CN101003360A - Method for preparing magnesium based hydrogen storage material - Google Patents
Method for preparing magnesium based hydrogen storage material Download PDFInfo
- Publication number
- CN101003360A CN101003360A CN 200710061451 CN200710061451A CN101003360A CN 101003360 A CN101003360 A CN 101003360A CN 200710061451 CN200710061451 CN 200710061451 CN 200710061451 A CN200710061451 A CN 200710061451A CN 101003360 A CN101003360 A CN 101003360A
- Authority
- CN
- China
- Prior art keywords
- hydrogen
- magnesium
- hydrogenation
- storage material
- time
- 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
Landscapes
- Hydrogen, Water And Hydrids (AREA)
- Powder Metallurgy (AREA)
Abstract
This invention relates to a method for preparing Mg-based hydrogen-storage material, especially a method for rapidly preparing hydride. The method comprises: (1) loading pure Mg powder into a reactor, and partially hydriding Mg at 473-723 K and 1-6 MPa hydrogen pressure for 2-12 h; (2) ball-milling the obtained MgH2 for 30 min-12 h; (3) re-loading into the reactor, performing desorption/adsorption of hydrogen to completely convert the material into MgH2 in a short time. The method has such advantages as simple process, no need for any additive, high sample purity, and low hydride cost. The prepared MgH2 has excellent hydrogen-storage performance and good mechanical properties. The hydrogen discharge amount is 2.3-4.5 wt. %. After second hydriding, the purity of MgH2 is higher than 95%. This invention provides a new route to prepare practible Mg-based hydrogen-storage material.
Description
Technical field
The preparation method of a kind of magnesium-base hydrogen storage material of the present invention belongs to the preparation field of hydrogen storage material, is specifically related to a kind of preparation method of magnesium-base hydrogen storage material, particularly a kind of quick method for preparing hydride.
Background technology
Known hydrogenation that can hydrogen-absorbing material, its hydrogenation for the first time may be unusual difficulties, because have the natural oxide film of one deck usually on the surface of material, these oxide films have seriously hindered the infiltration of hydrogen.For this reason, we must destroy the hydrogenation first time that obstacle carries out this material, and hydrogenation is subsequently just carried out easily.The hydrogenation first time that destruction is coated on the oxide compound on hydrogen storage material surface is called " activation ".Usually hydrogen storage material is exposed to high temperature and high hydrogen pressure is realized this activation.The required temperature and pressure of hydrogenation is low more, and then activation is easy more, and hydrogenation time is short more.
The magnesium-base metal hydrogen storage material is big, in light weight owing to its hydrogen-storage amount, low price, and aboundresources is to be considered to the ideal hydrogen storage material always.But also there are three shortcomings in magnesium and alloy thereof as hydrogen storage material: (1) speed for hydrogen absorbing and releasing is slower, the reaction kinetics poor performance; (2) hydride is more stable, and putting hydrogen needs higher temperature; (3) surface of magnesium and alloy thereof forms easily the oxide film of one deck densification, more than these shortcomings seriously hindered the practicalization of magnesium-base metal hydrogen storage material.
Magnesium is a kind of activatory hydrogen storage material that is difficult to especially.For this reason, the investigator of various countries attempts to be set out by MAGNESIUM METAL, produces magnesium hydride fast with low cost, but does not obtain big success.
The hydrogenation of magnesium powder method commonly used has following several:
People such as Jean-Pierre Bastide, be entitled as " POLYMORPHISEM DEL ' HYDRURE DEMAGNESIUM SOUS HAUTE PRESSION " (Mat.Res.Bull., Vol.15,1215-1224,1980)-and mention hydrogen pressure in the literary composition at 600 crust (60MPa), can form magnesium hydride (greater than 96%) during 673K.
Using extreme condition in the ordinary method impels the investigator to attempt using catalyzer to promote the hydrogenation first time of magnesium.1993, the U.S.P.5198207 of TH.GOLDSCHMIDT AG discloses and used other metals, and was magnesium-doped as aluminium, indium, iron etc., the hydrogenation that comes catalysis magnesium, but do not obtain very big success.
Above-mentioned currently known methods all based on making magnesium at high temperature stand high hydrogen pressure, generates magnesium hydride, but is difficult to obtain pure magnesium hydride.
But, the someone finds, at room temperature produces magnesium hydride by mechanical alloying, and this method is based on making the magnesium powder stand violent mechanical ball milling in the presence of pressurized hydrogen.Be entitled as " forming metal hydride " (J.Of Alloys and Compounds by mechanical alloying, 217 (1994), 181) in the literary composition, Y.CHEN mentions, 240kPa (about 2.4 crust) hydrogen pressure under violent ball-milling magnesium powder after 47.5 hours, a large amount of magnesium are converted into magnesium hydride.But it is quite long and not exclusively to finish the hydrogenant time.
Be entitled as " by the hydrogenation-dehydrogenation behavior of the magnesium base composite material that obtains with graphite carbon mechanical mill " (International Journal of Hydrogen Energy, 25 (2000) 837-843) in the article, people such as H.IMAMURA confirm, be exposed to mixture under the hydrogen pressure of 66.7kPa (about 0.7 crust) at 353K after the grinding, if in the presence of hexanaphthene (CH) or tetrahydrofuran (THF) (THF), with or without catalyzer (Pd), the magnesium powder grinds with graphite, and the matrix material that obtains (Mg/C or Mg/C/Pd) is than the hydrogenation more quickly of independent magnesium.Only grind magnesium (promptly not having CH or THF) with graphite and will obtain very not active matrix material, it only absorbed 5% hydrogen in 20 hours.But, when in the presence of hexanaphthene, carrying out the grinding of magnesium and graphite, after 20 hours again 80% magnesium be converted into hydride.
Above content for the magnesium powder is converted into magnesium hydride fully, needs very harsh hydrogen pressure as can be seen usually, long time at least tens hours, even add other materials such as catalyzer and cause the purity of magnesium hydride not high.Consider the importance of magnesium as hydrogen storage material, from technology and technology, it will be exciting and interested that a kind of cost and time method that can significantly reduce the manufacturing magnesium hydride is provided.
Summary of the invention
Its purpose of the preparation method of a kind of magnesium-base hydrogen storage material of the present invention is to overcome and solves above-mentioned problems of the prior art, thereby the technical scheme of the high magnesium hydride method of a kind of quick preparation purity is provided.
The preparation method of a kind of magnesium-base hydrogen storage material of the present invention is characterized in that it being a kind of method for preparing magnesium hydride, it is characterized in that it being a kind of method for preparing magnesium hydride, and the processing step of its preparation is:
The first step is carried out the not exclusively hydrogenation first time in the reactor of earlier pure magnesium being packed into, and hydrogen pressure is 1MPa～6MPa, and temperature is 473K～723K, time 2～12h;
Second step, get above-mentioned sample mechanical ball milling 0.5～12 hour under argon gas or hydrogen atmosphere, atmosphere pressures is 0.5atm～1.5atm (0.05MPa～0.15MPa);
The 3rd step, get behind the ball milling sample hydrogenation fully in the reactor of packing into, its hydrogen pressure is 0.5MPa～6MPa, and temperature is 373K～723K, and hydrogenation time is 30 minutes～12 hours, and magnesium hydride purity is greater than 95% after the hydrogenation.
The preparation method of aforesaid a kind of magnesium-base hydrogen storage material is characterized in that described its purity of pure magnesium is 99%, granularity 100～200 orders.
The preparation method of aforesaid a kind of magnesium-base hydrogen storage material is characterized in that described Magnuminium is that Mg-M is an alloy, and M is Ni, Cu, Al or La.
The preparation method's of a kind of magnesium-base hydrogen storage material of the present invention advantage is: preparation technology is simple, and preparation gained material does not add any catalyzer, and the sample purity height can directly carry out the dynamic performance test; This result causes reducing manufacturing hydride, particularly makes the cost of magnesium hydride; Prepared magnesium hydride has excellent hydrogen storage property, has significant dynamic performance when keeping higher hydrogen-storage amount, and hydrogen desorption capacity is 2.3wt.%～4.5wt.%, once more after the hydrogenation magnesium hydride purity greater than 95%.
Embodiment
Embodiment 1:
The first step, with the hydrogenation for the first time in the reactor of packing into of the pure magnesium of 10.0g, hydrogen pressure is 6MPa, temperature is 673K, time 6h, 10.4 samples.
In second step, get above-mentioned sample 2g ball milling 9h, argon atmospher (1atm).
The 3rd step, get sample 0.5g behind the ball milling, in 613K, the 4MPa hydrogen pressure is put hydrogenation 3h in the hydrogen production device P-C-T tester in suction, does to put hydrogen for the first time and test to such an extent that hydrogen desorption capacity is 2.78wt.%.
Embodiment 2:
The first step, with the hydrogenation for the first time in the reactor of packing into of the pure magnesium of 9.5g, hydrogen pressure is 5MPa, temperature is 723K, time 12h, the 9.8g sample.
In second step, get above-mentioned sample 2g ball milling 3h, argon atmospher (1atm).
The 3rd step, get sample 0.5g behind the ball milling, in 623K, the 3MPa hydrogen pressure is put hydrogenation 2.5h in the hydrogen production device P-C-T tester in suction, does to put hydrogen for the first time and test to such an extent that hydrogen desorption capacity is 4.30wt.%.
Embodiment 3:
The first step, with the hydrogenation for the first time in the reactor of packing into of the pure magnesium of 10.0g, hydrogen pressure is 6MPa, temperature is 723K, time 6h, the 10.4g sample.
In second step, get above-mentioned sample 2g ball milling 12h, argon atmospher (1atm).
The 3rd step, get sample 0.5g behind the ball milling, in 603K, the 5MPa hydrogen pressure is put hydrogenation 2h in the hydrogen production device P-C-T tester in suction, does to put hydrogen for the first time and test to such an extent that hydrogen desorption capacity is 2.30wt.%.
Embodiment 4:
The first step, with the hydrogenation for the first time in the reactor of packing into of the pure magnesium of 9.5g, hydrogen pressure is 5MPa, temperature is 673K, time 12h, the 9.8g sample.
In second step, get above-mentioned sample 2g ball milling 6h, argon atmospher (1atm).
The 3rd step, get sample 0.5g behind the ball milling, in 623K, the 5MPa hydrogen pressure is put hydrogenation 2h in the hydrogen production device P-C-T tester in suction, does to put hydrogen for the first time and test to such an extent that hydrogen desorption capacity is 4.23wt.%.
Embodiment 5:
The first step, with the hydrogenation for the first time in the reactor of packing into of the pure magnesium of 10.0g, hydrogen pressure is 3.0MPa, temperature is 673K, time 6h, 10.4 samples.
In second step, got above-mentioned sample 2g ball milling 30 minutes, nitrogen atmosphere (1atm).
The 3rd step, get sample 0.5g behind the ball milling, in 613K, the 4MPa hydrogen pressure is put hydrogenation 3h in the hydrogen production device P-C-T tester in suction, does to put hydrogen for the first time and test to such an extent that hydrogen desorption capacity is 4.43wt.%.
Embodiment 6:
The first step, with the hydrogenation for the first time in the reactor of packing into of the pure magnesium of 9.5g, hydrogen pressure is 4.5MPa, temperature is 723K, time 12h, the 9.8g sample.
In second step, get above-mentioned sample 2g ball milling 3h, nitrogen atmosphere (1atm).
The 3rd step, get sample 0.5g behind the ball milling, in 623K, the 3MPa hydrogen pressure is put hydrogenation 2.5h in the hydrogen production device P-C-T tester in suction, does to put hydrogen for the first time and test to such an extent that hydrogen desorption capacity is 4.32wt.%.
Embodiment 7:
The first step, with the hydrogenation for the first time in the reactor of packing into of the pure magnesium of 10.0g, hydrogen pressure is 6MPa, temperature is 723K, time 6h, the 10.4g sample.
In second step, get above-mentioned sample 2g ball milling 12h, nitrogen atmosphere (1atm).
The 3rd step, get sample 0.5g behind the ball milling, in 603K, the 5MPa hydrogen pressure is put hydrogenation 2h in the hydrogen production device P-C-T tester in suction, does to put hydrogen for the first time and test to such an extent that hydrogen desorption capacity is 3.10wt.%.
Embodiment 8:
The first step, with the hydrogenation for the first time in the reactor of packing into of the pure magnesium of 9.5g, hydrogen pressure is 5MPa, temperature is 673K, time 12h, the 9.8g sample.
In second step, get above-mentioned sample 2g ball milling 6h, nitrogen atmosphere (1atm).
The 3rd step, get sample 0.5g behind the ball milling, in 623K, the 5MPa hydrogen pressure is put hydrogenation 2h in the hydrogen production device P-C-T tester in suction, does to put hydrogen for the first time and test to such an extent that hydrogen desorption capacity is 4.50wt.%.
Embodiment 9:
The first step is with 10.0gMg
2The Ni hydrogenation for the first time in the reactor of packing into, hydrogen pressure is 1.4MPa, temperature is 473K, time 3h, the 10.2g sample.
In second step, get above-mentioned sample 2g ball milling 12h, argon atmospher (1atm).
The 3rd step, get sample 0.5g behind the ball milling, in 573K, the 5MPa hydrogen pressure is put hydrogenation 3h in the hydrogen production device P-C-T tester in suction, does to put hydrogen for the first time and test to such an extent that hydrogen desorption capacity is 2.60wt.%.
Claims (3)
1. the preparation method of a magnesium-base hydrogen storage material, it is characterized in that it being a kind of method for preparing magnesium hydride, the processing step of its preparation is: the first step, earlier pure magnesium and Magnuminium are packed into and carry out incomplete hydrogenation first time in the reactor, hydrogen pressure is 1MPa～6MPa, temperature is 473K～723K, time 2～12h; Second step, get above-mentioned sample mechanical ball milling 0.5～12 hour under argon gas or hydrogen atmosphere, atmosphere pressures is 0.5atm～1.5atm (0.05MPa～0.15MPa); The 3rd step, get behind the ball milling sample hydrogenation fully in the reactor of packing into, its hydrogen pressure is 0.5MPa～6MPa, and temperature is 373K～723K, and hydrogenation time is 30 minutes～12 hours, and magnesium hydride purity is greater than 95% after the hydrogenation.
2. according to the preparation method of the described a kind of magnesium-base hydrogen storage material of claim 1, it is characterized in that described its purity of pure magnesium is 99%, granularity 100～200 orders.
3. according to the preparation method of the described a kind of magnesium-base hydrogen storage material of claim 1, it is characterized in that described Magnuminium is that Mg-M is an alloy, M is Ni, Cu, Al or La.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100614516A CN100431945C (en) | 2007-01-23 | 2007-01-23 | Method for preparing magnesium based hydrogen storage material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100614516A CN100431945C (en) | 2007-01-23 | 2007-01-23 | Method for preparing magnesium based hydrogen storage material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101003360A true CN101003360A (en) | 2007-07-25 |
| CN100431945C CN100431945C (en) | 2008-11-12 |
Family
ID=38702796
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007100614516A Expired - Fee Related CN100431945C (en) | 2007-01-23 | 2007-01-23 | Method for preparing magnesium based hydrogen storage material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100431945C (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101709396B (en) * | 2009-11-23 | 2011-01-05 | 广西大学 | Preparation method of magnesium-titanium-based hydrogen storage alloy |
| CN102583244A (en) * | 2012-02-17 | 2012-07-18 | 上海交通大学 | Method and device for preparing magnesium hydride |
| CN101910052B (en) * | 2009-03-05 | 2012-09-05 | 生物焦炭技术研究株式会社 | Method for producing magnesium-based hydride |
| CN105517951A (en) * | 2013-09-25 | 2016-04-20 | 太平洋水泥株式会社 | Method for producing metal hydride |
| CN108103337A (en) * | 2017-11-21 | 2018-06-01 | 上海交通大学 | The preparation method of magnesium-base hydrogen storage material |
| RU2686898C1 (en) * | 2018-05-30 | 2019-05-06 | Общество с ограниченной ответственностью "ХитЛаб" | Method of producing magnesium hydride for chemical generator of hydrogen |
| CN109972159A (en) * | 2019-04-08 | 2019-07-05 | 镁格氢动能源技术(苏州)有限公司 | Water power energy-storage system based on solid hydrogen technology |
| CN110877894A (en) * | 2018-09-06 | 2020-03-13 | 氢储(上海)能源科技有限公司 | Hydrogen storage and discharge method and system based on magnesium-based hydrogen storage material |
| CN112609102A (en) * | 2020-12-09 | 2021-04-06 | 浙江大学 | Preparation method of magnesium-based hydrogen storage material coated by rare earth oxide and nano nickel-boron |
| CN114180517A (en) * | 2021-12-16 | 2022-03-15 | 氢华能源技术(武汉)有限公司 | Method for preparing hydrogen storage material |
| CN115636390A (en) * | 2022-12-01 | 2023-01-24 | 世能氢电科技有限公司 | Magnesium-based composite hydrogen storage material and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ATE77602T1 (en) * | 1982-12-22 | 1992-07-15 | Studiengesellschaft Kohle Mbh | PROCESS FOR MANUFACTURING ACTIVE MAGNESIUM HYDRIDE MAGNESIUM HYDROGEN STORAGE SYSTEMS. |
| DE4419456A1 (en) * | 1994-06-03 | 1995-12-07 | Goldschmidt Ag Th | Process for the production of magnesium hydride |
| CN1169987C (en) * | 2000-10-26 | 2004-10-06 | 中国科学院金属研究所 | Process for preparing hydrogen-bearing Mg-base composition |
| US6680042B1 (en) * | 2000-11-07 | 2004-01-20 | Hydro-Quebec | Method of rapidly carrying out a hydrogenation of a hydrogen storage material |
| ES2265282B1 (en) * | 2005-07-06 | 2008-02-01 | Consejo Superior Investigaciones Cientificas | NANOPARTICULATED MAGNESIUM HYDRIDE, PREPARATION AND USE PROCEDURE. |
-
2007
- 2007-01-23 CN CNB2007100614516A patent/CN100431945C/en not_active Expired - Fee Related
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101910052B (en) * | 2009-03-05 | 2012-09-05 | 生物焦炭技术研究株式会社 | Method for producing magnesium-based hydride |
| CN101709396B (en) * | 2009-11-23 | 2011-01-05 | 广西大学 | Preparation method of magnesium-titanium-based hydrogen storage alloy |
| CN102583244A (en) * | 2012-02-17 | 2012-07-18 | 上海交通大学 | Method and device for preparing magnesium hydride |
| CN105517951A (en) * | 2013-09-25 | 2016-04-20 | 太平洋水泥株式会社 | Method for producing metal hydride |
| US9650247B2 (en) | 2013-09-25 | 2017-05-16 | Taiheiyo Cement Corporation | Method for producing metal hydride |
| CN105517951B (en) * | 2013-09-25 | 2017-11-14 | 太平洋水泥株式会社 | The manufacture method of metal hydride |
| CN108103337A (en) * | 2017-11-21 | 2018-06-01 | 上海交通大学 | The preparation method of magnesium-base hydrogen storage material |
| RU2686898C1 (en) * | 2018-05-30 | 2019-05-06 | Общество с ограниченной ответственностью "ХитЛаб" | Method of producing magnesium hydride for chemical generator of hydrogen |
| CN110877894B (en) * | 2018-09-06 | 2022-06-21 | 氢储(上海)能源科技有限公司 | Hydrogen storage and discharge method and system based on magnesium-based hydrogen storage material |
| CN110877894A (en) * | 2018-09-06 | 2020-03-13 | 氢储(上海)能源科技有限公司 | Hydrogen storage and discharge method and system based on magnesium-based hydrogen storage material |
| CN109972159A (en) * | 2019-04-08 | 2019-07-05 | 镁格氢动能源技术(苏州)有限公司 | Water power energy-storage system based on solid hydrogen technology |
| CN112609102B (en) * | 2020-12-09 | 2021-09-10 | 浙江大学 | Preparation method of magnesium-based hydrogen storage material coated by rare earth oxide and nano nickel-boron |
| CN112609102A (en) * | 2020-12-09 | 2021-04-06 | 浙江大学 | Preparation method of magnesium-based hydrogen storage material coated by rare earth oxide and nano nickel-boron |
| CN114180517A (en) * | 2021-12-16 | 2022-03-15 | 氢华能源技术(武汉)有限公司 | Method for preparing hydrogen storage material |
| CN114180517B (en) * | 2021-12-16 | 2022-06-07 | 氢华能源技术(武汉)有限公司 | Method for preparing hydrogen storage material |
| CN115636390A (en) * | 2022-12-01 | 2023-01-24 | 世能氢电科技有限公司 | Magnesium-based composite hydrogen storage material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100431945C (en) | 2008-11-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100431945C (en) | Method for preparing magnesium based hydrogen storage material | |
| CN101457321B (en) | Magnesium base composite hydrogen storage material and preparation method | |
| US6680042B1 (en) | Method of rapidly carrying out a hydrogenation of a hydrogen storage material | |
| CN100360695C (en) | Nano Mg base composite material, preparing process and use thereof | |
| CN102586660B (en) | Magnesium-based hydrogen storage alloy composite material with added metal sulfide | |
| CN112680645B (en) | Rare earth Sm-containing self-foaming porous magnesium alloy and preparation method thereof | |
| CN109972010A (en) | A kind of nano Mg base composite hydrogen storage material and preparation method | |
| CN112680643B (en) | Rare earth Y-containing self-foaming porous magnesium alloy and preparation method thereof | |
| CN106756361B (en) | A kind of Nanocrystalline Magnesium aluminium base hydrogen storage material and preparation method | |
| CN102674245B (en) | MgH2/Mg transition metal boride composite hydrogen storage material and preparation method thereof | |
| Grigorova et al. | Effect of additives on the hydrogen sorption properties of mechanically alloyed composites based on Mg and Mg2Ni | |
| US8163267B1 (en) | Method of synthesizing magnesium-cobalt pentahydride | |
| Hudson et al. | Studies on synthesis and dehydrogenation behavior of magnesium alanate and magnesium–sodium alanate mixture | |
| JP4187970B2 (en) | Hydrogen generation method | |
| EP1534870A1 (en) | Reactive milling process for the manufacture of a hydrogen storage alloy | |
| CN101293630B (en) | Nano-catalysis complex nitride hydrogen storing material and method for preparing the same | |
| CN109467048A (en) | Composite hydrogen storage material and its preparation method and application | |
| CN102556971A (en) | Li-Mg-based composite hydrogen storage material and preparation method thereof | |
| JP2004204309A (en) | Hydrogen storage material, and production method therefor | |
| Qu et al. | Comparative catalytic effects of NiCl 2, TiC and TiN on hydrogen storage properties of LiAlH 4 | |
| CN101992056B (en) | Composite hydrogen storage material for complexing hydrides and hydrogen storage alloys | |
| CN108193113B (en) | Preparation method of nano-confinement magnesium-rich alloy | |
| CN114293046A (en) | Preparation method of low-oxygen-content powder metallurgy porous titanium/zirconium-based hydrogen storage alloy | |
| KR100896454B1 (en) | Method for manufacturing magnesium based hydrogen storage alloy powder with fine-crystalline phase showing fast dehydriding kinetic and magnesium based hydrogen storage alloy powder with fine-crystalline phase showing fast dehydriding kinetic made of the method | |
| CN114105090B (en) | Mg-based composite hydrogen storage material for in-situ catalysis of high-entropy alloy and preparation method thereof |
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: 20081112 Termination date: 20100223 |