CN103864069B - A kind of with discontinuous tube wall carbon nanotube for the method for Graphene prepared by raw material - Google Patents

A kind of with discontinuous tube wall carbon nanotube for the method for Graphene prepared by raw material Download PDF

Info

Publication number
CN103864069B
CN103864069B CN201410115856.3A CN201410115856A CN103864069B CN 103864069 B CN103864069 B CN 103864069B CN 201410115856 A CN201410115856 A CN 201410115856A CN 103864069 B CN103864069 B CN 103864069B
Authority
CN
China
Prior art keywords
tube wall
graphene
carbon pipe
carbon nanotube
raw material
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.)
Expired - Fee Related
Application number
CN201410115856.3A
Other languages
Chinese (zh)
Other versions
CN103864069A (en
Inventor
李德军
冯建民
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.)
Tianjin Normal University
Original Assignee
Tianjin Normal University
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 Tianjin Normal University filed Critical Tianjin Normal University
Priority to CN201410115856.3A priority Critical patent/CN103864069B/en
Publication of CN103864069A publication Critical patent/CN103864069A/en
Application granted granted Critical
Publication of CN103864069B publication Critical patent/CN103864069B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Abstract

The invention discloses a kind of with discontinuous tube wall carbon nanotube for the method for Graphene prepared by raw material.Comprise: with discontinuous tube wall carbon nanotube for raw material, adopt strong oxidizer expansion partition method, obtain graphene oxide, obtain Graphene by reduction treatment; Wherein said discontinuous tube wall carbon nanotube is Bamboo-shaped carbon pipe, herring-bone form carbon pipe.Described strong oxidizer is the mixture of mineral acid and potassium permanganate.The invention has the advantages that and adopt the carbon pipe of discontinuous tube wall to be raw material; the graphite linings of composition carbon tube wall is interrupted; and size is at Nano grade; it is short that strong oxidizer diffuses into oxidation expansion distance; required time is few; the preparation of high efficiency Graphene can be realized, be conducive to mass-producing and prepare Graphene.

Description

A kind of with discontinuous tube wall carbon nanotube for the method for Graphene prepared by raw material
Present patent application obtains the subsidy of Tianjin application foundation and cutting edge technology research plan (Natural Science Fund In The Light) emphasis Funded Projects (13JCZDJC33900) and National Nature fund general project (51272176).
Technical field
The present invention relates to a kind of with discontinuous tube wall carbon nanotube for the method for Graphene prepared by raw material, belong to technical field of graphene preparation.
Background technology
Graphene has excellent electricity, and mechanical property and other functional performance, can be applicable to the fields such as high performance composite, electrochemical capacitance and battery.The preparation method of current Graphene can be divided into by process: from top to bottom and from bottom to top.Mainly adopt strong oxidizer to be separated by graphite expansion from top to bottom and obtain graphene oxide, it is rare that then reduction obtains graphite.Be adopt carbon compound, pyrolysis under high temperature from bottom to top, under metal catalyst katalysis, in metallic surface, growth forms Graphene.Two kinds of processes are compared, and are easier to large-scale production from top to bottom, but the preparation process time of Graphene is long, and efficiency is low, are the major obstacles of puzzlement Graphene industrialization.
In the preparation process of Graphene, to diffuse into the expansion process of graphite linings consuming time the longest for strong oxidizer, is the major cause causing Graphene preparation efficiency.Based on this, the application is with discontinuous tube wall carbon pipe for raw material, and utilize strong oxidizer the discontinuous graphite linings of composition carbon tube wall to be opened, obtain graphene oxide, reduction obtains Graphene.
Be with the key that discontinuous tube wall carbon pipe can realize efficiently preparing Graphene for raw material, form discontinuous carbon tube wall graphite linings scantlings of the structure (5-500 nanometer) between several nanometer to hundreds of nanometer, and the raw materials graphite that current Graphene generally adopts, size is generally at micron order (1-10 micron).Strong oxidizer diffusion length with enter compared with micron order graphite diffusion distance at present, there is the difference of the order of magnitude.Therefore with discontinuous tube wall carbon pipe for Graphene prepared by raw material, strong oxidizer diffusion length is short, and expansion separation needs the time short, thus effectively can improve the preparation efficiency of Graphene.
Although there is report carbon pipe being cast aside preparation graphene band before this, is that the carbon pipe with continuous tube wall is processed, is different from the application.And the tube wall due to continuous carbon pipe is complete graphite-structure, be difficult to open, opening procedure complex process, elapsed time is long, and efficiency is low.
Summary of the invention
To the object of the present invention is to provide with discontinuous tube wall carbon nanotube as the method for Graphene prepared by raw material, it is characterized in that improve Graphene preparation efficiency, reduce preparation cost, be conducive to suitability for industrialized production.
For achieving the above object, the present invention is realized by following technical proposals:
With discontinuous tube wall carbon nanotube for the method for Graphene prepared by raw material, it is characterized in that it is with discontinuous tube wall carbon nanotube for raw material, adopt strong oxidizer expansion partition method, obtain graphene oxide, obtain Graphene by reduction treatment; Wherein said discontinuous tube wall carbon nanotube, refers to that the tube wall of carbon pipe is made up of interrupted graphite linings, is typically Bamboo-shaped carbon pipe or herring-bone form carbon pipe; Described strong oxidizer is the mixture of mineral acid and potassium permanganate.
Carbon pipe described in claim comprises common carbon pipe and nitrogen-doped carbon pipe.Described Graphene comprises common graphite alkene and nitrogen-doped graphene.
The preferred preparation method of the present invention, it is characterized in that described oxidation expansion partition method is mixed with potassium permanganate by discontinuous tube wall carbon nanotube, mixing solutions is mixed to form again with mineral acid, control solution temperature 30-60 oC, magnetic agitation 2-6 h, mixing solutions is directed on ice cube, ice cube dissolves, drip 30% hydrogen peroxide and become yellow to solution, centrifugation obtains graphene oxide suspension, settlement separate, add hydrochloric acid and distilled water successively, centrifuge washing pH value of solution is to 6-8, be separated and obtain graphene oxide, dry, in 1000 oC argon gas stream, reduction obtains Graphene.Wherein said mineral acid comprises sulfuric acid and the mixture with phosphoric acid thereof.
The proportioning of described mineral acid and carbon pipe is 1.0 g with carbon pipe quality, corresponding mineral acid volume 100 ml to 500 ml; Potassium permanganate and carbon pipe proportioning, with carbon pipe quality for 1, corresponding potassium permanganate and carbon pipe quality are between 4 to 7.Described mineral acid and potassium permanganate mixture, be typically phosphoric acid, sulfuric acid and potassium permanganate mixture, and wherein phosphoric acid is 1, and sulfuric acid and phosphoric acid volume ratio are 5 to 10, potassium permanganate and mineral acid proportioning, potassium permanganate 1.0 g, and corresponding mineral acid is 30-300 ml.
With discontinuous tube wall carbon pipe for raw material, adopt strong oxidizer to expand and be oxidized partition method, obtain graphene oxide, obtain Graphene by reduction treatment.Described discontinuous tube wall carbon pipe is ring carbon pipe, also can be herring-bone form carbon pipe and other has the carbon pipe of discontinuous structural pipe wall feature; Described strong oxidizer is the mixture of mineral acid and strong oxidizer, is typically sulfuric acid, phosphoric acid and potassium permanganate mixture.
The present invention can the high-level efficiency key of the preparing Graphene carbon pipe that is have employed discontinuous tube wall be the raw material preparing Graphene, the tube wall graphite linings size forming carbon pipe is little, as formed the graphite flake layer size of ring carbon pipe at 5-500 nm, form the graphite flake layer size of herring-bone form carbon pipe at 3-50 nm, and the graphite flake layer size of flaky graphite is at 1000-3000 nm, even larger.And the intercalation that the oxidation preparation process of Graphene is first mineral acid enters between graphite flake layer, then obtain graphene oxide with strong oxidizer oxidation, reduction obtains Graphene.Wherein intercalation process is key prepared by Graphene, is also part the most consuming time.Shortening mineral acid and strong oxidizer diffuse into the distance of graphite linings, are the keys improving Graphene preparation efficiency.
Simultaneous test is as follows:
The graphene product feature that the present invention is prepared for raw material with discontinuous tube wall carbon nanotube is as follows:
(1) size is little, is generally less than 500 nm;
(2) surface folding defect is many;
(3) between constituent structure and carbon pipe, there is inheritance, by controlling for control realization constituent structure carbon control.
The invention reside in provide a kind of with discontinuous tube wall carbon nanotube for the method for Graphene efficiently prepared by raw material, reduce Graphene preparation cost, promote Graphene commercial application.The method synthesizing graphite alkene has the feature that size is little, activity is high and structure is adjustable.
Accompanying drawing explanation
Fig. 1: the transmission electron microscope picture of the ring carbon pipe that the invention process example uses;
Fig. 2: the high power transmission electron microscope picture of the ring carbon pipe that the invention process example uses;
Fig. 3: the x-ray photoelectron energy spectrogram of the nitrogenous ring carbon pipe that the invention process example uses;
Fig. 4: the invention process example 1 obtains the transmission electron microscope picture of product.
Embodiment
Below in conjunction with embodiment, the present invention is described, the scheme of embodiment described here, do not limit the present invention, one of skill in the art can make improvements and change according to spirit of the present invention, described these improve and change all should be considered as in scope of the present invention, and the requirement of all having the right of scope of the present invention and essence limits; Wherein said ring carbon nanotube and nitrogenous ring carbon pipe synthesis specifically see ( feng et al., Mater. Sci. Eng.A. 473,238 (2008).), herring-bone form carbon pipe synthesis see ( i. Martin-Gullon et al., Carbon. 44,1572 (2006)), the reagent used by other is by commercially available.
Embodiment 1:
Synthesis ring carbon pipe, take ring carbon nanotube 0.29 g, potassium permanganate 1.74 g, mixing, put into there-necked flask, successively add 10 ml phosphoric acid and 90 ml sulfuric acid, water-bath 50 oC, magnetic agitation 4 h, is directed at mixing solutions on ice cube, ice cube dissolves, drip hydrogen peroxide 5 ml, centrifugation obtains graphene oxide suspension, settlement separate, add 10% hydrochloric acid 800ml successively and distilled water 1200 ml washs solution ph to 5-7, centrifugation obtains graphene oxide, dry, and in 1000oC argon gas stream, reduction obtains Graphene.
Embodiment 2:
With example 1, the amount changing phosphoric acid and sulfuric acid is 10 ml phosphoric acid and 50 ml sulfuric acid, obtains Graphene.
Embodiment 3:
With example 1, the amount changing phosphoric acid and sulfuric acid is 10 ml phosphoric acid and 100 ml sulfuric acid, obtains Graphene.
Embodiment 4:
With example 1, change potassium permanganate is 2.03g, obtains Graphene.
Embodiment 5:
With example 1, change potassium permanganate is 1.16g, obtains Graphene.
Embodiment 6:
Synthesis ring carbon pipe, claim 20 g sulfuric acid, pour beaker into, claim 1.0 g bamboo-like carbon nano tubes, slowly pour beaker into, ice bath stirs 30 min, slow gradation adds 3.0g potassium permanganate, stir 50 min, ice bath changes 35 oC water-baths, continues stirring 30 min, syringe is utilized to inject 45 ml distilled water, stir 15 min, then inject the hydrogen peroxide of 3.5 ml 30% and the distilled water of 26.5 ml successively respectively, centrifugation, three times are cleaned respectively with hydrochloric acid and distilled water, obtain graphene oxide, dry, in 1000 oC argon gas stream, reduction obtains Graphene.
Embodiment 7:
Synthesis herring-bone form carbon pipe, take fish-bone carbon nanotube 0.29 g, potassium permanganate 1.74 g, mixing, put into there-necked flask, successively add 10 ml phosphoric acid and 90 ml sulfuric acid, water-bath 50 oC, magnetic agitation 4 h, is directed at mixing solutions on ice cube, ice cube dissolves, drip hydrogen peroxide 5 ml, centrifugation obtains graphene oxide suspension, settlement separate, add 10% hydrochloric acid 800 ml successively and distilled water 1200 ml washs solution ph to 5-7, centrifugation obtains graphene oxide, dry, and in 1000 oC argon gas stream, reduction obtains Graphene.
Embodiment 8:
Synthesize nitrogenous ring pipe, take nitrogenous ring carbon nanotube 0.29 g, potassium permanganate 1.74 g, mixing, put into there-necked flask, successively add 10 ml phosphoric acid and 90 ml sulfuric acid, water-bath 50 oC, magnetic agitation 4 h, is directed at mixing solutions on ice cube, ice cube dissolves, drip hydrogen peroxide 5 ml, centrifugation obtains graphene oxide suspension, settlement separate, add 10% hydrochloric acid 800 ml successively and distilled water 1200 ml washs solution ph to 5-7, centrifugation obtains graphene oxide, dry, and in 1000 oC argon gas stream, reduction obtains Graphene.
Embodiment 9:
Simultaneous test
The control of ring carbon is for Graphene
Take ring carbon nanotube 1.50 g, potassium permanganate 9.0 g, mixing, put into there-necked flask, successively add 20 ml phosphoric acid and 180 ml sulfuric acid, water-bath 50 oC, magnetic agitation 4 h, be directed at by mixing solutions on ice cube, ice cube dissolves, and drips hydrogen peroxide 5.0 ml, centrifugation obtains graphene oxide suspension, settlement separate, add 10% hydrochloric acid 800 ml successively and distilled water 1200 ml washs solution ph to 5-7, centrifugation obtains graphene oxide, drying, in 1000 oC argon gas stream, reduction obtains Graphene.
Preparing graphite alkene
Take crystalline flake graphite 0.50 g, potassium permanganate 9.0 g, mixing, put into there-necked flask, successively add 20 ml phosphoric acid and 180 ml sulfuric acid, water-bath 50 oC, magnetic agitation 4 h, be directed at by mixing solutions on ice cube, ice cube dissolves, and drips hydrogen peroxide 5ml, centrifugation, obtaining product is graphene oxide and the mixture not being fully oxidized the graphite granule be separated that expands.
The carbon control of continuous tube wall is for Graphene
Take multi-walled carbon nano-tubes 1.50 g, potassium permanganate 9.0 g, mixing, puts into there-necked flask, successively adds 20 ml phosphoric acid and 180 ml sulfuric acid, water-bath 50 oC, magnetic agitation 4 h, is directed at mixing solutions on ice cube, and ice cube dissolves, drip hydrogen peroxide 5 ml, centrifugation, adds 10% hydrochloric acid 800 ml successively and distilled water 1200 ml washs solution ph to 5-7, and centrifugation obtains product observation and is still mainly carbon nanotube.
Embodiment 10
Graphene product prepared by the present invention is applied to lithium cell, get this product 0.85 g, add conductive agent 0.10 g acetylene black, 0.05 g polyfluortetraethylene of binding element (PTFE), ground and mixed is even, on steel plate, flakiness is rolled with rod iron, diameter 10 about mm is washed into steel drift, the thin rounded flakes of weight 2-10 mg, as lithium battery electrode plate packed battery, be to electrode with lithium sheet, be assembled into button cell, when charge-discharge velocity is 40 mAh/g, battery initial discharge capacity is at 800-1600 mAh/g, stable circulation charge/discharge capacity is at 500-900 mAh/g, with current with compared with commercial graphite theoretical capacity 372 mAh/g that is electrode material, there is clear superiority.

Claims (2)

1. with discontinuous tube wall carbon nanotube for the method for Graphene prepared by raw material, it is characterized in that it is with discontinuous tube wall carbon nanotube for raw material, adopt strong oxidizer expansion partition method, obtain graphene oxide, obtain Graphene by reduction treatment; Wherein said discontinuous tube wall carbon nanotube, refer to that the tube wall of carbon pipe is made up of interrupted graphite linings, described strong oxidizer is the mixture of mineral acid and potassium permanganate;
Described discontinuous tube wall carbon nanotube is Bamboo-shaped carbon pipe or herring-bone form carbon pipe;
Described carbon pipe comprises common carbon pipe and nitrogen-doped carbon pipe; The proportioning of mineral acid and carbon pipe, with carbon pipe quality for 1g, corresponding mineral acid volume 100 ml to 500 ml; Potassium permanganate and carbon pipe proportioning, with carbon pipe quality for 1, corresponding potassium permanganate and carbon pipe quality are that Graphene is common graphite alkene or nitrogen-doped graphene between 4 to 7;
Described Strong oxdiative expansion partition method is mixed with potassium permanganate by discontinuous tube wall carbon nanotube, mixing solutions is mixed to form again with mineral acid, control solution temperature 30-60oC, magnetic agitation 2-6 h, mixing solutions is directed on ice cube, ice cube dissolves, drip 30% hydrogen peroxide and become yellow to solution, centrifugation obtains graphene oxide suspension, settlement separate, adds hydrochloric acid and distilled water successively, centrifuge washing pH value of solution is to 6-8, be separated and obtain graphene oxide, dry, in 1000 DEG C of argon gas stream, reduction obtains Graphene.
2. preparation method according to claim 1, wherein said mineral acid is the mixture of sulfuric acid and phosphoric acid.
CN201410115856.3A 2014-03-26 2014-03-26 A kind of with discontinuous tube wall carbon nanotube for the method for Graphene prepared by raw material Expired - Fee Related CN103864069B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410115856.3A CN103864069B (en) 2014-03-26 2014-03-26 A kind of with discontinuous tube wall carbon nanotube for the method for Graphene prepared by raw material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410115856.3A CN103864069B (en) 2014-03-26 2014-03-26 A kind of with discontinuous tube wall carbon nanotube for the method for Graphene prepared by raw material

Publications (2)

Publication Number Publication Date
CN103864069A CN103864069A (en) 2014-06-18
CN103864069B true CN103864069B (en) 2015-09-09

Family

ID=50903173

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410115856.3A Expired - Fee Related CN103864069B (en) 2014-03-26 2014-03-26 A kind of with discontinuous tube wall carbon nanotube for the method for Graphene prepared by raw material

Country Status (1)

Country Link
CN (1) CN103864069B (en)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104730124A (en) * 2015-03-20 2015-06-24 福州大学 Carbon nano material with glucose detection performance and preparation method thereof
CN104852021B (en) * 2015-03-24 2017-03-22 天津师范大学 Preparation method of graphene/carbon nanotube composite material
CN105214522B (en) * 2015-09-14 2018-02-09 中国石油大学(华东) A kind of gas separation membrane based on CNT/graphene oxide polyimides
CN106315565A (en) * 2016-08-10 2017-01-11 安徽省宁国天成电工有限公司 Graphene for temperature sensor and preparation method of graphene
CN107804838A (en) * 2017-11-22 2018-03-16 哈尔滨工业大学 A kind of preparation method of low defect graphene ribbon sponge ultracapacitor
CN107814379A (en) * 2017-11-22 2018-03-20 哈尔滨工业大学 A kind of method that low defect graphene ribbon sponge is prepared using CNT sponge
CN107758647A (en) * 2017-11-22 2018-03-06 哈尔滨工业大学 A kind of preparation method of low defect graphene ribbon sponge composite
CN108529608B (en) * 2018-07-01 2021-10-08 曲靖师范学院 Method for preparing high-quality graphene nanosheets from carbon nanotubes

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101898760A (en) * 2010-07-23 2010-12-01 东北林业大学 Method for catalyzing polymer with multi-metallic catalyst to compound carbon nano-tube in situ
CN101905881A (en) * 2010-08-02 2010-12-08 无锡诚信碳材料科技有限公司 Preparation method of nano-carbon material with high graphitization degree
CN102602918A (en) * 2012-03-22 2012-07-25 天津大学 Graphene band prepared with acid oxidized flat carbon nano-tube and method for preparing graphene band
CN103247802A (en) * 2013-05-03 2013-08-14 深圳市贝特瑞新能源材料股份有限公司 Graphite composite negative electrode material for lithium ion battery, preparation method of material, and lithium ion battery

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101898760A (en) * 2010-07-23 2010-12-01 东北林业大学 Method for catalyzing polymer with multi-metallic catalyst to compound carbon nano-tube in situ
CN101905881A (en) * 2010-08-02 2010-12-08 无锡诚信碳材料科技有限公司 Preparation method of nano-carbon material with high graphitization degree
CN102602918A (en) * 2012-03-22 2012-07-25 天津大学 Graphene band prepared with acid oxidized flat carbon nano-tube and method for preparing graphene band
CN103247802A (en) * 2013-05-03 2013-08-14 深圳市贝特瑞新能源材料股份有限公司 Graphite composite negative electrode material for lithium ion battery, preparation method of material, and lithium ion battery

Also Published As

Publication number Publication date
CN103864069A (en) 2014-06-18

Similar Documents

Publication Publication Date Title
CN103864069B (en) A kind of with discontinuous tube wall carbon nanotube for the method for Graphene prepared by raw material
Wu et al. Designing nanostructured Si anodes for high energy lithium ion batteries
CN104852021B (en) Preparation method of graphene/carbon nanotube composite material
Zhang et al. Pine wood-derived hollow carbon fibers@ NiO@ rGO hybrids as sustainable anodes for lithium-ion batteries
CN111477873A (en) Lithium-sulfur battery conductive agent based on nano transition metal phosphide/carbon composite material and preparation method and application thereof
CN104591177B (en) Method for preparing self-supporting three-dimensional porous graphene composite microsphere
Guo et al. Vertically aligned ultrathin MoS2 nanosheets grown on graphene-wrapped hollow carbon microtubes derived from loofah sponge as advanced anodes for highly reversible lithium storage
Xue et al. Fabrication of GeO2 microspheres/hierarchical porous N-doped carbon with superior cyclic stability for Li-ion batteries
CN108736012B (en) Biomass microtube and carbon nanotube hybrid carbon material and preparation method thereof
CN102169987B (en) Graphene-supported porous nickel oxide and preparation method thereof, and application of graphene-supported porous nickel oxide in lithium ion battery anode material
Liu et al. Fe 3 O 4 nanoparticles encapsulated in multi-walled carbon nanotubes possess superior lithium storage capability
CN103730638A (en) Preparation method of nitrogen-doped carbon material
CN111704138A (en) Preparation method of two-dimensional nanocomposite material self-assembled layer by layer
Yu et al. Fe3O4 nanoparticles embedded in carbon-framework as anode material for high performance lithium-ion batteries
Yao et al. Interlayer-expanded MoS2 nanosheets/nitrogen-doped carbon as a high-performance anode for sodium-ion batteries
CN103721750B (en) A kind of Large Diameter Pipeline carbon nano-tube catalyst and preparation method thereof
Kong et al. Hydrothermal synthesis of β-nickel hydroxide microspheres with flakelike nanostructures and their electrochemical properties
CN107240685B (en) Iron trifluoride/lithium hexafluoroferrate composite positive electrode material, preparation and application thereof
Hou et al. Large-scale self-template synthesis of NiCo2O4 nanotubes derived from alginate for high-rate lithium storage properties stimulated by capacitive effects
CN109037623B (en) Positive electrode material of magnesium secondary battery and preparation method thereof
Liu et al. Nanosized monometallic selenides heterostructures implanted into metal organic frameworks-derived carbon for efficient lithium storage
Mi et al. Anchoring nanoarchitectonics of 1T’-MoS2 nanoflakes on holey graphene sheets for lithium-ion batteries with outstanding high-rate performance
Wang et al. Investigation on process mechanism of a novel energy-saving synthesis for high performance Li4Ti5O12 anode material
Liu et al. Implanting MnO into a three-dimensional carbon network as superior anode materials for lithium-ion batteries
Zhao et al. Layered NiPS3 nanoparticles anchored on two-dimensional nitrogen-doped biochar nanosheets for ultra-high rate sodium-ion storage

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20150909

Termination date: 20160326

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