid-keeping property of barrier film, thus ensures
The ionic conductivity of barrier film and the cycle performance of battery.Selected organic polymer should possess suitable creep ability and with
The wettability of packing material, in order to preferably reunite and wrap packing material.
Described first packing material, it is the inorganic particle of particle diameter 1-2000nm, preferably 10-1000nm, the most excellent
Elect 50-500nm as.Described first packing material is inorganic nanoparticles, primarily serves filling non-woven fabrics hole, improves barrier film height
Temperature stability action, includes but not limited to as inorganic oxide nanoparticles, inorganic nitride nano-particle, Ore nano-particle
In one or more.Described inorganic oxide nanoparticles is silicon dioxide, aluminium oxide, titanium dioxide, zirconium oxide, oxidation
At least one in magnesium, magnesium hydroxide, yittrium oxide, zinc oxide, ferrum oxide and ceria；Described inorganic nitride nanometer
Grain is at least one in silicon nitride, titanium nitride and boron nitride；Described Ore nano-particle is calcium carbonate, calcium sulfate, hydrogen-oxygen
Change aluminum, potassium titanate, Barium metatitanate., Talcum, kaolin clay, kaolinite, pyrophillite, montmorillonite, Muscovitum, bentonite, calcium silicates, silicon
At least one in acid magnesium, kieselguhr and silica sand.The shape of described first packing material can be spherical, subsphaeroidal, dumbbell shape,
Bar-shaped type etc..
Described second packing material, it is the fiber grain of particle diameter 1-10000nm, and preferable particle size is 100-5000nm, enters
One step is preferably 300-3000nm.Playing potentiation in barrier film, described second packing material is fiber grain, described fiber
Granule is wollastonite fibre, glass fibre, lignin, cellulose nano-fibrous, acrylic fiber, nylon fibre, polyster fibre, virtue
One or more kinds of mixing in synthetic fibre fiber, polyimide fiber etc..
Preferably, during described modification nonwoven cloth substrate material is polyester, polyolefin, cyanogen polymer and polyimides
Plant or several mixing.Described first packing material is inorganic oxide particles.Described second packing material be wollastonite fibre,
One or several mixing in lignin, cellulose.
The preparation method of a kind of modification nonwoven cloth lithium ion battery separator, comprises the steps:
A. non-woven fabrics fiber layer is made: materials with high melting point and low melting material are processed into non-woven fabrics fiber layer, described
Processing technique can be the one in melt-blown, spun-bond process, papermaking, spun lacing, acupuncture, Hot rolling, and wherein materials with high melting point weight accounts for system
Becoming the 85-99.9% of non-woven fabrics fiber layer gross weight, surplus is low melting material；Above-mentioned technique can be to nothing by adjusting parameter
Pore size and the porosity of spinning measuring fiber layer are controlled.
Described materials with high melting point is the polyester of fusing point >=200 DEG C, polyolefin, nitrile polymer, aromatic polyimide, polyethers
In one or more；
Described low melting material be fusing point be 50-199 DEG C polyolefin, polyvinyl alcohol, polystyrene, heat bonding polyester,
Fluorine-based polymer；
B. making modification nonwoven cloth base material:
Make modification nonwoven cloth base material: the non-woven fabrics fiber layer of step a gained is carried out fusion-crystallization process；Described melted
Crystallization treatment refers to heat low melting material used in step a on the fusing point of low melting material at a temperature of 0-10 DEG C
Making it melt, then cooling is allowed to cool the process of crystallization.Described melted temperature is low melting material used in step a
On fusing point 0-10 DEG C so that the low melting material that weight portion is few softens melted, and changes original fiber morphology, re-forms
The uniform structure of surfacing, and the many high-melting-point material of main part of weight portion is not changed in because of its high-temperature stability, works as stopping
When heating, temperature reduce, high-melting-point substances is closely combined with each other by the crystallisation by cooling of the molten low melting point thing of thawing, promotes
The intensity of whole base material.Again the non-woven fabrics that fusion-crystallization processed is dried, it is ensured that non-woven fabrics moisture is the lowest.
C. filler slurry is prepared: the first packing material, the second packing material are carried out drying and processing.By organic polymer
Thing, the first solvent and the second solvent are 1:(5～50 according to weight ratio): (0.1～10) mix, and agitating heating is dissolved to clarification,
Add the first packing material and/or the second packing material, mix homogeneously dried；
Described organic polymer be the one in fluorine-based polymer, rubber, esters polymer, cellulose, starch etc. or
Two or more combinations；Described fluorine-based polymer include but not limited to Kynoar, Kynoar-hexafluoropropene, poly-four
Fluorothene, polyvinylidene fluoride-trichloro ethylene；Described rubber includes but not limited to butadiene-styrene rubber, carboxylic styrene-butadiene rubber, butyronitrile rubber
Glue, silicone rubber；Described esters polymer includes but not limited to polymethyl methacrylate, polyethyl methacrylate, poly-methyl
Butyl acrylate, polyacrylic acid glycerol ester, polyacrylic acid glycol ester, polyethylene vinyl acetate, polyvinyl acetate；Institute
State cellulose and include but not limited to cellulose acetate, cellulose acetate-butyrate, cellulose-acetate propionate, cyanethyl cellulose, carboxylic
Methylcellulose and mixture thereof；Described starch includes but not limited to cyanoethyl pullulan, amylopectin etc..
Described first solvent is that the one or two kinds of of ketones solvent, amide solvent and esters solvent is mixed above；Its
Middle ketones solvent includes but not limited to acetone, butanone and N-Methyl pyrrolidone；Amide solvent includes but not limited to N-N diformazan
Yl acetamide, N-N dimethylformamide；Esters solvent includes but not limited to triethyl phosphate, trimethyl phosphate and ethyl acetate.
Described second solvent is that the one or two kinds of in water, alcoholic solvent, halogenated hydrocarbon solvent is mixed above；Second solvent is
One or two kinds of in water, alcoholic solvent, halogenated hydrocarbon solvent is mixed above；Described alcoholic solvent include but not limited to methanol, ethanol,
Propanol, isopropanol, isobutanol, ethylene glycol, n-butyl alcohol, glycerol；Described halogenated hydrocarbon solvent include but not limited to chloroform, two
Chloromethanes.
The second selected solvent boiling point is high compared with the first solvent boiling point more than 10 DEG C.Wherein agitating heating temperature should be first
Below the boiling point of solvent, the preferably shorter than first solvent boiling point less than 10 DEG C.If described heating-up temperature is too high, then solvent volatilized
Hurry up, cause slurry easily to cause caking phenomenon because local temperature is too high.
D. non-woven fabrics is filled: filler slurry step c prepared is enterprising at the modification nonwoven cloth base material prepared through b step
Row is filled；
E. solvent is removed: the non-woven fabrics fiber layer processed through Step d uses the modes such as extraction, drying remove solvent,
Obtain preliminary non-woven fabrics lithium ion battery separator；
F. post processing: the preliminary non-woven fabrics lithium ion battery separator prepared through step e is heated to described organic poly-
Above 5-30 DEG C of compound fusing point；
Or being bathed in the 3rd solvent, described 3rd solvent is water, ketones solvent, amide solvent, esters solvent, alcohol
One or two kinds of in solvent and halogenated hydrocarbon solvent is mixed above.
Through the process of f step, organic polymer can the most closely wrap packing material, and makes barrier film moisture contain
Amount is less, and intensity is higher.Although organic polymer is it may happen that creep in this process, coating porosity structure changes, but
The microcellular structure in coating space can't change so that barrier film will not occur big thermal contraction.And inorganic particulate is by organic polymer
Thing wraps, inorganic particulate most surfaces all with air exclusion, greatly reduce the water absorption of inorganic particulate.After process every
Film is placed in the air of ambient temperature and moisture after some months, still keeps low water content.
Described 3rd solvent can be same with the first solvent phase, it is also possible to different, preferably acetone, water, N-N dimethyl sulfoxide.
Under this solvent bath, organic polymer is likely to occur dissolving, thus changes coating porosity structure, but should not affect the excellent of barrier film
Opposite sex energy.
In order to preferably promote the performance of coating paste, in step c, preferably add corresponding auxiliary agent as required, added
The auxiliary agent added has certain help to film forming, but battery system should not cause any harmful effect.Described auxiliary agent can include
But it is not limited to one or more of dispersant, defoamer, surfactant etc..
Described dispersant can be commercial dispersants, such as polyvinylpyrrolidone (PVP), sodium carboxymethyl cellulose, polypropylene
One or more of acid sodium-salt etc..
Described surfactant commercially, such as fluorine-containing surfactant, silicon-containing surfactant, polyethers surface activity
One or more of agent etc..
Described defoamer commercially, such as the one of natural oil, silicon class defoamer, higher alcohols, polyethers defoamer etc.
Or it is multiple.
Further, in described step c: described first packing material, the gross weight of the second packing material are gathered with organic
The weight ratio of compound is (1:5)-(5:1)；Second packing material accounts for the gross weight of the first packing material and the second packing material
Ratio is 0-50%.
In order to promote the performance of this battery diaphragm prepared further, can be as required to prepared lithium electricity after f step
Sub-battery diaphragm increases or compound extra mechanical treatment, as hot calender, centrifugal, stretch processing etc. one or more.As
Porosity need to be increased, it is contemplated that increase stretch processing；As porosity need to be reduced, it is contemplated that increase calendering or centrifugal treating.
The invention provides a kind of lithium ion battery separator, it is possible to realize following technique effect: the nonwoven fabric base of its uniqueness
Material enables to the bigger raising of barrier film intensity, it is ensured that meet battery winding processability, improves finished battery rate.Special is organic poly-
Compound coated inorganic particle structure enables to the water absorption of battery diaphragm and is greatly reduced, and reduces moisture and enters battery system
Probability, thus avoid the react battery air-blowing caused, interior resistive of too much moisture and electrolyte big, thus promote battery
Multiplying power discharging property and service life.Present invention also offers the preparation method of a kind of lithium ion battery separator, the method is grasped
Making simple, low cost, the product moisture content prepared is few, chemical stability good, mechanical strength is high, improves the finished product of battery
Rate, service life and safety.
Below in conjunction with the accompanying drawings and the present invention is described in further detail by detailed description of the invention.
Accompanying drawing
The structural representation of the modification nonwoven cloth lithium ion battery separator of Fig. 1: embodiment 1.
1, modification nonwoven cloth base material；2, filler.
Detailed description of the invention
Embodiment 1:
By the high-melting-point PET that 95g fusing point is 250 DEG C, 5g fusing point is that 150 DEG C of low-melting point PET fiber utilization wet methods are made
Paper mode manufactures paper with pulp into non-woven fabrics fiber stratum reticulare, and non-woven fabrics fiber stratum reticulare is carried out fusion-crystallization process, and temperature is 155 DEG C, then
Cooling, prepared porosity is 58%, and average pore size is 11um, and puncture strength is 3.0N, and 150 DEG C of 1h thermal contractions are 1%, and thickness is
The modification nonwoven cloth base material 1 of 16um；
Taking filler 2, described filler includes aluminium sesquioxide, PVDF；
The non-woven fabrics processed by fusion-crystallization is dried, and drying temperature is 90 DEG C, and the time is that 1min, 40g particle diameter is
Baking oven put into by the aluminium sesquioxide of 250nm, and temperature is 100 DEG C.Time is 4h.
The acetone of PVDF, 500g and the ethanol Hybrid Heating of 20g that 20g fusing point is 165 DEG C are stirred, stirs 60 DEG C of heating
Mix to clarification, the aluminium sesquioxide dried, 0.5gPVP and 1g fluorine-containing surfactant are added in mixed liquor, continues stirring
15-30min obtains preliminary scattered slurry, this slurry is put into dispersion in separating apparatus and within 15-20 minute, obtains filling paste.
Above filling paste employing immersion way is filled on the PET modification nonwoven cloth base material possessing bimodal fusing point, quiet
After putting 5-10min, put into oven drying 10-20min, obtain preliminary non-woven fabric compounded barrier film；
By above-mentioned preliminary non-woven fabric compounded barrier film hot pressing at a temperature of 160 DEG C, obtaining thickness of the present invention is 20um's
Modification nonwoven cloth lithium ion battery separator.In conjunction with Fig. 1, prepared modification nonwoven cloth lithium ion battery separator includes modification nonwoven cloth
Base material 1 and filler 2, in wherein filler 2 is filled in the hole of modification nonwoven cloth base material 1 and extend outward by whole modified nothing
Spin cloth base material 1 to be coated with.
Embodiment 2:
Preparing modification nonwoven cloth lithium ion battery separator according to the method for embodiment 1, difference is only to the addition of
0.5g fusing point is 150 DEG C of low-melting point PET fibers, and prepared puncture strength is 2.2N, and 150 DEG C of 1h thermal contractions are the non-woven fabrics of 0.5%
Base material.
Embodiment 3:
Preparing modification nonwoven cloth lithium ion battery separator according to the method for embodiment 1, difference is to the addition of 16.8g
Fusing point is 150 DEG C of low-melting point PET fibers, and prepared puncture strength is 3.2N, and 150 DEG C of 1h thermal contractions are the non-woven fabrics base material of 5%.
Embodiment 4:
Prepare modification nonwoven cloth lithium ion battery separator according to the method for embodiment 1, difference be fill after every
Film thickness non-woven fabrics base material before being not filled by, it is all 16um.
Embodiment 5:
Preparing modification nonwoven cloth lithium ion battery separator according to the method for embodiment 1, difference is to use melt-blown
Technique makes modification nonwoven cloth base material.
Embodiment 6:
Prepare modification nonwoven cloth lithium ion battery separator according to the method for embodiment 1, difference be by 40g particle diameter be
Baking oven put into by the aluminium sesquioxide of 250nm, and temperature is 80 DEG C, and the time is 1min.
Embodiment 7:
Preparing modification nonwoven cloth lithium ion battery separator according to the method for embodiment 1, difference is to add 20g grain
Footpath is the wollastonite fibre granule of 1200nm.
Embodiment 8:
Preparing modification nonwoven cloth lithium ion battery separator according to the method for embodiment 1, difference is organic polymer
The PVDF-HFP having selected fusing point to be 145 DEG C, butanone selected by the first solvent.
Embodiment 9:
Preparing modification nonwoven cloth lithium ion battery separator according to the method for embodiment 1, difference is the first filling material
Material have employed the magnesium hydroxide that particle diameter is 800nm.
Embodiment 10:
Preparing modification nonwoven cloth lithium ion battery separator according to the method for embodiment 1, difference is aftertreatment technology
Use preliminary non-woven fabric compounded barrier film (1-5) submerged in water min, be then dried to obtain modified nonwoven of the present invention
Cloth lithium ion battery separator.
Embodiment 11:
Preparing modification nonwoven cloth lithium ion battery separator according to the method for embodiment 1, difference is preliminary nonwoven
The hot pressing at a temperature of 180 DEG C of cloth composite diaphragm.
Comparative example 1:
Preparing lithium ion battery separator according to the method for embodiment 1, difference is not add 150 DEG C of low melting points
PET material makes modification nonwoven cloth base material.
Comparative example 2:
Preparing lithium ion battery separator according to the method for embodiment 1, difference is that with the addition of 24g fusing point is 150 DEG C
Low-melting point PET material makes modification nonwoven cloth base material.
Comparative example 3:
Preparing lithium ion battery separator according to the method for embodiment 1, difference is non-woven fabrics base material and three oxidations two
Aluminum is not the most through drying and processing.
Comparative example 4:
Preparing lithium ion battery separator according to the method for embodiment 1, difference is without any postprocessing working procedures.
Comparative example 5:
Preparing lithium ion battery composite separation membrane according to the method for embodiment 1, difference is that base material uses monolayer PE film.
Comparative example 6:
Conventional ceramic barrier film.
Comparative example 7:
Common non-woven fabric barrier film.
Battery performance test:
Positive pole uses cobalt acid lithium LiCoO2 to make, and negative pole uses graphite, electrolyte employing ethylene carbonate (EC) of battery:
Diethyl carbonate (DEC): the solution of dimethyl carbonate (DMC) volume ratio=1:1:1, the solute that electrolyte adds is 1mol/L's
Lithium hexafluoro phosphate LiPF6, is respectively adopted embodiment 1-6, the barrier film of comparative example 1-5 does cell performance evaluation.
Water content method of testing and test result:
Each embodiment sample in the baking oven of 85 DEG C through different baking times, respectively 6h, 12h, 24h, 48h,
Then sample is done water content test.Test result is as shown in table 1.
Table 1 thermal contraction and intensity key property test result
Showing from the test result of table 1, compared with conventional ceramic barrier film, barrier film of the present invention has relatively low heat-shrinkable
Energy.Compared with comparative example 1,2,4,7, the specific high low melting point feature of non-woven fabrics base material of the present invention the barrier film prepared,
Ensure there is relatively low thermal contraction performance while there is again enough puncture hot strengths, it is ensured that diaphragm cell processed finished products rate and
Safety.
Water content test result after the different baking time of table 2
Showing from the test result of table 2, compared with conventional ceramic barrier film, barrier film water content of the present invention is relatively low.With comparative example
3,4,6 compare, the barrier film being made up of base material of the present invention and interstitital texture, because of particularity and the organic polymer bag of processing
The structure covering inorganic particulate makes barrier film water content relatively low, needs less baking time.
The puncture short of resistance to insulating properties method of testing and test result:
Each embodiment prepares 100 batteries, and during preparing battery, battery core is toasted in the vacuum drying oven of 85 DEG C
24h, is then done the puncture short of resistance to insulating properties test, and is added up the battery of different voltage testers by number battery core.
Test result is as shown in table 3.
Table 3 puncture short of resistance to insulating properties test result
Showing from the test result of table 3, compared with common non-woven fabric barrier film, the resistance to insulating properties of barrier film of the present invention is preferable,
250V puncture short test percent of pass reaches 100%, and common non-woven fabric barrier film percent of pass is 5%.Compared with comparative example 1,4, by
Base material of the present invention and the barrier film of filler structure composition, because the particularity of base material and the filler structure of covering property make
The bigger raising of the resistance to insulating properties of barrier film, finished battery rate improves.
Testing Method of Safety and test result:
Each embodiment prepares 100 batteries, and battery does security performance test, and to battery by number and test
Situation is added up.
Thermal shock: test by GB GB/T18287-2013 method, it is judged that standard is no leakage, the most on fire, the most quick-fried
Fried.
Acupuncture: at room temperature, with 0.5C electric current constant-current charge to charging limit voltage 4.2V time, turn constant-voltage charge 3.5H or
Electric current is down to cut-off charging during 0.02C, by the battery after charging with a diameter of 3.0～the iron nail of 8.0mm, with 21-40mm/sec
Speed vertically pierce through battery, it is judged that standard for the most on fire, do not explode.
Short circuit: test by GB GB/T18287-2013 method, it is judged that standard for the most on fire, do not explode, outer surface
Temperature is less than 150 DEG C.
Overcharge: test by GB GB/T18287-2013 method, it is judged that standard for the most on fire, do not explode.
Test result is as shown in table 4.
Table 4 safety test result
Table 4 test result shows, the battery prepared by barrier film of the present invention shows more superior in terms of security performance test, says
Bright barrier film of the present invention possesses good high-temperature stability and safety.When occurring that thermal runaway or external force collision etc. are unexpected, more
The accidents such as battery catches fire blast can be effectively prevented from occur.
Electric performance test method and test result:
Each embodiment prepares 100 batteries, battery does electric performance test, and takes the average of 10 battery testing data
Value inserts table 5.
Multiplying power discharging: test by GB GB/T18287-2013 method.
Cycle performance: use instrument and equipment BS-9300 ability meter, with 1C rate charge-discharge loop test, uses perseverance
Stream constant-voltage charge system (CC-CV) and constant-current discharge system, charging/discharging voltage scope 3.0～4.2V, first with 1C constant-current charge
To 4.2V, then it is less than 20mA to charge to electric current under 4.2V constant voltage, then with 1C constant-current discharge to final voltage as 3.0V, so
Circulate 500 times, gather loop-around data.
Internal resistance: test by GB GB/T18287-2013 method.
Test result is as shown in table 5.
Table 5 electric performance test result
Table 5 test result shows, the internal resistance of cell prepared by barrier film of the present invention is less, high-rate discharge ability and cyclicity
Can be more excellent.Base material of the present invention and filler give the uniform thickness of barrier film and pore size, good electrochemically stable
Property, excellent imbibition liquid-keeping property and minimum water absorption so that the battery prepared by barrier film of the present invention possess excellence times
Rate discharge performance and cycle life.
Above-mentioned embodiment is only the preferred embodiment of the present invention, it is impossible to limit the scope of protection of the invention with this,
The change of any unsubstantiality that those skilled in the art is done on the basis of the present invention and replacement belong to institute of the present invention
Claimed scope.
Claims (10)
1. a modification nonwoven cloth lithium ion battery separator, it is characterised in that: described barrier film include modification nonwoven cloth base material and
Compound filler:
Described modification nonwoven cloth base material:
Hole that evenly distributed size be 1-50000nm is distributed on it, and porosity is 30-95%；
It includes low melting material and materials with high melting point: described low melting material processes through fusion-crystallization, and materials with high melting point is
The 85-99.9% of modification nonwoven cloth base material gross weight, remaining is low melting point；Described materials with high melting point be fusing point be >=200
DEG C polyester, polyolefin, nitrile polymer, polyimides, one or more in polyethers be mixed, described low melting point is
Fusing point be 50-199 DEG C polyolefin, polyvinyl alcohol, heat bonding polyester, polystyrene, one or more in fluorine-based polymer
It is mixed；
Filler compound on described modification nonwoven cloth base material, including organic polymer, and the first packing material and second is filled out
Fill the one or two kinds of in material to mix:
Described organic polymer be one or two kinds of in fluorine-based polymer, rubber, esters polymer, cellulose and starch with
On combination；
Described first packing material, it is the inorganic particle of particle diameter 1-2000nm, and described inorganic particle is inorganic oxide nanometer
One or more combination in granule, inorganic nitride nano-particle, Ore nano-particle；
Described second packing material, it is the fiber grain of particle diameter 1-10000nm, and described fiber grain is wollastonite fibre, glass
Glass fiber, lignin, cellulose nano-fibrous, acrylic fiber, nylon fibre, polyster fibre, aramid fiber, polyimide fiber
In one or more kinds of combinations；
Described filler is filled in the hole of modification nonwoven cloth base material；Described filler in the hole of modification nonwoven cloth base material outward
Extend and whole modification nonwoven cloth base material is coated with.
Modification nonwoven cloth lithium ion battery separator the most according to claim 1, it is characterised in that: the thickness of described barrier film is
1-10 times of modification nonwoven cloth base material thickness.
Modification nonwoven cloth lithium ion battery separator the most according to claim 2, it is characterised in that: the thickness of described barrier film is
1-2 times of modification nonwoven cloth base material thickness.
Modification nonwoven cloth lithium ion battery separator the most according to claim 1, it is characterised in that: described first packing material
Particle diameter be 10-1000nm, the particle diameter of described second packing material is 100-5000nm.
Modification nonwoven cloth lithium ion battery separator the most according to claim 1, it is characterised in that: described fusion-crystallization processes
Refer on low melting material fusing point, at a temperature of 0-10 DEG C, heat non-woven fabrics base material, make low melting material soften melted,
And materials with high melting point is not changed in, then cooling is allowed to cool crystallization.
6., according to the preparation method of the modification nonwoven cloth lithium ion battery separator described in any one of claim 1-5, its feature exists
In comprising the steps:
A. non-woven fabrics fiber layer is made: materials with high melting point and low melting material are processed into non-woven fabrics fiber layer, described processing
Technique is the one in melt-blown, spun-bond process, wet papermaking, spun lacing, acupuncture, Hot rolling, and wherein materials with high melting point weight accounts for and makes
The 85-99.9% of non-woven fabrics fiber layer gross weight, surplus is low melting material；
Described materials with high melting point be the one in the polyester of fusing point >=200 DEG C, polyolefin, nitrile polymer, polyimides, polyethers or
Multiple；
Described low melting material be fusing point be 50-199 DEG C polyolefin, polyvinyl alcohol, heat bonding polyester, polystyrene, fluorine class
One or more in polymer；
B. modification nonwoven cloth base material is made: the non-woven fabrics fiber layer of step a gained is carried out fusion-crystallization process；
Described fusion-crystallization processes and refers to non-woven fabrics base material used in step a on the fusing point of low melting material 0-10 DEG C
At a temperature of heat, make low melting material soften melted, and materials with high melting point be not changed in, then cooling is allowed to cool crystallization
Process；
C. filler slurry is prepared: the first packing material and/or the second packing material are carried out drying and processing, by organic polymer
Thing, the first solvent and the second solvent are 1:(5～50 according to weight ratio): (0.1～10) mix, and agitating heating is dissolved to clarification,
Then the first packing material through drying and processing and/or the second packing material, mix homogeneously are added；
Described organic polymer be one or two kinds of in fluorine-based polymer, rubber, esters polymer, cellulose, starch with
On combination；
Described first solvent is that the one or two kinds of of ketones solvent, amide solvent and esters solvent is mixed above；
Described second solvent is that the one or two kinds of in water, alcoholic solvent, halogenated hydrocarbon solvent is mixed above；
D. non-woven fabrics is filled: filler slurry step c prepared is being filled out on the modification nonwoven cloth base material that b step prepares
Fill；
E. remove solvent: carry out extracting or being dried by the non-woven fabrics fiber layer processed through Step d, obtain preliminary non-woven fabrics lithium
Ion battery barrier film；
F. post processing: the preliminary non-woven fabrics lithium ion battery separator prepared through step e is heated to described organic polymer
Above 5-30 DEG C of fusing point；
Or being bathed in the 3rd solvent, described 3rd solvent is water, ketones solvent, amide solvent, esters solvent, alcoholic solvent
Mixed above with the one or two kinds of in halogenated hydrocarbon solvent.
The preparation method of modification nonwoven cloth lithium ion battery separator the most according to claim 6, it is characterised in that: described c
In step:
Described first packing material, the gross weight of the second packing material and the weight ratio of organic polymer are (1:5)-(5:1)；
The ratio of the gross weight that the second packing material accounts for the first packing material, the second packing material is 0-50%.
The preparation method of modification nonwoven cloth lithium ion battery separator the most according to claim 6, it is characterised in that: described
Adding auxiliary agent in step c, described auxiliary agent is one or both in dispersant, defoamer.
The preparation method of modification nonwoven cloth lithium ion battery separator the most according to claim 6, it is characterised in that: described d
Step fill use film, soak, extrude, cast, roller coat, blade coating or intaglio plate coating.
The preparation method of modification nonwoven cloth lithium ion battery separator the most according to claim 6, it is characterised in that: will system
Modification nonwoven cloth lithium ion battery separator carry out mechanical treatment, described mechanical treatment is in hot calender, centrifugal, stretching
Plant or multiple.
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| CN201410144003.2A CN103928649B (en) | 2014-04-10 | 2014-04-10 | A kind of modification nonwoven cloth lithium ion battery separator and preparation method thereof |
| JP2016561758A JP6133520B2 (en) | 2014-04-10 | 2014-04-30 | New modified non-woven lithium ion battery separator and method of manufacturing the same |
| PCT/CN2014/076666 WO2015154320A1 (en) | 2014-04-10 | 2014-04-30 | Novel modified non-woven fabric lithium-ion battery diaphragm and preparation method therefor |
| KR1020167027015A KR20160129868A (en) | 2014-04-10 | 2014-04-30 | Novel modified non-woven fabric lithium-ion battery diaphragm and preparation method therefor |
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| CN201410144003.2A CN103928649B (en) | 2014-04-10 | 2014-04-10 | A kind of modification nonwoven cloth lithium ion battery separator and preparation method thereof |
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| JP (1) | JP6133520B2 (en) |
| KR (1) | KR20160129868A (en) |
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Families Citing this family (39)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104201309B (en) * | 2014-08-15 | 2016-08-31 | 中科院广州化学有限公司 | The composite membrane of polyolefin porous membrane and aramid nano-fiber and complex method and application |
| CN104300104A (en) * | 2014-09-28 | 2015-01-21 | 苏州长盛机电有限公司 | Preparation method of low-conductivity diaphragm for lithium-ion battery |
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| CN118073778B (en) * | 2024-04-19 | 2024-07-19 | 蜂巢能源科技股份有限公司 | Composite diaphragm, preparation method thereof and battery |
| CN118281484B (en) * | 2024-05-31 | 2024-09-20 | 新乡市中科膜材料科技有限公司 | High-performance flame-retardant cast battery diaphragm and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4410394B2 (en) * | 2000-06-27 | 2010-02-03 | 日本バイリーン株式会社 | Battery separator |
| JP4185748B2 (en) * | 2002-09-30 | 2008-11-26 | 日本バイリーン株式会社 | Nonwoven fabric and separator for lithium ion secondary battery |
| DE602004026035D1 (en) * | 2003-01-23 | 2010-04-29 | Daiwa Spinning Co Ltd | METHOD FOR PRODUCING A SEPARATOR FOR AN ALKALI SECONDARY BATTERY |
| CN1238914C (en) * | 2003-05-15 | 2006-01-25 | 厦门大学 | Diaphragm of lithium ion cell of compound polymer without need of extraction and its manufacture method |
| JP5447395B2 (en) * | 2008-02-20 | 2014-03-19 | カール・フロイデンベルク・カー・ゲー | Fleece cloth containing cross-linked material |
| JP2010239061A (en) * | 2009-03-31 | 2010-10-21 | Tomoegawa Paper Co Ltd | Separator for electric storage device |
| WO2011013300A1 (en) * | 2009-07-31 | 2011-02-03 | パナソニック株式会社 | Nonaqueous electrolyte secondary battery and method for manufacturing same |
| JP2013163881A (en) * | 2012-02-13 | 2013-08-22 | Kri Inc | Polymer alloy nonwoven fabric and method for producing the same, battery separator and lithium ion secondary battery |
| KR101334888B1 (en) * | 2012-03-16 | 2013-11-29 | 강원대학교산학협력단 | Separator for lithium ion secondary battery and method for manufacturing the same |
| TW201412385A (en) * | 2012-08-30 | 2014-04-01 | Dainippon Ink & Chemicals | Microporous film, method for fabricating the same, separator for battery, and resin composition for nonaqueous electrolyte secondary cell separator |
| KR101256968B1 (en) * | 2012-10-25 | 2013-04-30 | 톱텍에이치앤에스 주식회사 | Pet non-woven fabric for separator of secondary battery and separator of secondary battery having the same |
| JP2014179279A (en) * | 2013-03-15 | 2014-09-25 | Japan Vilene Co Ltd | Separator for electrochemical element |
| CN103682217B (en) * | 2013-12-13 | 2017-04-12 | 中科院广州化学有限公司 | High-temperature resistant non-woven composite membrane for power lithium-ion battery and preparation method for high-temperature resistant non-woven composite membrane |
-
2014
- 2014-04-10 CN CN201410144003.2A patent/CN103928649B/en active Active
- 2014-04-30 WO PCT/CN2014/076666 patent/WO2015154320A1/en active Application Filing
- 2014-04-30 KR KR1020167027015A patent/KR20160129868A/en not_active Application Discontinuation
- 2014-04-30 JP JP2016561758A patent/JP6133520B2/en active Active
Also Published As
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|---|---|
| WO2015154320A1 (en) | 2015-10-15 |
| CN103928649A (en) | 2014-07-16 |
| JP6133520B2 (en) | 2017-05-24 |
| KR20160129868A (en) | 2016-11-09 |
| JP2017510960A (en) | 2017-04-13 |
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