CN101122040A - Method for preparing carbon nano-tube loading ruthenium oxide hydration composite material - Google Patents
Method for preparing carbon nano-tube loading ruthenium oxide hydration composite material Download PDFInfo
- Publication number
- CN101122040A CN101122040A CNA2007100722296A CN200710072229A CN101122040A CN 101122040 A CN101122040 A CN 101122040A CN A2007100722296 A CNA2007100722296 A CN A2007100722296A CN 200710072229 A CN200710072229 A CN 200710072229A CN 101122040 A CN101122040 A CN 101122040A
- Authority
- CN
- China
- Prior art keywords
- carbon nano
- ruthenium oxide
- composite material
- oxide hydration
- tube loading
- 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
Images
Abstract
The invention provides a method of preparing a carbon nano pipe load hydrous ruthenium oxide composite material. First, an electric deposition solution is prepared, and then the carbon nano pipes are spread in the main solution; the ruthenium hydroxide is deposited and loaded on the carbon nano pipes through the electric deposition method, to form the precursor of the carbon nano pipe load hydrous ruthenium oxide composite material; the carbon nano pipes/ ruthenium hydroxide settling after the electric deposition are put into a drying box to receive heat treatment, and after natural cooling, the carbon nano pipe load hydrous ruthenium oxide nano powder composite material is obtained. The invention has simple preparing conditions, easy to realize, does not include the complicated technology of re-oxidation treatment after traditional deposition of ruthenium trichloride and alkalinesubstance, so as to prevent introduction of impurity ion, make sure of high purity of products, prevent deficiencies of low output and difficulty in realizng industrialization, can prepare a large amount of carbon nano pipe/ hydrous ruthenium oxide compound powder, and helps in industrial large-scale production.
Description
(1) technical field
The invention belongs to technical field of inorganic nonmetallic materials, be specifically related to a kind of method for preparing carbon nano-tube loading ruthenium oxide hydration composite material.
(2) background technology
The chemical property that ruthenium oxide is outstanding and its vast capacity and excellent cycle performance are used its research aspect electrode material for super capacitor and are received much concern.Scientific research person finds that the capacitive property that ruthenium dioxide is good mainly ascribes RuO to
2The hydration undefined structure, the ruthenium oxide hydration of nano-scale has more excellent electrochemical activity, thereby preparation grain diameter is little, ruthenium oxide hydration that dispersity is high becomes domestic and international research important content.Because RuO
2Cost an arm and a leg, the transient large current discharge poor performance is unfavorable for the large-scale industrialization application.In order to reduce RuO
2Consumption, realize the low cost and the high specific capacitance of ultracapacitor, improve the transient large current discharge performance, current, main adopt with have than bigger serface, electrochemical stability and specific conductivity preferably raw material of wood-charcoal material (as gac, carbon nanotube etc.) be solid support material, prepare the ultra-fine electrode active material ruthenium oxide hydration of high dispersing/carbon material matrix material.
In recent years, the research report that carries ruthenium oxide about carbon has a lot, carbon nanotube is because its unique hollow nano tubular construction, good electrical conductivity, even aperture distribution advantages such as (being mesopore), make CNTs have good power characteristic and frequency response characteristic and high-specific surface area utilization ratio, can be used as electrode material for super capacitor.Adopt carbon nanotube to disperse RuO as carrier height
2More and more be subjected to people's attention.Main preparation methods has three classes: one, use conventional methods, and be to adopt alkaline matter that ruthenium chloride is precipitated, preparation carbon nanotube/ruthenium oxide hydration nano powder composite material, the powder characteristic of preparation is better relatively, but technology is complicated, wayward; They are two years old, adopt oxygenant direct oxidation ruthenium chloride, prepare carbon nanotube supported nanometer hydrated ruthenium oxide, for example: Chinese invention patent application number 200610033782.4, a kind of " preparation method of carbon nanotube supported nanometer hydrated ruthenium oxide " disclosed, this method is that carrier joins in the ruthenium trichloride solution by carbon nanotube, and using hydrogen peroxide is oxygenant direct oxidation ruthenium trichloride, the preparation carbon nanotube supported nanometer hydrated ruthenium oxide; Its three, adopt cyclic voltammetry on the matrix of carbon nano-tube, to prepare carbon nanotube/aqua oxidation ruthenium electrode, directly be deposited on the matrix, output is lower, is difficult to realize industrialization.
In addition, also deliver both at home and abroad relevant for the research paper of carbon nanotube loaded ruthenium dioxide, people such as Arabale are at (ChemistryPhysical Letter) 2003, the article that 376:207-213 delivers be adopt absorption-oxidation style at first by chemisorption with RuCl
3Be scattered in carbon nano tube surface, obtaining mass percent by oxidation then is 1% RuO
2/ CNT combined electrode is pressed into electrode with active substance at last, and the electrode of this method preparation reaches by original 30F/g than electric capacity brings up to 80F/g; (2000, the article of 30:112-116) delivering is that carbon nanotube is mixed with ruthenium chloride solution to people such as the Ma Renzhi of Tsing-Hua University, adopts NaOH to precipitate, and obtains mixed powder, adds binding agent then with powder pressing forming at Chinese science (E collects).When the content of ruthenium oxide is 75%, can reach 600F/g by the combined electrode of this preparation than electric capacity.Carbon nanotube/ruthenium oxide hydration nano powder composite material that preparation has excellent electrochemical performance has become one of the most popular in recent years research field both at home and abroad.
(3) summary of the invention
The method for preparing carbon nano-tube loading ruthenium oxide hydration composite material that the object of the present invention is to provide a kind of technology simply to be easy to control.
The carbon nano-tube loading ruthenium oxide hydration composite material of the present invention's preparation, its chemical formula is RuO
xNH
2O/CNTs.
Preparation method of the present invention comprises following processing step:
1), the preparation electric depositing solution, electric depositing solution is ruthenium trichloride, a nitrate and tensio-active agent mixing solutions by a certain percentage;
2), carbon nanotube is scattered in the main body solution;
3), by electro-deposition method, hydroxide ruthenium deposition is loaded on the carbon nanotube, be the precursor of carbon nano-tube loading ruthenium oxide hydration composite material;
4), the control electrodeposition time, the pH value in the regulator solution continue to stir precipitation is stablized;
5), carbon nanotube/hydroxide ruthenium throw out that galvanic deposit is good puts into baking oven thermal treatment certain hour under the certain temperature condition, obtains the carbon nano-tube loading ruthenium oxide hydration nano powder composite material behind the naturally cooling.
The present invention also has some technical characterictics like this:
1, described nitrate is ammonium nitrate, SODIUMNITRATE or saltpetre; Tensio-active agent is polyoxyethylene glycol, polyvinyl alcohol or Sodium dodecylbenzene sulfonate; And the concentration of each material be respectively ruthenium trichloride (0.5～50g/L), ammonium nitrate (5.0～500g/L), SODIUMNITRATE (5.0～1000g/L), saltpetre (5.0～300g/L), polyoxyethylene glycol (0.5～30g/L), polyvinyl alcohol (1.0～30g/L), Sodium dodecylbenzene sulfonate (1.0～30g/L);
2, described carbon nanotube is many walls and/or Single Walled Carbon Nanotube, and concentration is 0.5～20.0g/L;
3, the electrode selection is a negative electrode with platinized platinum, copper sheet, stainless steel substrates, Graphite Electrodes or DSA electrode in the described electro-deposition method, is anode with platinized platinum or DSA electrode; Current density is at 0.01～10A/cm
2Between;
4, the pH regulator of described electrodeposition process solution is between 4.0～11, and churning time is 1.0～6.0h;
5, described thermal treatment temp is 100～175 ℃, and roasting time is 2～15h;
6, described ruthenium trichloride, nitrate, tensio-active agent purity all are not less than chemical pure.
The present invention adopts the cathode electrodeposition legal system to be equipped with the precursor of carbon nanotube/ruthenium oxide hydration composite material, obtains carbon nanotube/ruthenium oxide hydration composite material through low-temperature heat treatment.The ruthenium oxide hydration of gained of the present invention high dispersing, particle size on carbon nanotube is little evenly, charge capacity is high, and median size is about 20nm.Preparation condition of the present invention is simple, realizes easily, reoxidizes the complicated technology of processing without traditional ruthenium trichloride and alkaline matter post precipitation, avoids introducing foreign ion, the high purity of assurance product.With respect to cyclic voltammetry, avoid output lower and be difficult to realize industrialized shortcoming, can prepare a large amount of carbon nanotubes/ruthenium oxide hydration mixture powder, be easy to industrialized mass.In conjunction with Fig. 1-Fig. 4, the carbon nanotube/ruthenium oxide hydration nano-powder combination electrode material of the present invention's preparation is at 1.0mol/LH
2SO
4Specific storage in the electrolytic solution has improved the utilization ratio of ruthenium oxide hydration up to 159F/g, and after 1000 big current cycle life-spans investigation tests, the specific storage decrement only is 7.6%.Have higher ratio electric capacity and good big current cycle performance with the allied substances of additive method preparation, have excellent capacitive property, make it to become a kind of electrode materials that gets a good chance of being used for ultracapacitor.
(4) description of drawings
Fig. 1 is carbon nanotube/ruthenium oxide hydration composite material stereoscan photograph of embodiment 1;
Fig. 2 is carbon nanotube/ruthenium oxide hydration combination electrode material transmission electron microscope photo of embodiment 1;
Fig. 3 sweeps CV curve under the speed for carbon nanotube/ruthenium oxide hydration composite material of embodiment 1 at 100mV/s;
Fig. 4 is the cycle performance test result of carbon nanotube/ruthenium oxide hydration composite material of embodiment 1.
(5) embodiment
The present invention will be further described below in conjunction with the drawings and specific embodiments:
It is as follows that present embodiment prepares the processing step of method of carbon nanotube/ruthenium oxide hydration nano powder composite material:
Implement one:
1), the preparation electric depositing solution, ruthenium trichloride 2.092g/L, SODIUMNITRATE 42.5g/L, polyvinyl alcohol 4.0g/L are mixed with the 250ml aqueous solution;
2), multi-walled carbon nano-tubes 4.0g/L is scattered in the main body solution;
3), be negative electrode with 20 * 20mm copper sheet, be anode with 20 * 20mm platinized platinum; The current density that adopts is 0.05A/cm
2
4), the control electrodeposition time, the pH value in the solution is adjusted in about 8, stir 5h, precipitation is stablized;
5), carbon nanotube/hydroxide ruthenium throw out that galvanic deposit is good puts into baking oven thermal treatment 6h under 150 ℃ of conditions, naturally cooling prepares carbon nanotube/ruthenium oxide hydration nano powder composite material;
6) cyclic voltammetry curve of test compound material such as Fig. 3.
Implement two:
1), the preparation electric depositing solution, ruthenium trichloride 2.092g/L, saltpetre 60g/L, polyoxyethylene glycol 4.0g/L are mixed with the 250ml aqueous solution;
2), multi-walled carbon nano-tubes 2.0g/L is scattered in the main body solution;
3), be negative electrode with 20 * 20mmDSA electrode, be anode with 20 * 20mm platinized platinum; The current density that adopts is 0.2A/cm
2
4), the control electrodeposition time, the pH value in the solution is adjusted in about 8, stir 5h, precipitation is stablized;
5), carbon nanotube/hydroxide ruthenium throw out that galvanic deposit is good puts into baking oven thermal treatment 6h under 150 ℃ of conditions, naturally cooling prepares carbon nanotube/ruthenium oxide hydration nano powder composite material;
Implement three:
1), the preparation electric depositing solution, ruthenium trichloride 5.0g/L, ammonium nitrate 80g/L, dodecylbenzene naphthenic acid sodium 10g/L are mixed with the 250ml aqueous solution;
2), multi-walled carbon nano-tubes 8.0g/L is scattered in the main body solution;
3), be negative electrode with 20 * 20mm platinized platinum, be anode with 20 * 20mm platinized platinum; The current density that adopts is 2.0A/cm
2
4), the control electrodeposition time, the pH value in the solution is adjusted in about 8, stir 5h, precipitation is stablized;
5), carbon nanotube/hydroxide ruthenium throw out that galvanic deposit is good puts into baking oven thermal treatment 6h under 150 ℃ of conditions, naturally cooling prepares carbon nanotube/ruthenium oxide hydration nano powder composite material.
Claims (6)
1. method for preparing carbon nano-tube loading ruthenium oxide hydration composite material, it is characterized in that: it comprises following processing step:
1), the preparation electric depositing solution, electric depositing solution is ruthenium trichloride, nitrate, a tensio-active agent mixed aqueous solution by a certain percentage;
2), carbon nanotube is scattered in the main body solution;
3), by electro-deposition method, hydroxide ruthenium deposition is loaded on the carbon nanotube, be the precursor of carbon nano-tube loading ruthenium oxide hydration composite material;
4), the control electrodeposition time, the pH value in the regulator solution continue to stir precipitation is stablized;
5), that galvanic deposit is good carbon nanotube/hydroxide ruthenium throw out is put into baking oven thermal treatment, is obtained the carbon nano-tube loading ruthenium oxide hydration nano powder composite material behind the naturally cooling.
2. a kind of method for preparing carbon nano-tube loading ruthenium oxide hydration composite material according to claim 1 is characterized in that described nitrate is ammonium nitrate, SODIUMNITRATE or saltpetre; Tensio-active agent is polyoxyethylene glycol, polyvinyl alcohol or Sodium dodecylbenzene sulfonate; And the concentration of each material is respectively ruthenium trichloride 0.5～50g/L, ammonium nitrate 5.0～500g/L, SODIUMNITRATE 5.0～1000g/L, saltpetre 5.0～300g/L, polyoxyethylene glycol 0.5～30g/L, polyvinyl alcohol 1.0～30g/L, Sodium dodecylbenzene sulfonate 1.0～30g/L.
3. a kind of method for preparing carbon nano-tube loading ruthenium oxide hydration composite material according to claim 1 it is characterized in that described carbon nanotube is many walls and/or Single Walled Carbon Nanotube, and concentration is 0.5～20.0g/L.
4. a kind of method for preparing carbon nano-tube loading ruthenium oxide hydration composite material according to claim 1, it is characterized in that electrode is a negative electrode with platinized platinum, copper sheet, stainless steel substrates, Graphite Electrodes or DSA electrode in the described electro-deposition method, is anode with platinized platinum or DSA electrode; Current density is at 0.01～10A/cm
2Between.
5. a kind of method for preparing carbon nano-tube loading ruthenium oxide hydration composite material according to claim 1, the pH regulator that it is characterized in that described electrodeposition process solution are between 4.0～11, and churning time is 1.0～6.0h.
6. a kind of method for preparing carbon nano-tube loading ruthenium oxide hydration composite material according to claim 1 is characterized in that described thermal treatment temp is 100～175 ℃, and roasting time is 2～15h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710072229A CN100588753C (en) | 2007-05-21 | 2007-05-21 | Method for preparing carbon nano-tube loading ruthenium oxide hydration composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710072229A CN100588753C (en) | 2007-05-21 | 2007-05-21 | Method for preparing carbon nano-tube loading ruthenium oxide hydration composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101122040A true CN101122040A (en) | 2008-02-13 |
| CN100588753C CN100588753C (en) | 2010-02-10 |
Family
ID=39084535
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200710072229A Expired - Fee Related CN100588753C (en) | 2007-05-21 | 2007-05-21 | Method for preparing carbon nano-tube loading ruthenium oxide hydration composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100588753C (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101533716B (en) * | 2009-04-15 | 2010-12-29 | 中南大学 | Preparation technique of composite film electrode used for a super capacitor |
| CN101525760B (en) * | 2009-04-17 | 2011-03-23 | 中南大学 | Electrodeposition technology for preparing electrode material of RuO2 of super capacitor |
| CN103632854A (en) * | 2012-08-24 | 2014-03-12 | 海洋王照明科技股份有限公司 | Preparation methods of ruthenium oxide-graphene composite material and capacitor |
| CN104021943A (en) * | 2014-05-19 | 2014-09-03 | 中国科学院过程工程研究所 | Ruthenium dioxide/carbon composite nano-material for super capacitor, and preparation method thereof |
| US20160268061A1 (en) * | 2013-11-05 | 2016-09-15 | The Regents Of The University Of California | Metal-oxide anchored graphene and carbon-nanotube hybrid foam |
| CN108461307A (en) * | 2018-05-11 | 2018-08-28 | 西北民族大学 | Lithium ion mixed capacitor ruthenic oxide@carbon nano-tube combination electrode materials and preparation method thereof |
| CN109659153A (en) * | 2018-12-18 | 2019-04-19 | 清华大学 | A kind of metal oxide and the compound micro comb energy storage electrode of carbon nanotube |
| CN110057486A (en) * | 2019-04-15 | 2019-07-26 | 绍兴文理学院元培学院 | A kind of ceramic thick film pressure sensor preparation process |
| CN110354848A (en) * | 2019-05-24 | 2019-10-22 | 深圳欧赛技术有限公司 | PtRu catalyst and its preparation method and application |
| CN114016103A (en) * | 2021-10-28 | 2022-02-08 | 浙江大学 | Amorphous transition metal hydroxide electrode material and preparation method thereof |
-
2007
- 2007-05-21 CN CN200710072229A patent/CN100588753C/en not_active Expired - Fee Related
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101533716B (en) * | 2009-04-15 | 2010-12-29 | 中南大学 | Preparation technique of composite film electrode used for a super capacitor |
| CN101525760B (en) * | 2009-04-17 | 2011-03-23 | 中南大学 | Electrodeposition technology for preparing electrode material of RuO2 of super capacitor |
| CN103632854A (en) * | 2012-08-24 | 2014-03-12 | 海洋王照明科技股份有限公司 | Preparation methods of ruthenium oxide-graphene composite material and capacitor |
| CN106463276B (en) * | 2013-11-05 | 2020-04-07 | 加利福尼亚大学董事会 | Metal oxide anchored graphene and carbon nanotube hybrid foam |
| US20160268061A1 (en) * | 2013-11-05 | 2016-09-15 | The Regents Of The University Of California | Metal-oxide anchored graphene and carbon-nanotube hybrid foam |
| CN106463276A (en) * | 2013-11-05 | 2017-02-22 | 加利福尼亚大学董事会 | Metal-oxide anchored graphene and carbon-nanotube hybrid foam |
| US10580591B2 (en) | 2013-11-05 | 2020-03-03 | The Regents Of California, Riverside | Metal-oxide anchored graphene and carbon-nanotube hybrid foam |
| CN104021943B (en) * | 2014-05-19 | 2017-02-01 | 中国科学院过程工程研究所 | Ruthenium dioxide/carbon composite nano-material for super capacitor, and preparation method thereof |
| CN104021943A (en) * | 2014-05-19 | 2014-09-03 | 中国科学院过程工程研究所 | Ruthenium dioxide/carbon composite nano-material for super capacitor, and preparation method thereof |
| CN108461307A (en) * | 2018-05-11 | 2018-08-28 | 西北民族大学 | Lithium ion mixed capacitor ruthenic oxide@carbon nano-tube combination electrode materials and preparation method thereof |
| CN109659153A (en) * | 2018-12-18 | 2019-04-19 | 清华大学 | A kind of metal oxide and the compound micro comb energy storage electrode of carbon nanotube |
| CN110057486A (en) * | 2019-04-15 | 2019-07-26 | 绍兴文理学院元培学院 | A kind of ceramic thick film pressure sensor preparation process |
| CN110354848A (en) * | 2019-05-24 | 2019-10-22 | 深圳欧赛技术有限公司 | PtRu catalyst and its preparation method and application |
| CN110354848B (en) * | 2019-05-24 | 2021-05-07 | 深圳欧赛技术有限公司 | PtRu catalyst and preparation method and application thereof |
| CN114016103A (en) * | 2021-10-28 | 2022-02-08 | 浙江大学 | Amorphous transition metal hydroxide electrode material and preparation method thereof |
| CN114016103B (en) * | 2021-10-28 | 2022-11-01 | 浙江大学 | Amorphous transition metal hydroxide electrode material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100588753C (en) | 2010-02-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100588753C (en) | Method for preparing carbon nano-tube loading ruthenium oxide hydration composite material | |
| Poudel et al. | Confinement of Zn-Mg-Al-layered double hydroxide and α-Fe2O3 nanorods on hollow porous carbon nanofibers: A free-standing electrode for solid-state symmetric supercapacitors | |
| Wu et al. | Rational design of cobalt–nickel double hydroxides for flexible asymmetric supercapacitor with improved electrochemical performance | |
| Peng et al. | N-doped carbon shell coated CoP nanocrystals encapsulated in porous N-doped carbon substrate as efficient electrocatalyst of water splitting | |
| Zhan et al. | Synthesis of mesoporous NiCo2O4 fibers and their electrocatalytic activity on direct oxidation of ethanol in alkaline media | |
| Tian et al. | Construction of Ni3S2 wrapped by rGO on carbon cloth for flexible supercapacitor application | |
| Wang et al. | Facile synthesis of reduced graphene oxide/NiMn2O4 nanorods hybrid materials for high-performance supercapacitors | |
| Gong et al. | High-performance desalination of three-dimensional nitrogen-doped carbon framework reinforced Prussian blue in capacitive deionization | |
| Tang et al. | Template-directed growth of hierarchically structured MOF-derived LDH cage hybrid arrays for supercapacitor electrode | |
| Reddy et al. | Highly porous metal organic framework derived NiO hollow spheres and flowers for oxygen evolution reaction and supercapacitors | |
| Li et al. | Nickel-cobalt layered double hydroxide nanosheets anchored to the inner wall of wood carbon tracheids by nitrogen-doped atoms for high-performance supercapacitors | |
| Li et al. | TiNb2O7 nanowires with high electrochemical performances as anodes for lithium ion batteries | |
| Yu et al. | Metal-organic frameworks derived carbon-incorporated cobalt/dicobalt phosphide microspheres as Mott–Schottky electrocatalyst for efficient and stable hydrogen evolution reaction in wide-pH environment | |
| Chen et al. | Uniform polypyrrole electrodeposition triggered by phytic acid-guided interface engineering for high energy density flexible supercapacitor | |
| Ji et al. | Bismuth oxide/nitrogen-doped carbon dots hollow and porous hierarchitectures for high-performance asymmetric supercapacitors | |
| Miao et al. | Nanocubic-Co3O4 coupled with nitrogen-doped carbon nanofiber network: a synergistic binder-free catalyst toward oxygen reduction reactions | |
| Liu et al. | Construction of hierarchical Cu2+ 1O@ NiCoAl-layered double hydroxide nanorod arrays electrode for high-performance supercapacitor | |
| Liu et al. | Electrospun NiO/C nanofibers as electrode materials for hybrid supercapacitors with superior electrochemical performance | |
| Wei et al. | Inherently porous Co3O4@ NiO core–shell hierarchical material for excellent electrochemical performance of supercapacitors | |
| Lv et al. | Novel freestanding N-doped carbon coated Fe3O4 nanocomposites with 3D carbon fibers network derived from bacterial cellulose for supercapacitor application | |
| Huang et al. | Hollow FeS2 nanospheres encapsulated in N/S co-doped carbon nanofibers as electrode material for electrochemical energy storage | |
| Zhang et al. | Facile synthesis, microstructure and electrochemical performance of peanut shell derived porous activated carbon/Co3O4 composite for hybrid supercapacitors | |
| Li et al. | Amorphous CoSx nanoparticles anchoring onto N-doped carbon nanotubes as high-performance electrodes for hybrid supercapacitors | |
| Cao et al. | Novel fabrication strategy of nanostructured NiCo-LDHs monolithic supercapacitor electrodes via inducing electrochemical in situ growth on etched nickel foams | |
| Wang et al. | Simple controllable foam structure NiCo2S4 for high-performance hybrid supercapacitors |
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 | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100210 Termination date: 20120521 |