CN102718209B - Method for preparing graphene based on reduction of divalent iron ion - Google Patents
Method for preparing graphene based on reduction of divalent iron ion Download PDFInfo
- Publication number
- CN102718209B CN102718209B CN2012101906194A CN201210190619A CN102718209B CN 102718209 B CN102718209 B CN 102718209B CN 2012101906194 A CN2012101906194 A CN 2012101906194A CN 201210190619 A CN201210190619 A CN 201210190619A CN 102718209 B CN102718209 B CN 102718209B
- Authority
- CN
- China
- Prior art keywords
- graphene
- ferrous ion
- preparation
- reaction
- method based
- 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
Images
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a method for preparing graphene based on reduction of divalent iron ion, and belongs to the technical field of materials. According to the method, a divalent iron ion salt is used as a reducing agent of graphene oxide, and the graphene oxide can be efficiently reduced in an alkaline environment and an inert protective atmosphere at room temperature to prepare the graphene. Compared with the traditional method for preparing the grapheme, the used reducing agent is green, safe, efficient and cheap, and has a significant industrial value.
Description
Technical field
The invention belongs to the material technology field, relate to the carbon nanomaterial technology of preparing, particularly graphene preparation method.
Background technology
Graphene (Graphene) is the two-dimentional carbon atom crystal of monatomic thickness, is considered to constitute the basic structural unit of soccerballene, carbon nanotube and graphite.Grapheme material has some advantageous properties of materials such as graphite and carbon nanotube concurrently, transmits performance etc. as outstanding heat conductivility, mechanical property and outstanding electronics.The excellent properties that Graphene and graphene-based nano composite material show makes it have important application prospects in fields such as lithium ion cell electrode, electrode of super capacitor, gas sensor, field emmision materials.
Efficiently, green, cheap graphene preparation method is the prerequisite of Graphene and the further investigation of graphene-based nano composite material performance and widespread use.The main preparation methods of Graphene has micromechanical forces to peel off (Novoselov KS at present, Geim AK, Morozov SV, et al.Science.2004,306 (5696): 666-9), chemical vapour deposition (Kim KS, Zhao Y, Jang H, et al.Nature.2009,457 (7230): 706-10), oriented growth (Forbeaux I, Themlin JM, Debever JM.Physical Review B.1998,58 (24): 16396-406), graphene oxide chemical reduction (Stankovich S, Dikin DA, Piner RD, et al.Carbon.2007,45 (7): method such as 1558-65).Micromechanical forces is peeled off, chemical vapour deposition and oriented growth preparation method owing to complicated operation, condition harshness, yielding poorly is not suitable for large-scale commercial applications production, so the graphene oxide chemical reduction method is considered to most possibly realize the extensive cheap effective ways of producing of Graphene.The graphene oxide chemical reduction at first is raw material with the crystalline flake graphite, and (Graphene oxide GO), is reduced to Graphene by certain reduction reaction with graphene oxide again through obtaining graphene oxide after strong oxidizer oxidation, the supersound process.The advantage of this method is that energy consumption is low, preparation process is simple, Graphene productive rate height, and the Graphene that obtains easily is scattered in water, the pure equal solvent, therefore is easy to be applied to prepare lithium ion cell electrode, electrode of super capacitor and other graphene-based matrix materials.The reductive agent that is used for redox graphene at present mainly contains hydrazine hydrate, dimethylhydrazine, sodium borohydride, quinhydrones etc., but this class reductive agent is owing to characteristics such as easy blast in high poison and the use are not suitable for using in extensive graphene oxide reduction process.Other novel reductive agent such as nanometer iron powder, aluminium powder, xitix (Chinese patent, though ZL200910054919.8) wait and to have eco-friendly characteristics, expensive, make that production cost is too high and be unfavorable for that large-scale industrialization uses.
Technology contents
The present invention proposes a kind of safe, efficient, cheap graphene preparation method; this method adopts ferrous ion salt as the reductive agent of graphene oxide; under alkaline environment, inert protective atmosphere and room temperature, can realize the efficient reduction to graphene oxide, prepare Graphene.Present method is compared with existing graphene preparation method, and the reductive agent system green of employing, safe, efficient, cheap has significant industrial application value.
Technical solution of the present invention is as follows:
A kind of graphene preparation method based on the ferrous ion reduction may further comprise the steps:
Step 1: the colloidal suspensions of preparation graphene oxide.
In natural flake graphite or the high oriented graphite powder of pyrolysis and strong oxidizer adding strongly acidic solution, after mixing system temperature is risen to 35 ~ 45 ℃, continue to stir after 1 ~ 3 hour and add deionized water, make system temperature rise to 80 ~ 100 ℃ and kept 1 hour, reaction finishes the back and drips a certain amount of H
2O
2, stop to stir standing demix, take off layer graphite oxide suspension and carry out pickling, washing successively until removing various gritty particles, handle the individual layer of realizing graphene oxide finally by ultrasonic agitation and peel off, obtain the graphene oxide colloidal suspensions.
Step 2: the preparation of Graphene.
Detailed process is: in reaction solvent; the graphene oxide colloidal suspensions that adds the step 1 preparation; stir and add basic solution adjusting pH to 10 ~ 13 down; the compound that adds ferrous ion under the inert protective atmosphere; stirring reaction under-10 ~ 50 ℃ temperature of reaction; reaction finishes the back solid-liquid separation, and separating obtained solid is used dilute hydrochloric acid, deionized water wash repeatedly successively, namely obtains Graphene after the drying.
Or: in reaction solvent; the graphene oxide colloidal suspensions that adds the step 1 preparation; the compound that adds ferrous ion under the inert protective atmosphere; stir and add basic solution adjusting pH to 10 ~ 13 down; stirring reaction under-10 ~ 50 ℃ temperature of reaction; reaction finishes the back solid-liquid separation, and separating obtained solid is used dilute hydrochloric acid, deionized water wash repeatedly successively, namely obtains Graphene after the drying.
In the technique scheme: 1, the compound of described ferrous ion comprises inorganic salt (as: one or more in iron protochloride, ferrous sulfate, Iron nitrate, iron protocarbonate or the ferrous phosphate) or the organic salt (as: one or more in Ferrox, Iron diacetate or the yellow prussiate of potash) that contains ferrous ion; 2, described inert protective atmosphere is by one or more realizations in nitrogen, argon gas or the helium; 3, basic solution described in the step 2 is one or more in ammoniacal liquor, sodium hydroxide, potassium hydroxide or the sodium ethylate aqueous solution; 4, temperature of reaction described in the step 2 is preferably 0 ~ 25 ℃, 10 seconds ~ 24 hours reaction times (being preferably 60 seconds ~ 2 hours); 5, reaction solvent described in the step 2 is one or more (preferably water, methyl alcohol or the ethanol) in water, alcohol, acetone and the dimethyl formamide; 6, strongly acidic solution described in the step 1 is one or more in the vitriol oil, oleum, concentrated nitric acid or the nitrosonitric acid; 7, strong oxidizer described in the step 1 is one or more in potassium permanganate, Potcrate or the potassium bichromate.
Essence of the present invention is to utilize the ferrous ion redox graphene, add alkaline matter (solution) and ferrous ion salt (solution) or ferrous ion salt (solution) and alkaline matter (solution) successively to the graphene oxide colloidal suspensions, under the condition that hydroxide radical exists, ferrous ion obtains Graphene as reductive agent and graphite oxide alkene reaction.
The used compound that contains ferrous ion is common cheap common reagent in above-mentioned preparation process, though the reductibility of ferrous ion in acidity or neutral environment is very weak, its reducing power is not enough to realize the height reduction of Graphene; But the reductibility of ferrous ion in alkaline environment can strengthen greatly; this is because the ferrous hydroxide that ferrous ion and hydroxide radical generate is strong reductant; because oxygen molecule or airborne oxygen that ferrous hydroxide is very easily dissolved in the solution are oxidized to ironic hydroxide, so the inert reaction environment that adopts shielding gas to provide realizes that ferrous hydroxide is to the height reduction of Graphene.
The graphene nano material synthetic according to present method has following remarkable advantage: (1) the present invention uses the method for ferrous ion redox graphene to prepare Graphene first, this method has been accelerated reduction rate, reduced reduction temperature, simple to operate, be conducive to the batch process of high quality Graphene; (2) as reductive agent, with respect to the hydrazine reducing agent with toxicity, ferrous ion is green fully reductive agent with the ferrous ion compound in the present invention; With respect to reductive agent nanometer iron powder, aluminium powder or the benzoquinones of costliness, the ferrous ion compound is industrial chemicals cheap and easy to get; (3) Graphene in prepared the be scattered in solution of the present invention can be widely used in lithium ion battery electrode material, in the industrialization products such as electrode material for super capacitor.
Figure of description
Fig. 1 is schematic flow sheet of the present invention.
Fig. 2 is the infrared spectrum of prepared graphene of the present invention and graphene oxide.
Fig. 3 is the X ray diffracting spectrum of prepared graphene of the present invention and graphene oxide.
Fig. 4 is the thermogravimetric analysis collection of illustrative plates of prepared graphene of the present invention and graphene oxide.
Embodiment
Embodiment 1: ferrous sulfate prepares Graphene as the reductive agent redox graphene.
(1) preparation of graphene oxide: in three mouthfuls of round-bottomed flasks, add the 55ml vitriol oil, add 1g natural flake graphite and 7g potassium permanganate then successively, mix, system temperature is risen to 35 ~ 45 ℃, continue to stir and add the 100ml deionized water after 1 ~ 3 hour, make system temperature rise to 80 ~ 100 ℃ and kept 1 hour, reaction finishes back Dropwise 5 mlH in the reaction system
2O
2Stop to stir standing demix, take off layer graphite oxide suspension and carry out pickling, washing successively until removing various gritty particles, utilize operating frequency to be 40kHz then, ultrasonic power is that the individual layer that the ultrasonic device of 350W carries out ultrasonic agitation processing realization graphene oxide to the graphite oxide colloidal suspensions peels off, thereby obtains the graphene oxide colloidal suspensions.
(2) preparation of Graphene: under the room temperature, configuration 50mL, 0.5mg/mL graphite oxide aqueous solution, place the 150mL Erlenmeyer flask, making in the Erlenmeyer flask with the interior oxygen of Erlenmeyer flask in the feeding nitrogen eliminating solution is oxygen-free atmosphere, and the adding 20mL of elder generation ammoniacal liquor adds the 2.5g ferrous sulfate then.Fully stir 10min, reaction finishes after-filtration and uses 200ml dilute hydrochloric acid and 500ml deionized water wash successively repeatedly, namely obtains Graphene behind the solid drying.
Resultant Graphene can stable dispersion in solution such as water, ethanol, dimethyl formamide, show the dispersed fine of Graphene.The infrared spectrum of resultant Graphene (referring to Fig. 2) shows that graphene oxide oxy radical after reduction is all sloughed basically, has formed Graphene lamella structure.Adopt X ray polycrystalline diffractometer that the product of gained is carried out material phase analysis, X ray diffracting spectrum (referring to Fig. 3) shows the reduction through ferrous ion, and graphene oxide has been reduced into Graphene, is characterized as (002) diffraction peak that occurs about 26 degree.By the thermogravimetric analysis collection of illustrative plates (referring to Fig. 4) of graphene oxide and Graphene as can be seen, after graphene oxide was reduced into Graphene, most of oxy radical was removed, made Graphene have extraordinary thermostability.
2: two oxalic acid hydrates of embodiment are ferrous to prepare Graphene as the reductive agent redox graphene.
(1) preparation of graphene oxide: referring to embodiment 1 step (1).
(2) preparation of Graphene: under the room temperature, configuration 50mL, 1mg/mL graphite oxide aqueous solution, place the 150mL Erlenmeyer flask, feed nitrogen and get rid of in the solution and the oxygen in the Erlenmeyer flask makes and is oxygen-free atmosphere in the Erlenmeyer flask, add 20mL ammoniacal liquor earlier, it is ferrous to add 2.0g two oxalic acid hydrates then.Fully stir 60min, reaction finishes after-filtration and uses 200ml dilute hydrochloric acid and 500ml deionized water wash successively repeatedly, namely obtains Graphene behind the solid drying.
Embodiment 3: Iron dichloride tetrahydrate prepares Graphene as the reductive agent redox graphene.
(1) preparation of graphene oxide: referring to embodiment 1 step (1).
(2) preparation of Graphene: under the room temperature, configuration 50mL, 1mg/mL graphene oxide ethanolic soln, place the 150mL Erlenmeyer flask, making in the Erlenmeyer flask with the interior oxygen of Erlenmeyer flask in the feeding argon gas eliminating solution is oxygen-free atmosphere, add 2g sodium hydrate solid powder earlier, add the 4.0g Iron dichloride tetrahydrate then.Fully stir 30min, reaction finishes after-filtration and uses 200ml dilute hydrochloric acid and 500ml deionized water wash successively repeatedly, namely obtains Graphene behind the solid drying.
Above embodiments of the invention have been done detailed description, embodiment is being to have provided detailed embodiment and concrete operating process under the prerequisite with the technical solution of the present invention, but protection scope of the present invention is not limited to the above embodiments.
Claims (10)
1. graphene preparation method based on ferrous ion reduction may further comprise the steps:
Step 1: the colloidal suspensions of preparation graphene oxide;
In natural flake graphite or the high oriented graphite powder of pyrolysis and strong oxidizer adding strongly acidic solution, after mixing system temperature is risen to 35～45 ℃, continue to stir after 1～3 hour and add deionized water, make system temperature rise to 80～100 ℃ and kept 1 hour, reaction finishes the back and drips a certain amount of H
2O
2, stop to stir standing demix, take off layer graphite oxide suspension and carry out pickling, washing successively until removing various gritty particles, handle the individual layer of realizing graphene oxide finally by ultrasonic agitation and peel off, obtain the graphene oxide colloidal suspensions;
Step 2: the preparation of Graphene;
Detailed process is: in reaction solvent, the graphene oxide colloidal suspensions that adds the step 1 preparation, stir and add basic solution adjusting pH to 10～13 down, the compound that adds ferrous ion under the inert protective atmosphere, stirring reaction under-10～50 ℃ temperature of reaction, reaction finishes the back solid-liquid separation, and separating obtained solid is used dilute hydrochloric acid, deionized water wash repeatedly successively, namely obtains Graphene after the drying;
Or: in reaction solvent; the graphene oxide colloidal suspensions that adds the step 1 preparation; the compound that adds ferrous ion under the inert protective atmosphere; stir and add basic solution adjusting pH to 10～13 down; stirring reaction under-10～50 ℃ temperature of reaction; reaction finishes the back solid-liquid separation, and separating obtained solid is used dilute hydrochloric acid, deionized water wash repeatedly successively, namely obtains Graphene after the drying.
2. the graphene preparation method based on the ferrous ion reduction according to claim 1 is characterized in that the compound of described ferrous ion comprises inorganic salt or the organic salt that contains ferrous ion.
3. the graphene preparation method based on the ferrous ion reduction according to claim 2 is characterized in that the described inorganic salt that contain ferrous ion are one or more in iron protochloride, ferrous sulfate, Iron nitrate, iron protocarbonate or the ferrous phosphate; The described organic salt that contains ferrous ion is one or more in Ferrox, Iron diacetate or the yellow prussiate of potash.
4. the graphene preparation method based on the ferrous ion reduction according to claim 1 is characterized in that described inert protective atmosphere is by one or more realizations in nitrogen, argon gas or the helium.
5. the graphene preparation method based on the ferrous ion reduction according to claim 1 is characterized in that basic solution described in the step 2 is one or more in ammoniacal liquor, sodium hydroxide, potassium hydroxide or the sodium ethylate aqueous solution.
6. the graphene preparation method based on the ferrous ion reduction according to claim 1 is characterized in that temperature of reaction described in the step 2 is 0～25 ℃, and the reaction times is 10 seconds～24 hours.
7. the graphene preparation method based on the ferrous ion reduction according to claim 6 is characterized in that the reaction times described in the step 2 is 60 seconds～2 hours.
8. the graphene preparation method based on the ferrous ion reduction according to claim 1 is characterized in that reaction solvent described in the step 2 is one or more in water, alcohol, acetone and the dimethyl formamide.
9. the graphene preparation method based on the ferrous ion reduction according to claim 1 is characterized in that strongly acidic solution described in the step 1 is one or more in the vitriol oil, oleum, concentrated nitric acid or the nitrosonitric acid.
10. the graphene preparation method based on the ferrous ion reduction according to claim 1 is characterized in that strong oxidizer described in the step 1 is one or more in potassium permanganate, Potcrate or the potassium bichromate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101906194A CN102718209B (en) | 2012-06-11 | 2012-06-11 | Method for preparing graphene based on reduction of divalent iron ion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101906194A CN102718209B (en) | 2012-06-11 | 2012-06-11 | Method for preparing graphene based on reduction of divalent iron ion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102718209A CN102718209A (en) | 2012-10-10 |
| CN102718209B true CN102718209B (en) | 2013-09-11 |
Family
ID=46944120
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012101906194A Expired - Fee Related CN102718209B (en) | 2012-06-11 | 2012-06-11 | Method for preparing graphene based on reduction of divalent iron ion |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102718209B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103407995A (en) * | 2013-07-17 | 2013-11-27 | 苏州艾特斯环保材料有限公司 | Graphite oxide preparation method |
| KR20150027870A (en) * | 2013-08-29 | 2015-03-13 | 연세대학교 산학협력단 | Method for synthesizing graphene-based nanocomposite and graphene-based nanocomposite synthesized using the method |
| EP2982974B1 (en) * | 2014-08-06 | 2016-10-26 | Martechnic GmbH | Method of determining the iron content in a lubricating oil |
| CN105271214B (en) * | 2015-11-25 | 2017-09-05 | 合肥国轩高科动力能源有限公司 | Graphene oxidation-reduction preparation method |
| CN105838115B (en) * | 2016-04-27 | 2018-03-06 | 中国科学院上海硅酸盐研究所 | A kind of preparation method of graphene-based Electro-conductive pearlescent pigment |
| CN113402946A (en) * | 2021-05-26 | 2021-09-17 | 广州盛门新材料科技有限公司 | High-molecular light-reflecting coating and preparation method thereof |
| CN113233448B (en) * | 2021-06-10 | 2022-04-08 | 北京航空航天大学 | Surface modification method for reduced graphene oxide |
| CN117894969B (en) * | 2024-03-15 | 2024-05-24 | 上海巴库斯超导新材料有限公司 | Graphene-containing negative electrode material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101941842A (en) * | 2010-10-11 | 2011-01-12 | 东华大学 | Method for preparing graphene loaded ferroferric oxide magnetic nanometer particle composite material |
-
2012
- 2012-06-11 CN CN2012101906194A patent/CN102718209B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101941842A (en) * | 2010-10-11 | 2011-01-12 | 东华大学 | Method for preparing graphene loaded ferroferric oxide magnetic nanometer particle composite material |
Non-Patent Citations (2)
| Title |
|---|
| Oxidizing metal ions with graphene oxide: the in situ formation of magnetic nanoparticles on self-reduced graphene sheets for multifunctional applications;Yuhua Xue et al.;《Chem. Commun.》;20111231;第47卷;pp:11689–11691 * |
| Yuhua Xue et al..Oxidizing metal ions with graphene oxide: the in situ formation of magnetic nanoparticles on self-reduced graphene sheets for multifunctional applications.《Chem. Commun.》.2011,第47卷pp:11689–11691. |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102718209A (en) | 2012-10-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102718209B (en) | Method for preparing graphene based on reduction of divalent iron ion | |
| CN103011129B (en) | Method for preparing high-specific-surface-area porous graphitic nanocarbon plate with coconut shells serving as raw materials | |
| CN102167314B (en) | Method for preparing graphene | |
| CN105293483B (en) | A kind of method that original position prepares transient metal doped porous graphene | |
| CN102145887B (en) | Method for preparing and purifying graphene oxide | |
| CN101456554B (en) | Method for preparing graphitization nano carbon | |
| CN103145199B (en) | Preparation method of cobalt oxide/graphene composite nano material | |
| CN102153077A (en) | Method for preparing single-layer graphene with high carbon-oxygen ratio | |
| CN104475753B (en) | Liquid phase reduction prepares graphene-supported nanometer of Cu3.8The method of Ni alloy | |
| CN104815637A (en) | Method for hydrothermal method preparation of graphene-loaded flower-type titanium dioxide composite material | |
| CN103112844B (en) | Macro preparation method for mesoporous ordered graphene | |
| CN102730664B (en) | Carbon nano-tube with fluorine-containing surface and preparation method thereof | |
| CN107418513B (en) | Graphene foam loaded nano Fe3O4Magnetic particle composite wave-absorbing material and preparation method thereof | |
| CN103011151B (en) | Method for preparing graphene/nickel nanocomposite material by utilizing gamma ray | |
| CN102786045A (en) | Method for preparing oxidized graphene | |
| CN103570004A (en) | Simple large-scale preparation and functionalization method of graphene | |
| CN102698666A (en) | Preparation method of graphene/nanometer particle composite materials based on infrared ray radiation | |
| CN104150470A (en) | Metal-solution reduction method for preparing graphene | |
| CN103570010A (en) | Preparation method of graphene powder material | |
| CN105540590A (en) | Preparation method of Fe3C nanowire filled and nitrogen doped carbon nanotube composite with high specific surface area | |
| CN104495825A (en) | Method for preparing porous nanometer graphite | |
| CN101966989B (en) | Method for realizing photocatalytic reduction of graphene oxide by quadrangular zinc oxide | |
| CN104353842A (en) | Preparation method of nanosilver-graphene composite material | |
| Feng et al. | Graphene family for hydrogen peroxide production in electrochemical system | |
| Wang et al. | Simple synthesis of hollow carbon spheres from glucose |
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 | ||
| ASS | Succession or assignment of patent right |
Free format text: FORMER OWNER: SHENZHEN E JETON TECHNOLOGY CO., LTD. Effective date: 20141008 Owner name: SHENZHEN E JETON TECHNOLOGY CO., LTD. Free format text: FORMER OWNER: UNIVERSITY OF ELECTRONIC SCIENCE AND TECHNOLOGY OF CHINA Effective date: 20141008 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 611731 CHENGDU, SICHUAN PROVINCE TO: 523750 DONGGUAN, GUANGDONG PROVINCE |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20141008 Address after: 523750 Guangdong city of Dongguan Province Huang Town Po Shing Road No. 13 cattle Patentee after: Shenzhen E-jeton Technology Co., Ltd. Address before: 611731 Chengdu province high tech Zone (West) West source Avenue, No. 2006 Patentee before: University of Electronic Science and Technology of China Patentee before: Shenzhen E-jeton Technology Co., Ltd. |
|
| ASS | Succession or assignment of patent right |
Owner name: DONGGUAN SENJIA MACHINERY CO., LTD. Free format text: FORMER OWNER: SHENZHEN E JETON TECHNOLOGY CO., LTD. Effective date: 20150505 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 523750 DONGGUAN, GUANGDONG PROVINCE TO: 523000 DONGGUAN, GUANGDONG PROVINCE |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20150505 Address after: Guangdong province Dongguan City Huangjiang Town 523000 village Fu Road No. 21 South Street Patentee after: Dongguan Senjia Machinery Co., Ltd. Address before: 523750 Guangdong city of Dongguan Province Huang Town Po Shing Road No. 13 cattle Patentee before: Shenzhen E-jeton Technology Co., Ltd. |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130911 Termination date: 20190611 |