CN103537322B - A kind of method of synthesis redox reactions eelctro-catalyst in enormous quantities - Google Patents
A kind of method of synthesis redox reactions eelctro-catalyst in enormous quantities Download PDFInfo
- Publication number
- CN103537322B CN103537322B CN201310452053.2A CN201310452053A CN103537322B CN 103537322 B CN103537322 B CN 103537322B CN 201310452053 A CN201310452053 A CN 201310452053A CN 103537322 B CN103537322 B CN 103537322B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- eelctro
- enormous quantities
- redox reactions
- salt
- 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
Links
Classifications
-
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a kind of method of synthesis redox reactions eelctro-catalyst in enormous quantities, ball-milling method is utilized to synthesize the structure of transition metal and containing n-donor ligand coordination in a large number, through very short time dry grinding and do not need to remove unreacted raw material, directly carry out roasting and can obtain active higher catalyst, simple and without the need to post processing.The present invention prepares the method simple and fast of eelctro-catalyst, the time and efficiency of preparing electrochemical catalyst can be increased substantially, and significantly reduce the cost of fuel cell, play positive effect by the application of fuel cell, metal-air battery homenergic memory device.
Description
Technical field
The present invention relates to the preparation field of catalyst, be specifically related to the fast preparation method of redox reactions eelctro-catalyst.
Background technology
Fuel cell, as the very promising energy storage device of one, has energy density high, clean and pollute few advantage.But due to the anode of fuel cell and electrochemical cathode dynamics all poor, especially negative electrode, therefore constrains the commercial applications of fuel cell.The catalyst being widely used in anode of fuel cell and negative electrode is at present that Pt and Pt is catalyst based, but the cost of these catalyst is higher, especially technology the most top is at present utilized, the loading of the catalyst of negative electrode also wants the 5-10 of anode doubly, in addition the easily poisoning and inactivation of noble metal catalyst, less stable, limits the large-scale production of fuel cell.And also need in redox reactions in metal air battery cathodes to add catalyst to improve dynamics, improve the effective energy density of battery.In order to address this problem, people begin one's study non-precious metal catalyst.
Current non-precious metal catalyst research can be divided into two large divisions: 1) metal-based catalyst, such as iron-based, manganese base and cobalt-base catalyst; 2) metal-free catalyst, the material with carbon element of such as N doping.The catalyst of Metal Substrate can dissolve in fuel cell operations, cause stability and cyclicity poor, but the existence of metal can promote the formation of the avtive spot of non-metallic catalyst, but the metal introduced in building-up process is difficult to eliminate.The concrete catalytic mechanism of these catalyst is also unintelligible at present, is difficult to the design concept of a formation system.
It is reported, the existence in micropore in catalyst, disordered carbon, graphited carbon and MNx site can improve the activity of catalytic oxygen reduction reaction.But, produce such avtive spot at synthesis phase very challenging, the formation from raw material to product, need very complicated process just can obtain having the synergistic catalyst of micropore, material with carbon element, nonmetal doping and transition metal.
Summary of the invention
In order to solve the problem, the invention provides a kind of simple and the synthetic method of eelctro-catalyst can be synthesized in a large number, solve the tedious steps of conventional synthesis ORR eelctro-catalyst, especially solve the trouble of solid-liquor separation, and the catalyst obtained unlatching gesture can compare favourably with the Pt/C of commercialization.
The present invention is based on the coordination structure of transition metal and containing n-donor ligand, after this structure collapses, meeting original position obtains the catalyst containing MNx site.Utilize ball-milling method can synthesize the structure of transition metal and containing n-donor ligand coordination in a large number.Do not need to remove unreacted raw material through the dry grinding of very short time in the present invention, and directly carry out roasting and can obtain active higher catalyst, simple and without the need to post processing.
The present invention relates to raw material simple and easy to get, operating procedure is simple, and concrete implementation step is as follows:
(1) be 1:10-1:1 mixing by transition metal salt and containing n-donor ligand according to mol ratio;
(2) ball-milling method dry grinding said mixture is used;
(3) mixture got after dry grinding is calcined under anaerobic, and calcining heat is 600-1200 DEG C, and calcination time is 10min-6h.
Described in said method step (1), transition metal salt is cobalt salt, or molysite, or the mixture of zinc salt and cobalt salt, or the mixture of zinc salt and molysite, wherein in the mixture of cobalt salt and zinc salt or the mixture of molysite and zinc salt, the ratio of cobalt salt and zinc salt is unrestricted, can be arbitrary proportion.
Above-mentioned cobalt salt is selected from its chloride, sulfate, nitrate, acetate, oxalates and metal oxide; Above-mentioned zinc salt is selected from its chloride, sulfate, acetate, oxalates and nitrate and metal oxide; Above-mentioned molysite is selected from its chloride, sulfate, nitrate, acetate, oxalates and metal oxide.
In said method step (1), containing n-donor ligand can be glyoxaline compound, pyrroles, pyrazoles, pyrazine, pyridine, pyrimidine, benzimidazole, phenanthrolene, bipyridyl etc.
Further, above-mentioned glyoxaline compound comprises substituting group is glyoxaline compound within four.
Further, above-mentioned substituting group is that glyoxaline compound within four comprises methylimidazole, 2-ethyl-4-methylimidazole and 2-phenylimidazole.
In said method step (2), ratio of grinding media to material is 1:1-10:1.
In said method step (2), the dry grinding time is 30-90min.
The present invention prepares the method simple and fast of eelctro-catalyst, the time and efficiency of preparing electrochemical catalyst can be increased substantially, and significantly reduce the cost of fuel cell, play positive effect by the application of fuel cell, metal-air battery homenergic memory device.
Accompanying drawing explanation
Fig. 1. in embodiment 1 after step (3) calcining the powder diffraction pattern of sample.
Fig. 2. in embodiment 1 after step (3) calcining the transmission electron microscope figure of sample.
Fig. 3. the linear sweep voltammetry figure of the sample in embodiment 1 after step (3) calcining.
Detailed description of the invention
The present invention is explained below by embodiment.But content of the present invention is not limited to these embodiments.
Embodiment 1
Cobalt acetate, zinc acetate and methylimidazole mol ratio are the eelctro-catalyst that 2:1:30 obtains.
(1) 20/3mmol cobalt acetate, 10/3mmol zinc acetate and 0.1mol methylimidazole are positioned in ball grinder, with the even compound of spoon (raw material has just started need use mortar porphyrize respectively).
(2) add the ball milling ball that 30 quality are 4g, after dry grinding 30min, take out sample.
(3) get the sample that 0.6g step (2) obtains and put into quartz boat, at 600 DEG C, calcine 6h.
Take out the sample after step (3) calcining, its X-ray pounder diff action and transmission electron microscope figure as illustrated in fig. 1 and 2, can find out, the image of the main cobalt simple substance containing fcc in sample, particle diameter is between 10-100nm.Elementary analysis and inductive coupling plasma emission spectrograph can determine the nitrogen containing 5wt%, the cobalt of 35wt%.Isothermal nitrogen adsorption show that the specific area of this sample is 320m
2/ g.Test electro-catalysis oxygen reduction in the basic conditions, its linear sweep voltammetry figure as shown in Figure 3, can find out, the unlatching gesture of this sample can reach-0.047V (vs.Ag/AgCl), and current density can reach 4.3mA/cm
2.
Embodiment 2
Cobalt nitrate, zinc acetate and benzimidazole mol ratio are the eelctro-catalyst that 8:1:18 obtains.
(1) 80/9mmol cobalt nitrate, 10/9mmol zinc acetate and 20mmol benzimidazole are positioned in ball grinder, with the even compound of spoon (raw material has just started need use mortar porphyrize respectively).
(2) adding 6 quality is the ball of 4g, takes out sample after dry grinding 60min.
(3) get the sample that 0.6g step (2) obtains and put into quartz boat, at 1200 DEG C, calcine 10min.
Take out the sample obtained through step (3).Elementary analysis and inductive coupling plasma emission spectrograph can determine the nitrogen containing 3wt%, the cobalt of 30wt%.Isothermal nitrogen adsorption show that the specific area of this sample is 300m
2/ g.Electro-catalysis oxygen reduction in the basic conditions, open gesture and can reach-0.02V (vs.Ag/AgCl), current density can reach 5mA/cm
2.
Embodiment 3
Cobalt chloride, zinc nitrate and phenanthrolene mol ratio are the eelctro-catalyst that 1:8:9 obtains.
(1) 10/9mmol cobalt chloride, 80/9mmol zinc nitrate and 10mmol phenanthrolene are positioned in ball grinder, with spoon Homogeneous phase mixing (raw material has just started need use mortar porphyrize respectively).
(2) adding 1 quality is the ball of 4g, takes out sample after dry grinding 90min.
(3) getting the sample that 0.6g step (2) obtains puts in quartz boat, at 900 DEG C, calcine 3h.
Take out the sample obtained through step (3).Elementary analysis and inductive coupling plasma emission spectrograph can determine the nitrogen containing 10wt%, the cobalt of 40wt%.Isothermal nitrogen adsorption show that the specific area of this sample is 200m
2/ g.Test electro-catalysis oxygen reduction in acid condition, open gesture and can reach 0.6V (vs.SCE), current density can reach 6mA/cm
2.
Embodiment 4
Cobaltous sulfate and pyrroles's mol ratio are the eelctro-catalyst that 1:3 obtains.
(1) 10mmol cobaltous sulfate 30mmol pyrroles is positioned in ball grinder, uses spoon Homogeneous phase mixing.
(2) adding 5 quality is the ball of 4g, takes out sample after dry grinding 40min, and dry.
(3) getting the sample that 0.6g step (2) obtains puts in quartz boat, at 900 DEG C, calcine 50min.
Take out the sample obtained through step (3).Elementary analysis and inductive coupling plasma emission spectrograph can determine the nitrogen containing 14wt%, the cobalt of 45wt%.Isothermal nitrogen adsorption show that the specific area of this sample is 254m
2/ g.Test electro-catalysis oxygen reduction in acid condition, open gesture and can reach 0.55V (vs.SCE), current density can reach 5mA/cm
2.
Embodiment 5
Cobalt acetate, zinc acetate and 2-ethyl-4-methylimidazole mol ratio are the eelctro-catalyst that 1:1:4 obtains.
(1) 10mmol cobalt acetate, 10mmol zinc acetate and 40mmol2-ethyl-4-methylimidazole are positioned in ball grinder, use spoon Homogeneous phase mixing.
(2) adding 10 quality is the ball of 4g, takes out sample after dry grinding 90min, and dry.
(3) getting the sample that 0.6g step (2) obtains puts in quartz boat, at 900 DEG C, calcine 25min.
Take out the sample obtained through step (3).Elementary analysis and inductive coupling plasma emission spectrograph can determine the nitrogen containing 12.5wt%, the cobalt of 40.5wt%.Isothermal nitrogen adsorption show that the specific area of this sample is 300m
2/ g.Test electro-catalysis oxygen reduction in acid condition, open gesture and can reach 0.50V (vs.SCE), current density can reach 6mA/cm
2.
Embodiment 6
Cobaltous sulfate, zinc nitrate and 2-phenylimidazole mol ratio are the eelctro-catalyst that 1:1:2 obtains.
(1) 10mmol cobaltous sulfate, 10mmol zinc nitrate and 20mmol2-phenylimidazole are positioned in ball grinder, use spoon Homogeneous phase mixing.
(2) adding 7 quality is the ball of 4g, takes out sample after dry grinding 50min, and dry.
(3) getting the sample that 0.6g step (2) obtains puts in quartz boat, at 900 DEG C, calcine 55min.
Take out the sample obtained through step (3).Elementary analysis and inductive coupling plasma emission spectrograph can determine the nitrogen containing 10wt%, the cobalt of 39wt%.Isothermal nitrogen adsorption show that the specific area of this sample is 200m
2/ g.Test electro-catalysis oxygen reduction in acid condition, open gesture and can reach 0.45V (vs.SCE), current density can reach 4.5mA/cm
2.
Embodiment 7
Ferric acetate, zinc sulfate and methylimidazole mol ratio are the eelctro-catalyst that 2:1:10 obtains.
(1) 20/3mmol ferric acetate, 10/3mmol zinc sulfate and 100/3mmol methylimidazole are positioned in ball grinder, with the even compound of spoon (raw material has just started need use mortar porphyrize respectively).
(2) add the ball milling ball that 10 quality are 4g, after dry grinding 50min, take out sample.
(3) get the sample that 0.6g step (2) obtains and put into quartz boat, at 900 DEG C, calcine 2h.
Take out the sample after step (3) calcining.The nitrogen containing 5.8wt% can be determined, the iron of 36.2wt% through elementary analysis and inductive coupling plasma emission spectrograph.Isothermal nitrogen adsorption show that the specific area of this sample is 100m
2/ g.Test electro-catalysis oxygen reduction in the basic conditions, the unlatching gesture of this sample can reach-0.09V (vs.Ag/AgCl), and current density can reach 5.0mA/cm
2.
Embodiment 8
Ferric nitrate, zinc chloride and benzimidazole mol ratio are the eelctro-catalyst that 1:1:10 obtains.
(1) 1mmol ferric nitrate, 1mmol zinc chloride and 10mmol benzimidazole are positioned in ball grinder, with the even compound of spoon (raw material has just started need use mortar porphyrize respectively).
(2) add the ball milling ball that 8 quality are 4g, after dry grinding 30min, take out sample.
(3) get the sample that 0.6g step (2) obtains and put into quartz boat, at 800 DEG C, calcine 1h.
Take out the sample after step (3) calcining.The nitrogen containing 6wt% can be determined, the iron of 32.5wt% through elementary analysis and inductive coupling plasma emission spectrograph.Isothermal nitrogen adsorption show that the specific area of this sample is 150m
2/ g.Test electro-catalysis oxygen reduction in acid condition, the unlatching gesture of this sample can reach 0.45V (vs.SCE), and current density can reach 6.0mA/cm
2.
Embodiment 9
Iron chloride and pyridine mol ratio are the eelctro-catalyst that 1:5 obtains.
(1) 2mmol iron chloride and 10mmol pyridine are positioned in ball grinder, with the even compound of spoon (raw material has just started need use mortar porphyrize respectively).
(2) add the ball milling ball that 10 quality are 4g, after dry grinding 40min, take out sample.
(3) get the sample that 0.6g step (2) obtains and put into quartz boat, at 700 DEG C, calcine 1.5h.
Take out the sample after step (3) calcining.The nitrogen containing 4.2wt% can be determined, the iron of 30.5wt% through elementary analysis and inductive coupling plasma emission spectrograph.Isothermal nitrogen adsorption show that the specific area of this sample is 213m
2/ g.Test electro-catalysis oxygen reduction in acid condition, the unlatching gesture of this sample can reach 0.40V (vs.SCE), and current density can reach 5.1mA/cm
2.
Claims (8)
1. a method for synthesis redox reactions eelctro-catalyst in enormous quantities, comprises the following steps:
(1) be 1:10-1:1 mixing by transition metal salt and containing n-donor ligand according to mol ratio, described transition metal salt is cobalt salt or molysite, or the mixture of cobalt salt and zinc salt, or the mixture of zinc salt and molysite;
(2) ball-milling method dry grinding said mixture is used;
(3) mixture got after dry grinding is calcined under anaerobic, and calcining heat is 600-1200 DEG C, and calcination time is 10min-6h.
2. the method for synthesis redox reactions eelctro-catalyst in enormous quantities as claimed in claim 1, it is characterized in that, described transition metal salt be cobalt salt or molysite time, described cobalt salt is selected from its chloride, sulfate, nitrate and metal oxide, and described molysite is selected from its chloride, sulfate, nitrate, acetate, oxalates and metal oxide.
3. the method for synthesis redox reactions eelctro-catalyst in enormous quantities as claimed in claim 1, it is characterized in that, described transition metal salt is the mixture of cobalt salt and zinc salt, or during the mixture of zinc salt and molysite, described cobalt salt is selected from its chloride, sulfate, nitrate, acetate, oxalates and metal oxide, described zinc salt is selected from its chloride, sulfate, acetate, oxalates and nitrate and metal oxide, and described molysite is selected from its chloride, sulfate, nitrate, acetate, oxalates and metal oxide.
4. the method for synthesis redox reactions eelctro-catalyst in enormous quantities as claimed in claim 1, it is characterized in that, described in step (1), containing n-donor ligand comprises glyoxaline compound, pyrroles, pyrazoles, pyrazine, pyridine, pyrimidine, benzimidazole, phenanthrolene, bipyridyl.
5. the method for synthesis redox reactions eelctro-catalyst as claimed in claim 4 in enormous quantities, is characterized in that, it is glyoxaline compound within four that described glyoxaline compound comprises substituting group.
6. the method for synthesis redox reactions eelctro-catalyst in enormous quantities as claimed in claim 5, it is characterized in that, described substituting group is that the glyoxaline compound within four comprises methylimidazole, 2-ethyl-4-methylimidazole and 2-phenylimidazole.
7. the method for synthesis redox reactions eelctro-catalyst in enormous quantities as claimed in claim 1, it is characterized in that, in step (2), ratio of grinding media to material is 1:1-10:1.
8. the method for synthesis redox reactions eelctro-catalyst in enormous quantities as claimed in claim 1, it is characterized in that, in step (2), the time of dry grinding is 30-90min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310452053.2A CN103537322B (en) | 2013-09-27 | 2013-09-27 | A kind of method of synthesis redox reactions eelctro-catalyst in enormous quantities |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310452053.2A CN103537322B (en) | 2013-09-27 | 2013-09-27 | A kind of method of synthesis redox reactions eelctro-catalyst in enormous quantities |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103537322A CN103537322A (en) | 2014-01-29 |
| CN103537322B true CN103537322B (en) | 2015-12-23 |
Family
ID=49961405
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310452053.2A Expired - Fee Related CN103537322B (en) | 2013-09-27 | 2013-09-27 | A kind of method of synthesis redox reactions eelctro-catalyst in enormous quantities |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103537322B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105576262B (en) * | 2016-03-02 | 2018-08-10 | 中国石油大学(华东) | A kind of iron/carbonization nitrogen co-doped composite material of high oxygen reduction activity for fuel battery negative pole |
| CN106268817B (en) * | 2016-07-18 | 2019-04-12 | 华中科技大学 | A kind of preparation method of non-precious metal catalyst and products thereof |
| CN108242549B (en) * | 2016-12-27 | 2021-08-17 | 中国科学技术大学 | Catalyst with dispersed VIII group single atoms and preparation method thereof |
| CN107749483B (en) * | 2017-06-12 | 2020-05-12 | 中国科学技术大学 | Catalyst for hydrogen-air fuel battery cathode material and preparation method thereof |
| CN109675632A (en) * | 2018-12-28 | 2019-04-26 | 西安交通大学 | A kind of carbon-based ZIF composite catalyst and preparation method thereof and the application in electro-catalysis reduction carbon dioxide reaction |
| CN110429290A (en) * | 2019-08-06 | 2019-11-08 | 四川轻化工大学 | A method of preparing nitrogen-doped carbon material load transition metal compound catalyst |
| CN114566654A (en) * | 2022-03-01 | 2022-05-31 | 安徽理工大学 | ZIF-derived Fe/Co-N-C electrocatalyst in shape of rich-edge round cake, preparation method and application thereof |
-
2013
- 2013-09-27 CN CN201310452053.2A patent/CN103537322B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN103537322A (en) | 2014-01-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103537322B (en) | A kind of method of synthesis redox reactions eelctro-catalyst in enormous quantities | |
| Xiao et al. | Nitrogen-coordinated single iron atom catalysts derived from metal organic frameworks for oxygen reduction reaction | |
| Wang et al. | BiVO4/Bi4Ti3O12 heterojunction enabling efficient photocatalytic reduction of CO2 with H2O to CH3OH and CO | |
| Najafpour et al. | Nano-sized manganese oxides as biomimetic catalysts for water oxidation in artificial photosynthesis: a review | |
| Sun et al. | Emerging strategies for developing high-performance perovskite-based materials for electrochemical water splitting | |
| Geng et al. | δ-MnO2–Mn3O4 nanocomposite for photochemical water oxidation: Active structure stabilized in the interface | |
| Gao et al. | Nanostructured heterogeneous catalysts for electrochemical reduction of CO2 | |
| An et al. | Improving the photocatalytic hydrogen evolution of UiO-67 by incorporating Ce4+-coordinated bipyridinedicarboxylate ligands | |
| Fereja et al. | High-entropy oxide derived from metal–organic framework as a bifunctional electrocatalyst for efficient urea oxidation and oxygen evolution reactions | |
| Najafpour et al. | Platinum/manganese oxide nanocomposites as water-oxidizing catalysts: new findings and current controversies | |
| CN108246330A (en) | A kind of method that monatomic catalyst is constructed based on lignin/metal supermolecular assembling | |
| Zhu et al. | Layered Fe-substituted LiNiO2 electrocatalysts for high-efficiency oxygen evolution reaction | |
| CN104353478B (en) | The cobalt tungsten bimetallic carbide of a kind of carbon cladding, preparation method and applications | |
| Liu et al. | Promoting photochemical water oxidation with metallic band structures | |
| Liu et al. | Promotional effect of Mn-doping on the catalytic performance of NiO sheets for the selective oxidation of styrene | |
| Gholamrezaei et al. | Multidisciplinary methods (co-precipitation, ultrasonic, microwave, reflux and hydrothermal) for synthesis and characterization of CaMn3O6 nanostructures and its photocatalytic water splitting performance | |
| Li et al. | Amorphous nickel-cobalt bimetal-organic framework nanosheets with crystalline motifs enable efficient oxygen evolution reaction: Ligands hybridization engineering | |
| Liu et al. | Correlations among structure, electronic properties, and photochemical water oxidation: a case study on lithium cobalt oxides | |
| CN110227474B (en) | LaCoO with oxygen vacancy3Preparation method and application of nano material | |
| CN104810518B (en) | A kind of cobalt manganese systems spinel nano material and its preparation method and application | |
| Shilpa et al. | Co–Ni layered double hydroxide for the electrocatalytic oxidation of organic molecules: An approach to lowering the overall cell voltage for the water splitting process | |
| Ye et al. | Tailoring Metal–Oxygen Bonds Boosts Oxygen Reaction Kinetics for High-Performance Zinc–Air Batteries | |
| Geng et al. | Architecture of biomimetic water oxidation catalyst with Mn4CaO5 clusterlike structure unit | |
| CN112941541A (en) | Monoatomic two-dimensional material and preparation method and application thereof | |
| Najafpour et al. | Nano-sized Mn3O4 and β-MnOOH from the decomposition of β-cyclodextrin-Mn: 2. The water-oxidizing activities |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for 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: 20151223 Termination date: 20190927 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |