CN106653400A - Flexible composite electrode material preparation method - Google Patents

Flexible composite electrode material preparation method Download PDF

Info

Publication number
CN106653400A
CN106653400A CN201611235311.1A CN201611235311A CN106653400A CN 106653400 A CN106653400 A CN 106653400A CN 201611235311 A CN201611235311 A CN 201611235311A CN 106653400 A CN106653400 A CN 106653400A
Authority
CN
China
Prior art keywords
mwcnt
electrode material
composite electrode
mixture
flexible composite
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
Application number
CN201611235311.1A
Other languages
Chinese (zh)
Other versions
CN106653400B (en
Inventor
张娜
房永征
丁艳花
张小磊
刘玉峰
刘静慧
卢诗琦
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Institute of Technology
Original Assignee
Shanghai Institute of Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shanghai Institute of Technology filed Critical Shanghai Institute of Technology
Priority to CN201611235311.1A priority Critical patent/CN106653400B/en
Publication of CN106653400A publication Critical patent/CN106653400A/en
Application granted granted Critical
Publication of CN106653400B publication Critical patent/CN106653400B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/46—Metal oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/48—Conductive polymers
    • 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
    • Y02E60/13—Energy storage using capacitors

Abstract

The present invention provides a flexible composite electrode material preparation method. The method comprises first, using an ozone oxidation method to purify and acidify the multi-walled carbon nanotube so as to obtain the functionalized f-MWCNT; weighing f-MWCNT, KMnO4 and aniline proportionally; dispersing the weighed raw material in deionized water, carrying out ultrasonic treatment, and obtaining an evenly dispersed precursor mixture; and transferring the obtained mixture into a water heating kettle, heating the mixture to 160 DEG C to 200 DEG C, and staying the mixture for 15-24 hours, carrying out suction filtration and washing on the mixture, and drying the mixture to obtain the MWCNT/MnO2/PANI composite electrode material. The flexible composite electrode material obtained by using the method provided by the present invention has good capacitance property, small impedance, and small pressure drop; the maximum specific capacitance of the flexible composite electrode material can be 364.1F/g, and after 1000 cycles, the specific capacitance remains 87.3% of the original; and the flexible composite electrode material can be used for electrodes of supercapacitors and ion batteries, and can be used for electrocatalysts of lithium-air batteries.

Description

A kind of preparation method of flexible composite electrode material
Technical field
The invention belongs to materialogy field, is related to a kind of inorganic-organic composite material, a kind of specifically flexible compound The preparation method of electrode material.
Background technology
With the further development of society, environment and energy problem become increasingly to project.Therefore people are in the urgent need to one Plant environmental friendliness and continuable energy storage form.Used as a kind of emerging energy storage device, ultracapacitor is electrochemistry electricity Container, is a kind of new type of energy storage device between traditional capacitor and secondary cell.Compared with traditional capacitor, electrochemistry Capacitor has higher specific capacity, and storable specific energy is 10-100 times of traditional capacitor；Compared with battery, with than The advantages of power is high, energy density is big, the charging interval is short, discharging efficiency is high and has extended cycle life.In mechanics of communication, electric automobile There is application prospect of crucial importance and wide with the field such as Aero-Space science and techniques of defence.
The capacitive property of ultracapacitor depends primarily on electrode material, currently used for the material of electric chemical super capacitor Mainly there are three classes, various material with carbon elements；The oxide of transition metal oxide, such as ruthenic oxide, manganese dioxide and nickel；It is conductive Polymeric material etc..Material with carbon element is to realize energy storage using the interfacial electric double layer formed between electrode and electrolyte, this Plant energy storage carries out activation polarization to realize by electrolyte solution, does not produce electrochemical reaction, therefore with good Cyclical stability well and higher specific power density, and CNT is the one-dimensional tubular nanometer knot curled into by Graphene Structure, with sp between carbon atom therein2Hybrid form is bonded so that CNT had both had very high mechanical strength, it may have Very high electrical conductivity and chemical property, are a kind of advanced flexible energy storage materials, but due to low specific capacitance and energy it is close Degree limits its application in practice., used as one kind of Typical transition metal oxide, extensively, price is low for resource for manganese dioxide Honest and clean, friendly to environment, electro-chemical activity is high, and theoretical specific capacitance can reach 1370F/g, be a kind of very promising electrode material Material, but its relatively low electric conductivity limits its practical application.Conducting polymer is to utilize redox reaction, it is doped and Doped mutual change is gone to bring storage energy, therefore conducting polymer is not only all present in interface but also in whole volume Highdensity electric charge, with big specific capacitance, and there is polyaniline raw material to be easy to get, and convieniently synthesized, conductance is high, unique doping machine Processed the characteristics of, there is very big development potentiality in conducting high polymers thing field, but because it is in energy storage process Redox reaction causes cyclical stability very poor, hinders its application in practice.It follows that the carbon materials of one-component When material is used as ultracapacitor, specific capacitance is not high；The metal oxide of one-component be used as ultracapacitor when, conductance compared with Low, electrochemistry cyclicity is undesirable；When the conducting polymer of one-component is used as ultracapacitor, cyclical stability is poor.In order to Overcome the shortcomings of that above homogenous material is present, be badly in need of research and development multi-element composite material to improve the performance of ultracapacitor.
At present, one kind is disclosed in patent CN102280263A using carbon nanotube/manganese oxide composite material as electrode Electrochemical capacitor, the composite using magnetron sputtering and chemical vapor deposition method synthesis, and more single oxygen Change manganese electrode and have that electric conductivity is higher and the higher advantage of specific capacitance, but the method not only high cost, complicated process of preparation, and Should not accomplish scale production.
A kind of superhigh-capacitance capacitor with composite carbon nanotube is disclosed in patent CN1388540A, the electrode is adopted Prepared with six kinds of materials：CNT and transition metal oxide compound, CNT and conducting polymer series compound, CNT is with transition metal oxide, conducting polymer while combination product, CNT and transition metal oxide, activity Simultaneously combination product, CNT and conducting polymer series, activated carbon are serial while combination product or CNT for charcoal series With transition metal oxide, conducting polymer, activated carbon series while combination product.But the metal oxygen used by above-mentioned compound Compound is only the oxide of nickel and cobalt, and does not investigate the chemical property of composite nano materials so as in actual applications Feasibility it is hindered.
The content of the invention
For above-mentioned technical problem of the prior art, the invention provides a kind of preparation side of flexible composite electrode material Method, the preparation method of described this flexible composite electrode material will solve the preparation cost of ultracapacitor in prior art The relatively low technical problem of height, complex process, specific capacitance.
The invention provides a kind of preparation method of flexible composite electrode material, comprises the steps：
1) a step of Ozonation prepares the f-MWCNT of functionalization, is dispersed in trifluoroacetic acid molten by multi-walled carbon nano-tubes In liquid, the material ratio of multi-walled carbon nano-tubes and trifluoroacetic acid solution is 0.1g：20 ~ 40mL, Bubbling method be passed through flow for 30 ~ The ozone of 50ml/min, after being heated to reflux 10 ~ 15h at 70 ~ 90 DEG C, obtains the f-MWCNT of functionalization；
2) f-MWCNT, KMnO are weighed4And aniline, f-MWCNT, KMnO4It is (0.05～0.08) g with the material ratio of aniline: (0.1～0.3) g:(200～500) μ L；
3) by step 2）In the stock dispersion that weighs in deionized water, 30～60min of ultrasound obtains finely dispersed presoma Mixed liquor；
4) by step 3）Gained presoma mixed liquor is proceeded in water heating kettle, is heated to 160～200 DEG C, and is kept after 15～24h, Suction filtration, washing, drying to obtain MWCNT/MnO2/ PANI combination electrode materials.
The present invention utilizes simple one kettle way, prepares multi-walled carbon nano-tubes/manganese dioxide/polyaniline ternary flexible compound Electrode material.This composite couples three kinds of conventional electrode material for super capacitor, polyaniline（PANI）With good Electric conductivity can strengthen the utilization rate of CNT/manganese dioxide active material；CNT/manganese dioxide is not only composite wood Material rigidity plays a supportive role, and electronics can be promoted axially to convey, and so can both utilize the electric double layer electricity of carbon Holding can utilize the Faraday pseudo-capacitance of manganese dioxide and polyaniline again, and collaboration plays the chemical property of three, so as to have Effect improves the specific capacity of ultracapacitor.
The method for preparing combination electrode material of the present invention is simple, can be completed using one kettle way, the KMnO of employing4Itself Used as oxidant, without others reductant-oxidant, environmental friendliness, equipment requirement is low, can carry out under lower temperature conditions, Short preparation period, is adapted to industrialized production.The present invention can be used for the electrode material of ultracapacitor and ion battery, lithium-air The elctro-catalyst of battery.Such electrode material has preferable capacitive properties, and impedance is little, and pressure drop is little, and highest specific capacitance is reachable 364.1F/g, after circulating 1000 times, specific capacitance remains in that original 87.3%.
The present invention prepares CNT/manganese dioxide/polyaniline trielement composite material using one kettle way, i.e., using simple Synthetic technology prepares high-performance super capacitor electrode material.Three kinds of unitary electrode materials are overcome in supercapacitor applications side Deficiency on face, gives full play to the synergy of material with carbon element, transition metal oxide and conducting polymer, and advantage is mutually tied Close, defect mutually weakens, and drastically increases the chemical property of material.
The present invention is compared with prior art, and its technological progress is significant.CNT/the manganese dioxide of the present invention/poly- Aniline trielement composite material, its preparation process is simple is controllable, low temperature, quick, condition more gentle, equipment requirement is low, raw material into This is cheap, and after assembling, gained composite has good cycle performance and high-specific capacitance super, is a kind of preferably super Capacitor electrode material, is especially suitable for industrialized production.
Description of the drawings
Fig. 1 is the SEM figures of the gained CNT of embodiment 1/manganese dioxide/polyaniline ternary composite electrode material.
Specific embodiment
Embodiment 1
1) Ozonation prepares the f-MWCNT of functionalization, by multi-walled carbon nano-tubes 0.1g, is dispersed in 30mL trifluoroacetic acid solutions In, Bubbling method is passed through the ozone that flow is 40ml/min, after being heated to reflux 12h at 80 DEG C, obtains the f-MWCNT of functionalization；
2) f-MWCNT, KMnO are weighed4And aniline, f-MWCNT, KMnO4It is 0.066g with the material ratio of aniline:0.15g :200μ L；
3) by step 2）In the stock dispersion that weighs in 40 ml deionized waters, ultrasonic 60min obtains finely dispersed forerunner Body mixed liquor；
4) by step 3）Gained presoma mixed liquor is proceeded in water heating kettle, is heated to 180 DEG C, and is kept after 24h, suction filtration, washing, Drying to obtain MWCNT/MnO2/ PANI combination electrode materials.
Pattern test, acquired results such as Fig. 1 are carried out to products obtained therefrom using Hitachi S-4800.MnO2For bar-shaped, carbon nanometer Wherein, macromolecule PANI has higher adhesive effect to uniform point of pipe, and three is formed into stable complex.
Using the chemical property of CHI660E model electrochemical workstation test samples.With constant current charge charging method Under 0.5A/g current densities, specific capacitance is measured for 364.1F/g.
Embodiment 2
1) Ozonation prepares the f-MWCNT of functionalization, by multi-walled carbon nano-tubes 0.1g, is dispersed in 30mL trifluoroacetic acid solutions In, Bubbling method is passed through the ozone that flow is 40ml/min, after being heated to reflux 12h at 80 DEG C, obtains the f-MWCNT of functionalization；
2) f-MWCNT, KMnO are weighed4And aniline, f-MWCNT, KMnO4It is 0.066g with the material ratio of aniline: 0.15g : 300μL；
3) by step 2）In the stock dispersion that weighs in 40 ml deionized waters, ultrasonic 60min obtains finely dispersed forerunner Body mixed liquor；
4) by step 3）Gained presoma mixed liquor is proceeded in water heating kettle, is heated to 180 DEG C, and is kept after 24h, suction filtration, washing, Drying to obtain MWCNT/MnO2/ PANI combination electrode materials.
Using the chemical property of CHI660E model electrochemical workstation test samples.With constant current charge charging method Under 0.5 A/g current densities, specific capacitance is measured for 317.3 F/g.
Embodiment 3
1) Ozonation prepares the f-MWCNT of functionalization, by multi-walled carbon nano-tubes 0.1g, is dispersed in 30mL trifluoroacetic acid solutions In, Bubbling method is passed through the ozone that flow is 40ml/min, after being heated to reflux 12h at 80 DEG C, obtains the f-MWCNT of functionalization；
2) f-MWCNT, KMnO are weighed4And aniline, f-MWCNT, KMnO4It is 0.066g with the material ratio of aniline:0.15g :400μ L；
3) by step 2）In the stock dispersion that weighs in 40ml deionized waters, ultrasonic 60min obtains finely dispersed presoma Mixed liquor；
4) by step 3）Gained presoma mixed liquor is proceeded in water heating kettle, is heated to 180 DEG C, and is kept after 24h, suction filtration, washing, Drying to obtain MWCNT/MnO2/ PANI combination electrode materials.
Using the chemical property of CHI660E model electrochemical workstation test samples.With constant current charge charging method Under 0.5A/g current densities, specific capacitance is measured for 308.9 F/g.

Claims (1)

1. a kind of preparation method of flexible composite electrode material, it is characterised in that comprise the steps：
1）The step of one Ozonation prepares the f-MWCNT of functionalization, is dispersed in trifluoroacetic acid molten by multi-walled carbon nano-tubes In liquid, the material ratio of multi-walled carbon nano-tubes and trifluoroacetic acid solution is 0.1g：20 ~ 40mL, Bubbling method be passed through flow for 30 ~ The ozone of 50ml/min, after being heated to reflux 10 ~ 15h at 70 ~ 90 DEG C, obtains the f-MWCNT of functionalization；
2）Weigh f-MWCNT, KMnO4And aniline, f-MWCNT, KMnO4It is (0.05～0.08) g with the material ratio of aniline: (0.1～0.3) g:(200～500) μ L；
3）By step 2）In the stock dispersion that weighs in deionized water, 30～60min of ultrasound obtains finely dispersed presoma Mixed liquor；
4）By step 3）Gained presoma mixed liquor is proceeded in water heating kettle, is heated to 160～200 DEG C, and is kept after 15～24h, Suction filtration, washing, drying to obtain MWCNT/MnO2/ PANI combination electrode materials.
CN201611235311.1A 2016-12-28 2016-12-28 A kind of preparation method of flexible composite electrode material Expired - Fee Related CN106653400B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201611235311.1A CN106653400B (en) 2016-12-28 2016-12-28 A kind of preparation method of flexible composite electrode material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201611235311.1A CN106653400B (en) 2016-12-28 2016-12-28 A kind of preparation method of flexible composite electrode material

Publications (2)

Publication Number Publication Date
CN106653400A true CN106653400A (en) 2017-05-10
CN106653400B CN106653400B (en) 2018-11-13

Family

ID=58832227

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201611235311.1A Expired - Fee Related CN106653400B (en) 2016-12-28 2016-12-28 A kind of preparation method of flexible composite electrode material

Country Status (1)

Country Link
CN (1) CN106653400B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108461726A (en) * 2018-03-12 2018-08-28 陕西科技大学 A kind of polycrystalline manganese dioxide/carbon nanotube composite material and its preparation method and application

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101547858A (en) * 2006-10-18 2009-09-30 新加坡科技研究局 Method of functionalizing a carbon material
CN105244186A (en) * 2015-10-15 2016-01-13 扬州大学 Preparation method of carbon-based ternary complex

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101547858A (en) * 2006-10-18 2009-09-30 新加坡科技研究局 Method of functionalizing a carbon material
US20110053050A1 (en) * 2006-10-18 2011-03-03 Agency For Science, Technology And Research Method of functionalizing a carbon material
CN105244186A (en) * 2015-10-15 2016-01-13 扬州大学 Preparation method of carbon-based ternary complex

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
李立: "基于碳纳米管构筑用作超级电容器电极的纳米复合材料", 《中国优秀硕士学位论文全文数据库工程科技II辑》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108461726A (en) * 2018-03-12 2018-08-28 陕西科技大学 A kind of polycrystalline manganese dioxide/carbon nanotube composite material and its preparation method and application
CN108461726B (en) * 2018-03-12 2020-09-29 陕西科技大学 Polycrystalline manganese dioxide/carbon nanotube composite material and preparation method and application thereof

Also Published As

Publication number Publication date
CN106653400B (en) 2018-11-13

Similar Documents

Publication Publication Date Title
Zhao et al. Bi-interface induced multi-active MCo2O4@ MCo2S4@ PPy (M= Ni, Zn) sandwich structure for energy storage and electrocatalysis
Liu et al. Realizing superior electrochemical performance of asymmetric capacitors through tailoring electrode architectures
CN101527202B (en) Oxidized grapheme/polyaniline super capacitor composite electrode material and preparation method
CN102568855B (en) Carbon material-loading manganese dioxide nanowire array composite and method for producing same
CN101599370B (en) Method for fast preparing conductive carbon/manganese dioxide composite electrode material
CN110581029B (en) Ternary composite electrode, preparation method thereof and application thereof in electroadsorption
Zolfaghari et al. Electrochemical study on zeolitic imidazolate framework-67 modified MnFe2O4/CNT nanocomposite for supercapacitor electrode
CN104021948B (en) Nanofiber-shaped three-dimensional nickel hydroxide/carbon nanotube composite material as well as preparation method and application thereof
CN106548876A (en) The carbon nano pipe array of superficial oxidation/graphene/manganese dioxide composite material electrode and its preparation method and application
CN106710885A (en) Nickel selenide/carbon nanotube composite nanometer material and preparation and application thereof
CN109767924A (en) A kind of LDH based super capacitor combination electrode material and preparation method and purposes
CN106067385B (en) The preparation method of manganese dioxide as ultracapacitor/conductive polymer nanometer network structure electrode material
CN105788884A (en) Preparation method of manganese dioxide/carbon paper composite electrode for super capacitor
Ahmed et al. Critical review on recent developments in conducting polymer nanocomposites for supercapacitors
Prasankumar et al. Functional carbons for energy applications
Li et al. Unique 3D bilayer nanostructure basic cobalt carbonate@ NiCo–layered double hydroxide nanosheets on carbon cloth for supercapacitor electrode material
Chen et al. High-performanced flexible solid supercapacitor based on the hierarchical MnCo2O4 micro-flower
CN105788881B (en) A kind of preparation method of nitrogen doped corrugated carbon nanotube
Lu et al. Reduced-graphene-oxide-modified self-supported NiSe2 nanospheres on nickel foam as a battery-type electrode material for high-efficiency supercapacitors
Liu et al. Hexadecyl trimethyl ammonium bromide assisted growth of NiCo 2 O 4@ reduced graphene oxide/nickel foam nanoneedle arrays with enhanced performance for supercapacitor electrodes
Guo et al. An excellent cycle performance of asymmetric supercapacitor based on ZIF-derived C/N-doped porous carbon nanostructures
Luo et al. From powders to freestanding electrodes: Assembly active particles into bacterial cellulose for high performance supercapacitors
Yang et al. Enhanced functional properties of porous carbon materials as high-performance electrode materials for supercapacitors
Teng et al. A novel copper nanoparticles/bean dregs-based activated carbon composite as pseudocapacitors
Meghanathan et al. Metal-organic framework-derived Nickle Tellurideporous structured composites electrode materials for asymmetric supercapacitor application

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for 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: 20181113

CF01 Termination of patent right due to non-payment of annual fee