CN104795525A - Melt-blowing polyphenylene sulphide non-woven fabric lithium battery diaphragm and preparation method thereof - Google Patents
Melt-blowing polyphenylene sulphide non-woven fabric lithium battery diaphragm and preparation method thereof Download PDFInfo
- Publication number
- CN104795525A CN104795525A CN201510240715.9A CN201510240715A CN104795525A CN 104795525 A CN104795525 A CN 104795525A CN 201510240715 A CN201510240715 A CN 201510240715A CN 104795525 A CN104795525 A CN 104795525A
- Authority
- CN
- China
- Prior art keywords
- polyphenylene sulfide
- melt
- lithium battery
- battery diaphragm
- temperature
- 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.)
- Granted
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
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
- D04H3/16—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between thermoplastic filaments produced in association with filament formation, e.g. immediately following extrusion
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H5/00—Non woven fabrics formed of mixtures of relatively short fibres and yarns or like filamentary material of substantial length
- D04H5/06—Non woven fabrics formed of mixtures of relatively short fibres and yarns or like filamentary material of substantial length strengthened or consolidated by welding-together thermoplastic fibres, filaments, or yarns
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H5/00—Non woven fabrics formed of mixtures of relatively short fibres and yarns or like filamentary material of substantial length
- D04H5/08—Non woven fabrics formed of mixtures of relatively short fibres and yarns or like filamentary material of substantial length characterised by the method of forming fleeces or layers, e.g. reorientation of fibres or yarns
-
- 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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Cell Separators (AREA)
- Nonwoven Fabrics (AREA)
Abstract
The invention relates to a melt-blowing polyphenylene sulphide non-woven fabric lithium battery diaphragm and a preparation method thereof. The preparation method of the melt-blowing polyphenylene sulphide non-woven fabric lithium battery diaphragm comprises the following steps: drying polyphenylene sulphide aggregates in a melt-blowing polyphenylene sulphide non-woven fabric preparation technology, carrying out melt extrusion, drafting with hot air, cooling, condensing a net, and optimizing technological conditions of hot rolling treatment and heat setting treatment on a polyphenylene sulphide ultrafine fiber net, so that the melt-blowing polyphenylene sulphide non-woven fabric lithium battery diaphragm is obtained. The prepared melt-blowing polyphenylene sulphide non-woven fabric lithium battery diaphragm has the advantages of high melting point, high diaphragm breaking temperature, good fire resistance, low thickness, smooth surface and good chemical and dimension stability, and the prepared melt-blowing polyphenylene sulphide non-woven fabric lithium battery diaphragm has good absorbency, small pore diameter and high porosity, so that requirements of the lithium battery diaphragm are met, safety of a lithium battery is improved, and service life of the lithium battery is prolonged.
Description
Technical field
The present invention relates to the preparation method of lithium battery diaphragm, specifically a kind of melt-blown polyphenylene sulfide nonwoven fabrics lithium battery diaphragm and preparation method thereof.
Background technology
Lithium battery obtains develop rapidly in recent years because have the advantages such as high-energy-density, long circulation life, memory-less effect, but the fail safe of lithium battery is the key issue of its development of restriction always.Barrier film concerns the key components of lithium battery fail safe just.Barrier film is the electrical insulating property film with loose structure, and Main Function is isolation positive and negative electrode and the electronics in battery can not be passed freely through, and ion (in electrolyte solution) can be allowed freely to pass through between both positive and negative polarity simultaneously.Its performance determines the interfacial structure, internal resistance etc. of battery, directly affects the characteristics such as the capacity of battery, cycle performance.Therefore barrier film need have high ion percent of pass, the character of good mechanical performance and solvent resistant (electrolyte).
Non-weaving cloth battery diaphragm is that non-weaving cloth is through certain physics or chemical treatment, to reach a kind of battery diaphragm of battery diaphragm performance requirement, its main species has dry non-woven cloth and wet laid nonwovens, current Foreign Nonwoven battery diaphragm production technology comparative maturity have the U.S., Japanese and German, as 20 μm of slim high-temperature-resistant membrane nonwoven product of German Feuderberg company exploitation, adopt wet-formed and hot blast aftertreatment technology, fibroreticulate filament diameter 3 ~ 4 μm, the heat resistance of product reaches 230 DEG C; The polyolefm non-woven cloth battery diaphragm of Vilence company of Japan exploitation uses 3 kinds of fibers, by the mass area ratio 40g/m of wet-laying mode
2, the diaphragm material of thickness 0.10mm; The melt blown non-woven battery diaphragm of Denso company of Japan exploitation, adopt 4-methylpentene polymer, obtained filament diameter is 0.8 ~ 5.0 μm, mass area ratio 9 ~ 30g/m
2battery diaphragm.And domestic South China Science & Engineering University's Pulp and Paper Engineering laboratory is in the research of lithium battery diaphragm, use PPTA (PPTA) high fibrillation dissolving pulp and PET chopped strand raw material, adopt wet laid nonwovens formation process, successfully obtain the series of products that thermal endurance is better than conventional polyolefins lithium battery diaphragm.
In the prior art, Chinese patent CN103887466A, publication date on June 25th, 2014, patent of invention name is called " preparation method of the melt-blown battery diaphragm of a kind of polypropylene fibre ", this invention with polypropylene fibre section for raw material, adopt in the course of processing, to add hydrophilic master batch and carry out hydrophilic finiss two kinds of modes to polypropylene fibre melt-blowing nonwoven and combine processing, and hot-rolled process is added on conventional polypropylene fibre melt spraying non-woven fabrics, improve the strength property of material, battery diaphragm prepared by the method has large specific area, high porosity, chemical purity is excellent, minimum dimensional contraction, the advantages such as good pliability and cheap price.But because the fusing point of polypropylene material is lower, the barrier film broken film temperature made is very low, and itself anti-flammability is bad, causes the fail safe of lithium battery bad.China Patent No. CN103205123A, publication date on July 17th, 2013, patent of invention name is called " a kind of production method of lithium battery polyphenylene sulfide diaphragm ", this invention is by polyphenylene sulfide high-temperature digestion, obtain homogeneous phase solution, homogeneous phase solution casting machine is extruded and Quench, obtain polyphenylene sulfide porous film, battery diaphragm broken film temperature prepared by the method is high, good flame resistance.But this kind of procedure is comparatively loaded down with trivial details, and the organic solvent of use mostly is toxic solvent, not environmentally.China Patent No. CN101736418A, publication date on June 16th, 2010, patent of invention name is called " a kind of manufacture method of polyphenylene sulfide meltblown fiber products ", this invention be 5 ~ 60,000 with weight average molecular weight and the polyphenylene sulfide meltblown fibers material of molecular weight distribution index between 1.8 ~ 19 for raw material, double screw extruder melting after high-speed stirred batch mixing, granulation, section melting, extrude spray silk, obtain polyphenylene sulfide meltblown short fiber, and use nitrogen quick refrigeration, the polyphenylene sulfide short fiber toughness that the method obtains is better, but, the related application of polyphenylene sulfide meltblown fiber for lithium battery diaphragm goods is developed, this patent does not relate to concrete technology parameter and technical scheme.China Patent No. CN103961939A, publication date on August 6th, 2014, patent of invention name is called " a kind of preparation method of polyphenylene sulfide composite filtering material ", this invention carries out compound by crossing array embedding inlay technique to melt-blown polyphenylene sulfide fibre net and polyphony thioether short fiber Netcom, then temperature programming technique is adopted to carry out thermal finalization process to composite filtering material, obtain a kind of polyphenylene sulfide composite filtering material, the method p-poly-phenyl thioether composite fiber web carries out thermal finalization process, obtain the composite filtering material that filterability is high, but, hot rolling process and thermal finalization process are carried out for the melt-blown polyphenylene sulfide fibre net of individual layer, this patent does not relate to concrete technology parameter and technical scheme.
The barrier film that current lithium battery uses is all polypropylene (PP) or polyethylene (PE) material mostly.And the fusing point of PP material or PE material is lower, cause the broken film temperature of barrier film very low, and itself anti-flammability is bad, causes the fail safe of lithium battery not high.
Summary of the invention
For above-mentioned technology Problems existing, the object of the invention is to provide a kind of melt-blown polyphenylene sulfide nonwoven fabrics lithium battery diaphragm and preparation method thereof, and obtain fusing point high, broken film temperature is high, the septum for lithium ion battery of good flame resistance.Because polyphenylene sulfide superfine fiber at high temperature has excellent intensity, rigidity and fatigue durability, stable for extended periods of time at 250 DEG C, it has excellent chemical resistance simultaneously.For achieving the above object, the present invention is achieved by the following technical solutions:
A kind of melt-blown polyphenylene sulfide nonwoven fabrics lithium battery diaphragm, in described melt-blown polyphenylene sulfide nonwoven fabrics lithium battery diaphragm, superfine fibre diameter is 0.5 ~ 10 μm, and thickness is 20 ~ 100 μm, and aperture is 0.1 ~ 2 μm, porosity is 30% ~ 60%, and unit are polyphenylene sulfide non-woven membrane grammes per square metre is 4 ~ 20g/m
2.
A preparation method for melt-blown polyphenylene sulfide nonwoven fabrics lithium battery diaphragm, the polyphenylene sulfide pellet comprised in melt-blown polyphenylene sulfide nonwoven fabrics preparation technology is dry, melt extrudes, hot blast drawing-off, cooling, solidifying net, p-poly-phenyl thioether superfine fibre net carries out hot rolling process and thermal finalization process, wherein:
The dried polyphenylene sulfide pellet of a is by melt extruding, through hot blast drawing-off, cooling, after solidifying net, the temperature of melt-blown polyphenylene sulfide superfine fiber net being carried out to hot rolling process is 60 ~ 120 DEG C, hot rolling pressure is 0.1 ~ 0.5MPa, and the hot rolling time is 20 ~ 80s, obtained melt-blown polyphenylene sulfide hot rolling process non-woven membrane;
The technique of b to the melt-blown polyphenylene sulfide hot rolling process non-woven membrane thermal finalization process after hot rolling process is thermal finalization process 6min under 85 ~ 95 DEG C of conditions, then thermal finalization process 5min under 100 ~ 120 DEG C of conditions, finally thermal finalization process 3min under 150 ~ 180 DEG C of conditions, obtained superfine fibre diameter is 0.5 ~ 10 μm, thickness is 20 ~ 100 μm, aperture is 0.1 ~ 2 μm, and porosity is 30% ~ 60%, and unit are polyphenylene sulfide non-woven membrane grammes per square metre is 4 ~ 20g/m
2melt-blown polyphenylene sulfide nonwoven fabrics lithium battery diaphragm.
Owing to have employed above technical scheme, the preparation method of melt-blown polyphenylene sulfide nonwoven fabrics lithium battery diaphragm of the present invention has the following advantages:
1 the present invention selects melt-blown polyphenylene sulfide nonwoven fabrics to prepare lithium battery diaphragm, polyphenylene sulfide superfine fiber is a kind of novel high-performance synthetic fibers, because polyphenylene sulfide fusing point is high, prepared superfine fibre at high temperature has excellent intensity, rigidity, fatigue durability and anti-flammability, stable for extended periods of time can be descended at 200 DEG C, there is excellent chemical stability, the requirement of lithium battery diaphragm to chemical resistance and thermal stability can be met, well can extend the life-span that lithium battery diaphragm uses, improve its fail safe simultaneously; And by polyphenylene sulfide nonwoven fabrics barrier film prepared by melt-blown process, there is smaller aperture due, larger specific area and high porosity, broken film temperature is high, good flame resistance, chemical stability are good advantage.
2 the present invention carry out surperficial hot rolling process to melt-blown polyphenylene sulfide fibre net, by changing the temperature of hot rolling, the pressure of hot rolling and the time of hot rolling, can obtain the polyphenylene sulfide nonwoven fabrics barrier film of different-thickness.Finally by thermal finalization process, the polyphenylene sulfide nonwoven fabrics barrier film of dimensionally stable can be obtained.Therefore, the polyphenylene sulfide nonwoven fabrics lithium battery diaphragm prepared by this kind of method meets the thickness of fibre fineness needed for lithium battery diaphragm, aperture, porosity and barrier film.
Melt-blown polyphenylene sulfide nonwoven fabrics lithium battery diaphragm prepared by the present invention has that fusing point is high, broken film temperature is high, the advantage of good flame resistance, thinner thickness, any surface finish, chemistry and good stability of the dimension, and this lithium battery diaphragm has good absorbency, less aperture and higher porosity, meet the requirement of lithium battery diaphragm, and improve the fail safe of lithium battery and extend its useful life.
Embodiment
Below in conjunction with instantiation, the present invention is described in further detail.
A kind of melt-blown polyphenylene sulfide nonwoven fabrics lithium battery diaphragm, in described melt-blown polyphenylene sulfide nonwoven fabrics lithium battery diaphragm, superfine fibre diameter is 0.5 ~ 10 μm, and thickness is 20 ~ 100 μm, and aperture is 0.1 ~ 2 μm, porosity is 30% ~ 60%, and unit are polyphenylene sulfide non-woven membrane grammes per square metre is 4 ~ 20g/m
2.
A kind of melt-blown polyphenylene sulfide nonwoven fabrics lithium battery diaphragm preparation method, preparation method carries out according to the following steps:
Melt-blown polyphenylene sulfide nonwoven fabrics lithium battery diaphragm processing:
A selects suitable polyphenylene sulfide pellet, is placed on vacuum drying oven vacuum treatment 24h, treatment temperature 100 ~ 150 DEG C, polyphenylene sulfide beads fuse index range 10 ~ 50g/10min;
B is by the polyphenylene sulfide pellet after a step process through melt spraying non-woven fabrics machine Screw Extrusion, and then p-poly-phenyl thioether melt carries out drawing-off cooling, then on solidifying lace curtaining, forms superfine fibre fibre net structure, obtained polyphenylene sulfide nonwoven fabrics.Wherein, the range of speeds 4 ~ the 10rpm of measuring pump in reinforced process, the feeding district temperature melt extruding barrel in process is 280 ~ 320 DEG C, compressional zone temperature is 300 ~ 340 DEG C, melting zone temperature is 300 ~ 340 DEG C, tip nozzles temperature is 310 ~ 330 DEG C, hot air temperature is 320 ~ 340 DEG C, in cooling procedure, cross air blasting speed is 0.1 ~ 0.5m/s, melt-blown receiving range is 50 ~ 60cm, and lapping speed is 0.1 ~ 2m/min;
C, to the polyphenylene sulfide nonwoven fabrics prepared through b step, carries out hot rolling process, the polyphenylene sulfide nonwoven fabrics of obtained thermal finalization, hot-rolled temperature 60 ~ 120 DEG C, hot rolling pressure 0.3 ~ 0.4MPa, and the hot rolling time is 10 ~ 80s;
The polyphenylene sulfide nonwoven fabrics prepared through step c adopts temperature programming technique to carry out thermal finalization process by d, wherein, described temperature programming technique is 85 ~ 95 DEG C of process 6min, then 100 ~ 120 DEG C of process 5min, last 150 ~ 180 DEG C of process 3min, obtained superfine fibre diameter is 0.5 ~ 10 μm, thickness is 20 ~ 100 μm, aperture is 0.1 ~ 2 μm, and porosity is 30% ~ 60%, and unit are polyphenylene sulfide non-woven membrane grammes per square metre is 4 ~ 20g/m
2melt-blown polyphenylene sulfide nonwoven fabrics lithium battery diaphragm.
Specific embodiment
embodiment 1
1 melt-blown polyphenylene sulfide nonwoven fabrics lithium battery diaphragm processing: selecting melt index to be 10 ~ 50g/10min polyphenylene sulfide slice is raw material, polyphenylene sulfide slice is put into vacuum drying chamber vacuumize 24h, temperature is set as 120 DEG C, then by the polyphenylene sulfide slice after drying process through HDF-6D type melt spraying non-woven fabrics machine Screw Extrusion, and p-poly-phenyl thioether melt carries out drawing-off cooling, then superfine fibre web frame is formed at solidifying lace curtaining, obtained polyphenylene sulfide nonwoven fabrics;
Screw extruder temperature sets: owing to selecting different melt index polyphenylene sulfide slice, different melt index needs to select different barrel temperature, set temperature value is that the feeding district temperature of barrel is 280 ~ 320 DEG C, compressional zone temperature is 300 ~ 340 DEG C, melting zone temperature is 300 ~ 340 DEG C, tip nozzles temperature is 310 ~ 330 DEG C, and hot air temperature is 320 ~ 340 DEG C;
Measuring pump flow control: measuring pump flow appreciable impact material fineness and the uniformity, for obtaining ultra-fine polyphenylene sulfide fibre, need reduce the flow of measuring pump, and the measure of production revolution speed is 4 ~ 10rmp;
In cooling procedure, cross air blasting speed is 0.1 ~ 0.5m/s, and melt-blown receiving range is 50 ~ 60cm, and lapping speed is 0.1 ~ 2m/min.
2 pairs of polyphenylene sulfide nonwoven fabrics prepared through upper step, carry out hot rolling process, and the polyphenylene sulfide nonwoven fabrics of obtained thermal finalization, hot-rolled temperature 60 DEG C, hot rolling pressure 0.1 ~ 0.5MPa, the hot rolling time is 80s.
Polyphenylene sulfide nonwoven fabrics after hot rolled adopts temperature programming technique to carry out thermal finalization process by 3, and wherein, heat setting temperature is 180 DEG C, and the time is 10min.
embodiment 2
1 melt-blown polyphenylene sulfide nonwoven fabrics lithium battery diaphragm processing: selecting melt index to be 10 ~ 50g/10min polyphenylene sulfide slice is raw material, polyphenylene sulfide slice is put into vacuum drying chamber vacuumize 24h, temperature is set as 120 DEG C, then by the polyphenylene sulfide slice after drying process through HDF-6D type melt spraying non-woven fabrics machine Screw Extrusion, and p-poly-phenyl thioether melt carries out drawing-off cooling, then superfine fibre web frame is formed at solidifying lace curtaining, obtained polyphenylene sulfide nonwoven fabrics;
Screw extruder temperature sets: owing to selecting different melt index polyphenylene sulfide slice, different melt index needs to select different barrel temperature, set temperature value is that the feeding district temperature of barrel is 280 ~ 320 DEG C, compressional zone temperature is 300 ~ 340 DEG C, melting zone temperature is 300 ~ 340 DEG C, tip nozzles temperature is 310 ~ 330 DEG C, and hot air temperature is 320 ~ 340 DEG C;
Measuring pump flow control: measuring pump flow appreciable impact material fineness and the uniformity, for obtaining ultra-fine polyphenylene sulfide fibre, need reduce the flow of measuring pump, and the measure of production revolution speed is 4 ~ 10rmp;
In cooling procedure, cross air blasting speed is 0.1 ~ 0.5m/s, and melt-blown receiving range is 50 ~ 60cm, and lapping speed is 0.1 ~ 2m/min.
2 pairs of polyphenylene sulfide nonwoven fabrics prepared through upper step, carry out hot rolling process, and the polyphenylene sulfide nonwoven fabrics of obtained thermal finalization, hot-rolled temperature 70 DEG C, hot rolling pressure 0.1 ~ 0.5MPa, the hot rolling time is 70s.
Polyphenylene sulfide nonwoven fabrics after hot rolled adopts temperature programming technique to carry out thermal finalization process by 3, and wherein, heat setting temperature is 170 DEG C, and the time is 12min.
embodiment 3
1 melt-blown polyphenylene sulfide nonwoven fabrics lithium battery diaphragm processing: selecting melt index to be 10 ~ 50g/10min polyphenylene sulfide slice is raw material, polyphenylene sulfide slice is put into vacuum drying chamber vacuumize 24h, temperature is set as 120 DEG C, then by the polyphenylene sulfide slice after drying process through HDF-6D type melt spraying non-woven fabrics machine Screw Extrusion, and p-poly-phenyl thioether melt carries out drawing-off cooling, then superfine fibre web frame is formed at solidifying lace curtaining, obtained polyphenylene sulfide nonwoven fabrics;
Screw extruder temperature sets: owing to selecting different melt index polyphenylene sulfide slice, different melt index needs to select different barrel temperature, set temperature value is that the feeding district temperature of barrel is 280 ~ 320 DEG C, compressional zone temperature is 300 ~ 340 DEG C, melting zone temperature is 300 ~ 340 DEG C, tip nozzles temperature is 310 ~ 330 DEG C, and hot air temperature is 320 ~ 340 DEG C;
Measuring pump flow control: measuring pump flow appreciable impact material fineness and the uniformity, for obtaining ultra-fine polyphenylene sulfide fibre, need reduce the flow of measuring pump, and the measure of production revolution speed is 4 ~ 10rmp;
In cooling procedure, cross air blasting speed is 0.1 ~ 0.5m/s, and melt-blown receiving range is 50 ~ 60cm, and lapping speed is 0.1 ~ 2m/min.
2 pairs of polyphenylene sulfide nonwoven fabrics prepared through upper step, carry out hot rolling process, and the polyphenylene sulfide nonwoven fabrics of obtained thermal finalization, hot-rolled temperature 80 DEG C, hot rolling pressure 0.1 ~ 0.5MPa, the hot rolling time is 60s.
Polyphenylene sulfide nonwoven fabrics after hot rolled adopts temperature programming technique to carry out thermal finalization process by 3, and wherein, heat setting temperature is 160 DEG C, and the time is 14min.
embodiment 4
1 melt-blown polyphenylene sulfide nonwoven fabrics lithium battery diaphragm processing: selecting melt index to be 10 ~ 50g/10min polyphenylene sulfide slice is raw material, polyphenylene sulfide slice is put into vacuum drying chamber vacuumize 24h, temperature is set as 120 DEG C, then by the polyphenylene sulfide slice after drying process through HDF-6D type melt spraying non-woven fabrics machine Screw Extrusion, and p-poly-phenyl thioether melt carries out drawing-off cooling, then superfine fibre web frame is formed at solidifying lace curtaining, obtained polyphenylene sulfide nonwoven fabrics;
Screw extruder temperature sets: owing to selecting different melt index polyphenylene sulfide slice, different melt index needs to select different barrel temperature, set temperature value is that the feeding district temperature of barrel is 280 ~ 320 DEG C, compressional zone temperature is 300 ~ 340 DEG C, melting zone temperature is 300 ~ 340 DEG C, tip nozzles temperature is 310 ~ 330 DEG C, and hot air temperature is 320 ~ 340 DEG C;
Measuring pump flow control: measuring pump flow appreciable impact material fineness and the uniformity, for obtaining ultra-fine polyphenylene sulfide fibre, need reduce the flow of measuring pump, and the measure of production revolution speed is 4 ~ 10rmp;
In cooling procedure, cross air blasting speed is 0.1 ~ 0.5m/s, and melt-blown receiving range is 50 ~ 60cm, and lapping speed is 0.1 ~ 2m/min.
2 pairs of polyphenylene sulfide nonwoven fabrics prepared through upper step, carry out hot rolling process, and the polyphenylene sulfide nonwoven fabrics of obtained thermal finalization, hot-rolled temperature 90 DEG C, hot rolling pressure 0.1 ~ 0.5MPa, the hot rolling time is 70s.
Polyphenylene sulfide nonwoven fabrics after hot rolled adopts temperature programming technique to carry out thermal finalization process by 3, and wherein, heat setting temperature is 150 DEG C, and the time is 16min.
embodiment 5
1 melt-blown polyphenylene sulfide nonwoven fabrics lithium battery diaphragm processing: selecting melt index to be 10 ~ 50g/10min polyphenylene sulfide slice is raw material, polyphenylene sulfide slice is put into vacuum drying chamber vacuumize 24h, temperature is set as 120 DEG C, then by the polyphenylene sulfide slice after drying process through HDF-6D type melt spraying non-woven fabrics machine Screw Extrusion, and p-poly-phenyl thioether melt carries out drawing-off cooling, then superfine fibre web frame is formed at solidifying lace curtaining, obtained polyphenylene sulfide nonwoven fabrics;
Screw extruder temperature sets: owing to selecting different melt index polyphenylene sulfide slice, different melt index needs to select different barrel temperature, set temperature value is that the feeding district temperature of barrel is 280 ~ 320 DEG C, compressional zone temperature is 300 ~ 340 DEG C, melting zone temperature is 300 ~ 340 DEG C, tip nozzles temperature is 310 ~ 330 DEG C, and hot air temperature is 320 ~ 340 DEG C;
Measuring pump flow control: measuring pump flow appreciable impact material fineness and the uniformity, for obtaining ultra-fine polyphenylene sulfide fibre, need reduce the flow of measuring pump, and the measure of production revolution speed is 4 ~ 10rmp;
In cooling procedure, cross air blasting speed is 0.1 ~ 0.5m/s, and melt-blown receiving range is 50 ~ 60cm, and lapping speed is 0.1 ~ 2m/min.
2 pairs of polyphenylene sulfide nonwoven fabrics prepared through upper step, carry out hot rolling process, and the polyphenylene sulfide nonwoven fabrics of obtained thermal finalization, hot-rolled temperature 100 DEG C, hot rolling pressure 0.1 ~ 0.5MPa, the hot rolling time is 40s.
Polyphenylene sulfide nonwoven fabrics after hot rolled adopts temperature programming technique to carry out thermal finalization process by 3, and wherein, heat setting temperature is 140 DEG C, and the time is 18min.
embodiment 6
1 melt-blown polyphenylene sulfide nonwoven fabrics lithium battery diaphragm processing: selecting melt index to be 10 ~ 50g/10min polyphenylene sulfide slice is raw material, polyphenylene sulfide slice is put into vacuum drying chamber vacuumize 24h, temperature is set as 120 DEG C, then by the polyphenylene sulfide slice after drying process through HDF-6D type melt spraying non-woven fabrics machine Screw Extrusion, and p-poly-phenyl thioether melt carries out drawing-off cooling, then superfine fibre web frame is formed at solidifying lace curtaining, obtained polyphenylene sulfide nonwoven fabrics;
Screw extruder temperature sets: owing to selecting different melt index polyphenylene sulfide slice, different melt index needs to select different barrel temperature, set temperature value is that the feeding district temperature of barrel is 280 ~ 320 DEG C, compressional zone temperature is 300 ~ 340 DEG C, melting zone temperature is 300 ~ 340 DEG C, tip nozzles temperature is 310 ~ 330 DEG C, and hot air temperature is 320 ~ 340 DEG C;
Measuring pump flow control: measuring pump flow appreciable impact material fineness and the uniformity, for obtaining ultra-fine polyphenylene sulfide fibre, need reduce the flow of measuring pump, and the measure of production revolution speed is 4 ~ 10rmp;
In cooling procedure, cross air blasting speed is 0.1 ~ 0.5m/s, and melt-blown receiving range is 50 ~ 60cm, and lapping speed is 0.1 ~ 2m/min.
2 pairs of polyphenylene sulfide nonwoven fabrics prepared through upper step, carry out hot rolling process, and the polyphenylene sulfide nonwoven fabrics of obtained thermal finalization, hot-rolled temperature 110 DEG C, hot rolling pressure 0.1 ~ 0.5MPa, the hot rolling time is 30s.
Polyphenylene sulfide nonwoven fabrics after hot rolled adopts temperature programming technique to carry out thermal finalization process by 3, and wherein, heat setting temperature is 130 DEG C, and the time is 20min.
embodiment 7
1 melt-blown polyphenylene sulfide nonwoven fabrics lithium battery diaphragm processing: selecting melt index to be 10 ~ 50g/10min polyphenylene sulfide slice is raw material, polyphenylene sulfide slice is put into vacuum drying chamber vacuumize 24h, temperature is set as 120 DEG C, then by the polyphenylene sulfide slice after drying process through HDF-6D type melt spraying non-woven fabrics machine Screw Extrusion, and p-poly-phenyl thioether melt carries out drawing-off cooling, then superfine fibre web frame is formed at solidifying lace curtaining, obtained polyphenylene sulfide nonwoven fabrics;
Screw extruder temperature sets: owing to selecting different melt index polyphenylene sulfide slice, different melt index needs to select different barrel temperature, set temperature value is that the feeding district temperature of barrel is 280 ~ 320 DEG C, compressional zone temperature is 300 ~ 340 DEG C, melting zone temperature is 300 ~ 340 DEG C, tip nozzles temperature is 310 ~ 330 DEG C, and hot air temperature is 320 ~ 340 DEG C;
Measuring pump flow control: measuring pump flow appreciable impact material fineness and the uniformity, for obtaining ultra-fine polyphenylene sulfide fibre, need reduce the flow of measuring pump, and the measure of production revolution speed is 4 ~ 10rmp;
In cooling procedure, cross air blasting speed is 0.1 ~ 0.5m/s, and melt-blown receiving range is 50 ~ 60cm, and lapping speed is 0.1 ~ 2m/min.
2 pairs of polyphenylene sulfide nonwoven fabrics prepared through upper step, carry out hot rolling process, and the polyphenylene sulfide nonwoven fabrics of obtained thermal finalization, hot-rolled temperature 120 DEG C, hot rolling pressure 0.1 ~ 0.5MPa, the hot rolling time is 20s.
Polyphenylene sulfide nonwoven fabrics after hot rolled adopts temperature programming technique to carry out thermal finalization process by 3, and wherein, heat setting temperature is 120 DEG C, and the time is 24min.
embodiment 8
1 melt-blown polyphenylene sulfide nonwoven fabrics lithium battery diaphragm processing: selecting melt index to be 10 ~ 50g/10min polyphenylene sulfide slice is raw material, polyphenylene sulfide slice is put into vacuum drying chamber vacuumize 24h, temperature is set as 120 DEG C, then by the polyphenylene sulfide slice after drying process through HDF-6D type melt spraying non-woven fabrics machine Screw Extrusion, and p-poly-phenyl thioether melt carries out drawing-off cooling, then superfine fibre web frame is formed at solidifying lace curtaining, obtained polyphenylene sulfide nonwoven fabrics;
Screw extruder temperature sets: owing to selecting different melt index polyphenylene sulfide slice, different melt index needs to select different barrel temperature, set temperature value is that the feeding district temperature of barrel is 280 ~ 320 DEG C, compressional zone temperature is 300 ~ 340 DEG C, melting zone temperature is 300 ~ 340 DEG C, tip nozzles temperature is 310 ~ 330 DEG C, and hot air temperature is 320 ~ 340 DEG C;
Measuring pump flow control: measuring pump flow appreciable impact material fineness and the uniformity, for obtaining ultra-fine polyphenylene sulfide fibre, need reduce the flow of measuring pump, and the measure of production revolution speed is 4 ~ 10rmp;
In cooling procedure, cross air blasting speed is 0.1 ~ 0.5m/s, and melt-blown receiving range is 50 ~ 60cm, and lapping speed is 0.1 ~ 2m/min.
2 pairs of polyphenylene sulfide nonwoven fabrics prepared through upper step, carry out hot rolling process, and the polyphenylene sulfide nonwoven fabrics of obtained thermal finalization, hot-rolled temperature 120 DEG C, hot rolling pressure 0.1 ~ 0.5MPa, the hot rolling time is 10s.
Polyphenylene sulfide nonwoven fabrics after hot rolled adopts temperature programming technique to carry out thermal finalization process by 3, and wherein, heat setting temperature is 110 DEG C, and the time is 28min.
embodiment 9
1 melt-blown polyphenylene sulfide nonwoven fabrics lithium battery diaphragm processing: selecting melt index to be 10 ~ 50g/10min polyphenylene sulfide slice is raw material, polyphenylene sulfide slice is put into vacuum drying chamber vacuumize 24h, temperature is set as 120 DEG C, then by the polyphenylene sulfide slice after drying process through HDF-6D type melt spraying non-woven fabrics machine Screw Extrusion, and p-poly-phenyl thioether melt carries out drawing-off cooling, then superfine fibre web frame is formed at solidifying lace curtaining, obtained polyphenylene sulfide nonwoven fabrics;
Screw extruder temperature sets: owing to selecting different melt index polyphenylene sulfide slice, different melt index needs to select different barrel temperature, set temperature value is that the feeding district temperature of barrel is 280 ~ 320 DEG C, compressional zone temperature is 300 ~ 340 DEG C, melting zone temperature is 300 ~ 340 DEG C, tip nozzles temperature is 310 ~ 330 DEG C, and hot air temperature is 320 ~ 340 DEG C;
Measuring pump flow control: measuring pump flow appreciable impact material fineness and the uniformity, for obtaining ultra-fine polyphenylene sulfide fibre, need reduce the flow of measuring pump, and the measure of production revolution speed is 4 ~ 10rmp;
In cooling procedure, cross air blasting speed is 0.1 ~ 0.5m/s, and melt-blown receiving range is 50 ~ 60cm, and lapping speed is 0.1 ~ 2m/min.
2 pairs of polyphenylene sulfide nonwoven fabrics prepared through upper step, carry out hot rolling process, and the polyphenylene sulfide nonwoven fabrics of obtained thermal finalization, hot-rolled temperature 120 DEG C, hot rolling pressure 0.1 ~ 0.5MPa, the hot rolling time is 10s.
Polyphenylene sulfide nonwoven fabrics after hot rolled adopts temperature programming technique to carry out thermal finalization process by 3, and wherein, heat setting temperature is 100 DEG C, and the time is 30min.
Claims (2)
1. a melt-blown polyphenylene sulfide nonwoven fabrics lithium battery diaphragm, it is characterized in that: in described melt-blown polyphenylene sulfide nonwoven fabrics lithium battery diaphragm, superfine fibre diameter is 0.5 ~ 10 μm, thickness is 20 ~ 100 μm, aperture is 0.1 ~ 2 μm, porosity is 30% ~ 60%, and unit are polyphenylene sulfide non-woven membrane grammes per square metre is 4 ~ 20g/m
2.
2. the preparation method of a melt-blown polyphenylene sulfide nonwoven fabrics lithium battery diaphragm, the polyphenylene sulfide pellet comprised in melt-blown polyphenylene sulfide nonwoven fabrics preparation technology is dry, melt extrude, hot blast drawing-off, cooling, solidifying net, p-poly-phenyl thioether superfine fibre net carries out hot rolling process and thermal finalization process, it is characterized in that:
The dried polyphenylene sulfide pellet of a is by melt extruding, through hot blast drawing-off, cooling, after solidifying net, the temperature of melt-blown polyphenylene sulfide superfine fiber net being carried out to hot rolling process is 60 ~ 120 DEG C, hot rolling pressure is 0.1 ~ 0.5MPa, and the hot rolling time is 20 ~ 80s, obtained melt-blown polyphenylene sulfide hot rolling process non-woven membrane;
The technique of b to the melt-blown polyphenylene sulfide hot rolling process non-woven membrane thermal finalization process after hot rolling process is thermal finalization process 6min under 85 ~ 95 DEG C of conditions, then thermal finalization process 5min under 100 ~ 120 DEG C of conditions, finally thermal finalization process 3min under 150 ~ 180 DEG C of conditions, obtained superfine fibre diameter is 0.5 ~ 10 μm, thickness is 20 ~ 100 μm, aperture is 0.1 ~ 2 μm, and porosity is 30% ~ 60%, and unit are polyphenylene sulfide non-woven membrane grammes per square metre is 4 ~ 20g/m
2melt-blown polyphenylene sulfide nonwoven fabrics lithium battery diaphragm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510240715.9A CN104795525B (en) | 2015-05-13 | A kind of melt-blown polyphenylene sulfide non-woven fabrics lithium battery diaphragm and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510240715.9A CN104795525B (en) | 2015-05-13 | A kind of melt-blown polyphenylene sulfide non-woven fabrics lithium battery diaphragm and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104795525A true CN104795525A (en) | 2015-07-22 |
| CN104795525B CN104795525B (en) | 2018-06-01 |
Family
ID=
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105428578A (en) * | 2015-12-24 | 2016-03-23 | 广东永畅兴精密制造股份有限公司 | Battery production method and fiber diaphragm formed thereby |
| CN105789536A (en) * | 2016-03-24 | 2016-07-20 | 武汉纺织大学 | Preparation of melt-blown polyphenylene sulfide non-woven fabric/aramid fiber nanofiber composite membrane |
| CN106906670A (en) * | 2017-03-30 | 2017-06-30 | 武汉纺织大学 | A kind of polyphenylene sulfide superfine fiber/Synthetic Leather bass and preparation method thereof |
| CN107722274A (en) * | 2017-11-15 | 2018-02-23 | 天津工业大学 | A kind of preparation method of melt-blown polyphenylene sulfide |
| CN108796822A (en) * | 2018-07-26 | 2018-11-13 | 武汉纺织大学 | A kind of melt-blown polyphenylene sulfide nonwoven cloth filter material and preparation method thereof for reducing tar content |
| CN110528314A (en) * | 2019-06-19 | 2019-12-03 | 武汉纺织大学 | A kind of composite sheet and its preparation method and application of the polyphenylene sulfide superfine fiber containing melt-blown |
| CN111690137A (en) * | 2020-06-19 | 2020-09-22 | 四川中科兴业高新材料有限公司 | Special type reusable melt-blown fabric material capable of being disinfected and preparation method thereof |
| CN112310557A (en) * | 2020-11-03 | 2021-02-02 | 天津工业大学 | Preparation method of polyphenylene sulfide-based diaphragm based on viscous flow modification technology |
| CN115863906A (en) * | 2022-12-20 | 2023-03-28 | 蜂巢能源科技(无锡)有限公司 | Composite diaphragm and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101736418A (en) * | 2009-11-26 | 2010-06-16 | 陈逊 | Method for manufacturing polyphenylene sulfide meltblown fiber products |
| CN102517978A (en) * | 2011-12-29 | 2012-06-27 | 中国纺织科学研究院 | Polyphenylene sulfide paper and preparation method thereof |
| WO2014046120A1 (en) * | 2012-09-21 | 2014-03-27 | 東レ株式会社 | Polyphenylene sulfide composite fiber and non-woven fabric |
| CN104603981A (en) * | 2012-06-29 | 2015-05-06 | 吉坤日矿日石能源株式会社 | Lithium-ion secondary battery separator |
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101736418A (en) * | 2009-11-26 | 2010-06-16 | 陈逊 | Method for manufacturing polyphenylene sulfide meltblown fiber products |
| CN102517978A (en) * | 2011-12-29 | 2012-06-27 | 中国纺织科学研究院 | Polyphenylene sulfide paper and preparation method thereof |
| CN104603981A (en) * | 2012-06-29 | 2015-05-06 | 吉坤日矿日石能源株式会社 | Lithium-ion secondary battery separator |
| WO2014046120A1 (en) * | 2012-09-21 | 2014-03-27 | 東レ株式会社 | Polyphenylene sulfide composite fiber and non-woven fabric |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105428578A (en) * | 2015-12-24 | 2016-03-23 | 广东永畅兴精密制造股份有限公司 | Battery production method and fiber diaphragm formed thereby |
| CN105789536A (en) * | 2016-03-24 | 2016-07-20 | 武汉纺织大学 | Preparation of melt-blown polyphenylene sulfide non-woven fabric/aramid fiber nanofiber composite membrane |
| CN105789536B (en) * | 2016-03-24 | 2019-06-28 | 武汉纺织大学 | A kind of melt-blown polyphenylene sulfide non-woven fabrics/aramid nano-fiber composite diaphragm preparation |
| CN106906670A (en) * | 2017-03-30 | 2017-06-30 | 武汉纺织大学 | A kind of polyphenylene sulfide superfine fiber/Synthetic Leather bass and preparation method thereof |
| CN107722274A (en) * | 2017-11-15 | 2018-02-23 | 天津工业大学 | A kind of preparation method of melt-blown polyphenylene sulfide |
| CN108796822A (en) * | 2018-07-26 | 2018-11-13 | 武汉纺织大学 | A kind of melt-blown polyphenylene sulfide nonwoven cloth filter material and preparation method thereof for reducing tar content |
| CN110528314A (en) * | 2019-06-19 | 2019-12-03 | 武汉纺织大学 | A kind of composite sheet and its preparation method and application of the polyphenylene sulfide superfine fiber containing melt-blown |
| CN110528314B (en) * | 2019-06-19 | 2022-07-01 | 武汉纺织大学 | Composite sheet containing melt-blown polyphenylene sulfide superfine fibers and preparation method and application thereof |
| CN111690137A (en) * | 2020-06-19 | 2020-09-22 | 四川中科兴业高新材料有限公司 | Special type reusable melt-blown fabric material capable of being disinfected and preparation method thereof |
| CN112310557A (en) * | 2020-11-03 | 2021-02-02 | 天津工业大学 | Preparation method of polyphenylene sulfide-based diaphragm based on viscous flow modification technology |
| CN112310557B (en) * | 2020-11-03 | 2022-12-23 | 天津工业大学 | Preparation method of polyphenylene sulfide-based diaphragm based on viscous flow modification technology |
| CN115863906A (en) * | 2022-12-20 | 2023-03-28 | 蜂巢能源科技(无锡)有限公司 | Composite diaphragm and preparation method and application thereof |
| CN115863906B (en) * | 2022-12-20 | 2024-02-23 | 蜂巢能源科技(无锡)有限公司 | Composite diaphragm and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103305960B (en) | Method for manufacturing polyester staple fibers through recycled polyester bottles | |
| CN101638813A (en) | Producing method for spinning heterogeneous colored terylene preoriented continuous yarn by recycled polyester bottle sheet materials | |
| CN103590139B (en) | A kind of powerful three-dimensional crimp memory fiber and manufacture method thereof | |
| CN103205902B (en) | Production method of polyester filament spunbonded needle-punched felt base | |
| CN104711764B (en) | High-tenacity long-acting electret superfine fibre PLA melt-blown non-woven material and preparation method | |
| CN101760903B (en) | Method for preparing polyphenylene sulfide spun-bonded needle punched non-woven fabrics | |
| CN102168320A (en) | Production technology for producing porous fine denier colored terylene pre-oriented filament by utilizing recycled polyester bottle flakes | |
| CN101857981B (en) | Process for producing nanometer bamboo carbon fiber by adopting polylactic acid group | |
| CN104727015A (en) | Manufacturing method for melt-blown nonwoven fabric | |
| CN102277690B (en) | Hydrophilic base fabric and making method thereof | |
| CN103352266B (en) | Preparation method for cellulose and thermoplastic polymer skin-core type composite fiber | |
| CN102864511A (en) | Method for producing hollow colored terylene pre-oriented filament yarn through recyclable polyester bottle pieces | |
| CN102162152A (en) | Polyester fiber and fabric | |
| CN108807791A (en) | A kind of composite diaphragm and preparation method thereof for lithium battery | |
| CN106003934A (en) | Anti-static nanofiber non-woven material and preparation method | |
| CN104264287B (en) | Method for preparing rope net ribbon-like filaments by drawing waste and old polyethylene terephthalate (PET) bottle sheets | |
| CN103173887B (en) | Production process of blending type regeneration polyester flame retardant staple fiber | |
| CN103628256A (en) | Method for producing conductive geotextile | |
| CN106906635A (en) | A kind of method for sorting of medical high-absorbility hydrophilic non-woven | |
| CN106012054A (en) | Bio-based nylon fiber and preparing method thereof | |
| CN108265394A (en) | A kind of biodegradable melt-blown poly butylene succinate non-woven fabrics and preparation method thereof | |
| CN102912461A (en) | Method for producing antibacterial fire-resistant polyester filaments by utilizing recycled polyester bottle chips | |
| CN109473613A (en) | Compound non-woven battery diaphragm of one kind and preparation method thereof | |
| CN109004154A (en) | A kind of method of wet process copy paper technique manufacture diaphragm of power lithium ion battery | |
| CN110129901A (en) | A kind of preparation method of creeping chill fiber |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180601 Termination date: 20210513 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |