CN104600232A - Method for modifying ultra-high molecular weight polyethylene microporous film - Google Patents
Method for modifying ultra-high molecular weight polyethylene microporous film Download PDFInfo
- Publication number
- CN104600232A CN104600232A CN201510012834.9A CN201510012834A CN104600232A CN 104600232 A CN104600232 A CN 104600232A CN 201510012834 A CN201510012834 A CN 201510012834A CN 104600232 A CN104600232 A CN 104600232A
- Authority
- CN
- China
- Prior art keywords
- ultra
- high molecular
- molecular mass
- micropore film
- polyethylene micropore
- 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
-
- 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
-
- 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
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Cell Separators (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention discloses a method for modifying an ultra-high molecular weight polyethylene microporous film. The method comprises the following steps of flatly paving the ultra-high molecular weight polyethylene microporous film on a receiving platform of an electrostatic spraying device; carrying out polymer spraying treatment on the ultra-high molecular weight polyethylene microporous film with pre-prepared polymer spraying solution by utilizing the electrostatic spraying device; and controlling the amount of microparticles on the surface of the ultra-high molecular weight polyethylene microporous film by controlling the spraying time so as to obtain the modified ultra-high molecular weight polyethylene microporous film. The ultra-high molecular weight polyethylene microporous film modified through the method has high porosity and charging and discharging capacity and good cycling performance.
Description
Technical field
The present invention relates to technical field of lithium batteries, particularly relate to a kind of method of modifying of ultra-high molecular mass polyethylene micropore film.
Background technology
At present, lithium ion battery forms primarily of positive electrode, negative material, electrolyte, barrier film and battery case packaging material.In lithium ion battery, barrier film has two effects: one is separated by the both positive and negative polarity of battery, prevents the two poles of the earth from contacting and short circuit; Two is that the lithium ion in electrolyte is passed through.The performance of barrier film determines interfacial structure, the internal resistance of battery, directly has influence on the capacity of battery, cycle performance and fail safe.
Because ultra-high molecular mass polyethylene micropore film has the ability of very strong external force resistance puncture, the short circuit ratio of lithium battery can be reduced when it uses as lithium battery diaphragm, thus improve the fail safe of lithium battery.But still there is the problems such as porosity is low, charge/discharge capacity is low in the ultra-high molecular mass polyethylene micropore film prepared by prior art.
Summary of the invention
The object of this invention is to provide a kind of method of modifying of ultra-high molecular mass polyethylene micropore film, by the ultra-high molecular mass polyethylene micropore film of the method modification, there is higher porosity, higher charge/discharge capacity and good cycle performance.
A method of modifying for ultra-high molecular mass polyethylene micropore film, described method comprises:
Ultra-high molecular mass polyethylene micropore film is laid on the receiving platform of electrostatic spraying apparatus;
Described electrostatic spraying apparatus is utilized to carry out polymer spray treatment with the polymer spray coating liquor prepared in advance to described ultra-high molecular mass polyethylene micropore film;
Controlling the amount of described ultra-high molecular mass polyethylene micropore film surface micron particles by controlling spray time, obtaining modified ultra-high molecular mass polyethylene micropore film.
Described ultra-high molecular mass polyethylene micropore film be adopt the molecular weight of polyethylene prepared of thermally induced phase separation be 800,000 ~ 1,000 ten thousand polyethene microporous membrane.
The described polymer spray coating liquor prepared in advance specifically comprises:
Specific dissolution of polymer is prepared the polymer spray coating liquor obtained in solvent, the mass concentration of described polymer spray coating liquor is 0.1-15%.
The mass concentration of described polymer spray coating liquor is preferably: 3%.
Described specific polymer comprises: the macromolecular material of the nanometer obtained by electrostatic spraying to micron particles that can be dissolved in solvent.
Described specific polymer comprises: Kynoar, the fine or polypropylene of polypropylene.
Prepare the solvent that described polymer spray coating liquor adopts to comprise: the one in acetone, DMF, DMA, first alcohol and water or several arbitrarily.
Prepare the solvent that described polymer spray coating liquor adopts to be preferably: by acetone and DMF formulated according to the mass ratio of 3:2.
Carrying out in the process of polymer spray treatment to described ultra-high molecular mass polyethylene micropore film:
Spray voltage is 0.1-30kV, and receiving range is 15 ㎝.
Described spray voltage is preferably 21kV.
As seen from the above technical solution provided by the invention, by the ultra-high molecular mass polyethylene micropore film of the method modification, there is higher porosity, higher charge/discharge capacity and good cycle performance.
Accompanying drawing explanation
In order to be illustrated more clearly in the technical scheme of the embodiment of the present invention, below the accompanying drawing used required in describing embodiment is briefly described, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawings can also be obtained according to these accompanying drawings.
Fig. 1 provides by the embodiment of the present invention method of modifying schematic flow sheet of ultra-high molecular mass polyethylene micropore film;
Fig. 2 is the discharge capacity curve synoptic diagram of ultra-high molecular mass polyethylene micropore film in lithium battery obtained according to example modification of the present invention;
Fig. 3 is the cyclical stability curve synoptic diagram of ultra-high molecular mass polyethylene micropore film in lithium battery obtained according to example modification of the present invention.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, be clearly and completely described the technical scheme in the embodiment of the present invention, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on embodiments of the invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to protection scope of the present invention.
Below in conjunction with accompanying drawing, the embodiment of the present invention is described in further detail, be illustrated in figure 1 the embodiment of the present invention the method for modifying schematic flow sheet of ultra-high molecular mass polyethylene micropore film is provided, described method comprises:
Step 11: ultra-high molecular mass polyethylene micropore film is laid on the receiving platform of electrostatic spraying apparatus;
In this step, ultra-high molecular mass polyethylene micropore film be adopt the molecular weight of polyethylene prepared of thermally induced phase separation be 800,000 ~ 1,000 ten thousand polyethene microporous membrane.
Step 12: utilize described electrostatic spraying apparatus to carry out polymer spray treatment with the polymer spray coating liquor prepared in advance to described ultra-high molecular mass polyethylene micropore film;
In this step, this polymer spray coating liquor prepared in advance specifically comprises:
Specific dissolution of polymer is prepared the polymer spray coating liquor obtained in solvent, the mass concentration of described polymer spray coating liquor is 0.1-15%, and preferred mass concentration is 3%.
Described specific polymer comprises: the macromolecular material of the nanometer obtained by electrostatic spraying to micron particles that can be dissolved in solvent.
In specific implementation, this polymer can be Kynoar PVDF, high molecular polymer, the polymer copolymerization compound such as fine or polypropylene of polypropylene.
In addition, the solvent that above-mentioned preparation described polymer spray coating liquor adopts can comprise: the one in acetone, DMF, DMA, first alcohol and water or several arbitrarily.
Preferred solvent is: by acetone and DMF formulated according to the mass ratio of 3:2.
Step 13: the amount controlling described ultra-high molecular mass polyethylene micropore film surface micron particles by controlling spray time, obtains modified ultra-high molecular mass polyethylene micropore film.
Carrying out in the process of polymer spray treatment to described ultra-high molecular mass polyethylene micropore film: spray voltage is 0.1-30kV, receiving range is 15 ㎝.
Further, preferred spray voltage is 21kV.
The operation principle of above-mentioned electrostatic spraying apparatus is: according to the physical phenomenon of electrophoresis, using coated article as anode, generally ground connection; Coating atomising mechanism is as negative electrode, and negative high voltage of connecting with the mains, just defines high-voltage electrostatic field at the two poles of the earth like this; Owing to producing corona discharge at negative electrode, ejection paint medium can be made charged, and be atomized further.According to " two like magnetic poles repel each other, there is a natural attraction between the sexes " principle, charged paint medium by electric field force effect, directionally flows to the coated article surface of positively charged along power line, just can become that one deck is even, the film of adhesion-tight by neutralization precipitation.
Below in conjunction with instantiation, preparation method of the present invention is described in detail:
Embodiment 1, weighing 0.31gPVDF powder are as polymer, and dicyandiamide solution presses acetone: DMF (DMF)=3:2 mass ratio preparation, obtains the PVDF solution that mass concentration is 3%;
Utilize solution electrostatic spraying apparatus, spinning voltage 21kV, receiving range is 15 ㎝; Ultra-high molecular mass polyethylene micropore film is laid on the receiving platform of electrostatic spraying apparatus, utilizes the PVDF solution prepared to spray;
Meanwhile, the spray time of control PVDF is 2min, and the microporous barrier obtained can be used as lithium battery diaphragm.
Embodiment 2, weighing 0.31gPVDF powder are as polymer, and dicyandiamide solution presses acetone: DMF (DMF)=3:2 mass ratio preparation, obtains the PVDF solution that mass concentration is 3%;
Utilize solution electrostatic spraying apparatus, spinning voltage 21kV, receiving range is 15 ㎝; Ultra-high molecular mass polyethylene micropore film is laid on the receiving platform of electrostatic spraying apparatus, utilizes the PVDF solution prepared to spray;
Meanwhile, the spray time of control PVDF is 4min, and the microporous barrier obtained can be used as lithium battery diaphragm.
Embodiment 3, weighing 0.31gPVDF powder are as polymer, and dicyandiamide solution presses acetone: DMF (DMF)=3:2 mass ratio preparation, obtains the PVDF solution that mass concentration is 3%;
Utilize solution electrostatic spraying apparatus, spinning voltage 21kV, receiving range is 15 ㎝; Ultra-high molecular mass polyethylene micropore film is laid on the receiving platform of electrostatic spraying apparatus, utilizes the PVDF solution prepared to spray;
Meanwhile, the spray time of control PVDF is 6min, and the microporous barrier obtained can be used as lithium battery diaphragm.
To be illustrated in figure 2 according to the present invention lift the discharge capacity curve synoptic diagram of ultra-high molecular mass polyethylene micropore film in lithium battery that three example modifications obtain; Be illustrated in figure 3 the cyclical stability curve synoptic diagram of this microporous barrier in lithium battery, from Fig. 2 and 3: the performance curve of the microporous barrier obtained when the spray time of control PVDF is respectively 2min, 4min and 6min, than the performance curve of microporous barrier not having modification, more excellent in discharge capacity and cyclical stability.
In sum, the ultra-high molecular mass polyethylene micropore film of the method modification provided by the embodiment of the present invention has the advantages such as higher porosity, higher charge/discharge capacity and good cycle performance; High porosity is conducive to lithium ion and passes freely through between both positive and negative polarity, the effect of isolation both positive and negative polarity can be played in the small size aperture of microporous barrier, and after being assembled into lithium ion battery, charge/discharge capacity is higher, and cyclical stability is good, the cycle performance of lithium battery is improved, and useful life extends.
The above; be only the present invention's preferably embodiment, but protection scope of the present invention is not limited thereto, is anyly familiar with those skilled in the art in the technical scope that the present invention discloses; the change that can expect easily or replacement, all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection range of claims.
Claims (10)
1. a method of modifying for ultra-high molecular mass polyethylene micropore film, is characterized in that, described method comprises:
Ultra-high molecular mass polyethylene micropore film is laid on the receiving platform of electrostatic spraying apparatus;
Described electrostatic spraying apparatus is utilized to carry out polymer spray treatment with the polymer spray coating liquor prepared in advance to described ultra-high molecular mass polyethylene micropore film;
Controlling the amount of described ultra-high molecular mass polyethylene micropore film surface micron particles by controlling spray time, obtaining modified ultra-high molecular mass polyethylene micropore film.
2. the method for modifying of ultra-high molecular mass polyethylene micropore film according to claim 1, is characterized in that,
Described ultra-high molecular mass polyethylene micropore film be adopt the molecular weight of polyethylene prepared of thermally induced phase separation be 800,000 ~ 1,000 ten thousand polyethene microporous membrane.
3. the method for modifying of ultra-high molecular mass polyethylene micropore film according to claim 1, it is characterized in that, the described polymer spray coating liquor prepared in advance specifically comprises:
Specific dissolution of polymer is prepared the polymer spray coating liquor obtained in solvent, the mass concentration of described polymer spray coating liquor is 0.1-15%.
4. the method for modifying of ultra-high molecular mass polyethylene micropore film according to claim 3, is characterized in that, the mass concentration of described polymer spray coating liquor is preferably: 3%.
5. the method for modifying of ultra-high molecular mass polyethylene micropore film according to claim 3, is characterized in that,
Described specific polymer comprises: the macromolecular material of the nanometer obtained by electrostatic spraying to micron particles that can be dissolved in solvent.
6. the method for modifying of ultra-high molecular mass polyethylene micropore film according to claim 3 or 5, it is characterized in that, described specific polymer comprises: Kynoar, the fine or polypropylene of polypropylene.
7. the method for modifying of ultra-high molecular mass polyethylene micropore film according to claim 3, is characterized in that,
Prepare the solvent that described polymer spray coating liquor adopts to comprise: the one in acetone, DMF, DMA, first alcohol and water or several arbitrarily.
8. the method for modifying of ultra-high molecular mass polyethylene micropore film according to claim 3 or 7, is characterized in that,
Prepare the solvent that described polymer spray coating liquor adopts to be preferably: by acetone and DMF formulated according to the mass ratio of 3:2.
9. the method for modifying of ultra-high molecular mass polyethylene micropore film according to claim 1, is characterized in that, carrying out in the process of polymer spray treatment to described ultra-high molecular mass polyethylene micropore film:
Spray voltage is 0.1-30kV, and receiving range is 15 ㎝.
10. the method for modifying of ultra-high molecular mass polyethylene micropore film according to claim 9, it is characterized in that, described spray voltage is preferably 21kV.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510012834.9A CN104600232B (en) | 2015-01-09 | 2015-01-09 | A kind of method of modifying of ultra-high molecular mass polyethylene micropore film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510012834.9A CN104600232B (en) | 2015-01-09 | 2015-01-09 | A kind of method of modifying of ultra-high molecular mass polyethylene micropore film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104600232A true CN104600232A (en) | 2015-05-06 |
| CN104600232B CN104600232B (en) | 2017-10-24 |
Family
ID=53125869
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510012834.9A Expired - Fee Related CN104600232B (en) | 2015-01-09 | 2015-01-09 | A kind of method of modifying of ultra-high molecular mass polyethylene micropore film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104600232B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105826505A (en) * | 2016-04-16 | 2016-08-03 | 佛山市南海区欣源电子有限公司 | Process for manufacturing diaphragm of wearable flexible battery |
| CN106268356A (en) * | 2015-05-20 | 2017-01-04 | 宁波大学 | A kind of Thermal inactive prepares the method for ultra-high molecular weight polyethylene composite hollow fibre |
| CN109485884A (en) * | 2018-11-02 | 2019-03-19 | 北京石油化工学院 | The preparation method of polyvinylidene difluoride film |
| CN110923954A (en) * | 2019-12-19 | 2020-03-27 | 广东工业大学 | High-molecular polymer fiber membrane with through hole structure and preparation method and application thereof |
| CN112259901A (en) * | 2019-07-03 | 2021-01-22 | 比亚迪股份有限公司 | Gluing diaphragm for lithium ion battery and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102218871A (en) * | 2011-04-14 | 2011-10-19 | 万向电动汽车有限公司 | Preparation method of modified diaphragm for lithium-ion secondary battery as well as product and preparation device thereof |
| CN102299287A (en) * | 2011-08-12 | 2011-12-28 | 沧州明珠塑料股份有限公司 | Composite nanometer fiber lithium ion battery diaphragm and preparation method thereof |
| CN102779964A (en) * | 2012-08-08 | 2012-11-14 | 龙能科技（苏州）有限公司 | Method for preparing multilayer composite membrane for secondary battery by using electrostatic spinning coating method |
| CN103137932A (en) * | 2013-03-04 | 2013-06-05 | 北京石油化工学院 | Microporous polymer isolating film having good wettability on electrolyte and preparation method |
-
2015
- 2015-01-09 CN CN201510012834.9A patent/CN104600232B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102218871A (en) * | 2011-04-14 | 2011-10-19 | 万向电动汽车有限公司 | Preparation method of modified diaphragm for lithium-ion secondary battery as well as product and preparation device thereof |
| CN102299287A (en) * | 2011-08-12 | 2011-12-28 | 沧州明珠塑料股份有限公司 | Composite nanometer fiber lithium ion battery diaphragm and preparation method thereof |
| CN102779964A (en) * | 2012-08-08 | 2012-11-14 | 龙能科技（苏州）有限公司 | Method for preparing multilayer composite membrane for secondary battery by using electrostatic spinning coating method |
| CN103137932A (en) * | 2013-03-04 | 2013-06-05 | 北京石油化工学院 | Microporous polymer isolating film having good wettability on electrolyte and preparation method |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106268356A (en) * | 2015-05-20 | 2017-01-04 | 宁波大学 | A kind of Thermal inactive prepares the method for ultra-high molecular weight polyethylene composite hollow fibre |
| CN105826505A (en) * | 2016-04-16 | 2016-08-03 | 佛山市南海区欣源电子有限公司 | Process for manufacturing diaphragm of wearable flexible battery |
| CN109485884A (en) * | 2018-11-02 | 2019-03-19 | 北京石油化工学院 | The preparation method of polyvinylidene difluoride film |
| CN109485884B (en) * | 2018-11-02 | 2021-07-09 | 北京石油化工学院 | Preparation method of polyvinylidene fluoride film |
| CN112259901A (en) * | 2019-07-03 | 2021-01-22 | 比亚迪股份有限公司 | Gluing diaphragm for lithium ion battery and preparation method and application thereof |
| CN112259901B (en) * | 2019-07-03 | 2022-03-18 | 比亚迪股份有限公司 | Gluing diaphragm for lithium ion battery and preparation method and application thereof |
| CN110923954A (en) * | 2019-12-19 | 2020-03-27 | 广东工业大学 | High-molecular polymer fiber membrane with through hole structure and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104600232B (en) | 2017-10-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104600232A (en) | Method for modifying ultra-high molecular weight polyethylene microporous film | |
| CN103413904B (en) | A kind of manufacture method of diaphragm for polymer lithium ion battery | |
| CN105576285B (en) | A kind of lithium ion battery anode glue size and its aqueous polyurethane/polyaniline bonding agent | |
| CN104201320A (en) | Method for pre-lithiating electrode material of lithium ion battery | |
| MY152442A (en) | Process for producing carbon particles for electrode, carbon particles for electrode, and negative-electrode material for lithium-ion secondary battery | |
| CN103682354A (en) | All-solid-state lithium ion battery composite electrode material and preparation method thereof and all-solid-state lithium ion battery | |
| CN109244332A (en) | Improve the lithium battery diaphragm of siliceous negative electrode material head effect and the lithium battery of production method, preparation | |
| US20190006677A1 (en) | Binder composition for non-aqueous secondary battery electrode, slurry composition for non-aqueous secondary battery electrode, non-aqueous secondary battery electrode, and non-aqueous secondary battery | |
| RU2014134028A (en) | CONCENTRATING INK COMPOSITION | |
| CN107068945A (en) | A kind of preparation method of lithium-sulfur cell composite diaphragm | |
| CN106972141A (en) | A kind of Ti3C2Tx/ graphene oxide/Celgard composite diaphragms | |
| CN104505553B (en) | A kind of lead-acid accumulator regenerated liquid concentrated solution and preparation method thereof | |
| CN102903974B (en) | Lithium-sulfur secondary battery | |
| CN104319361A (en) | Method for preparing composite diaphragm | |
| KR101742881B1 (en) | The coating composition contained ionic inorganic particles and membrane for redox flow battery using the same | |
| CN105870382B (en) | Lithium ion battery composite diaphragm and preparation method thereof | |
| KR20220018049A (en) | Adhesive-coated separator for lithium ion battery, method for preparing same, and use thereof | |
| KR20160051199A (en) | Electrode-adhesive layer composite, method of producing the same, and secondary battery comprising the same | |
| CN106876639A (en) | It is a kind of for the composite membrane of lithium metal secondary battery and its preparation and application | |
| Song et al. | TiO2 modified hen-egg-shell-membrane as separator for Li-ion batteries | |
| CN106192369A (en) | A kind of preparation method of nonwoven fabric base pvdf membrane | |
| CN103682256A (en) | Coating method for lithium titanate battery cathode piece | |
| CN106876637A (en) | A kind of Ti3C2Tx/PVDF/Celgard composite diaphragms | |
| CN103560276A (en) | Reactive polymer electrolyte and water-based lithium ion battery membrane electrode assembly thereof | |
| CN106981635A (en) | A kind of Nafion membrane/Ti3C2Tx/ sulphur composite |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into 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: 20171024 Termination date: 20210109 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |