CN100459250C - A lack phase adulated anode material for solid oxide fuel battery - Google Patents

A lack phase adulated anode material for solid oxide fuel battery Download PDF

Info

Publication number
CN100459250C
CN100459250C CNB2007101757396A CN200710175739A CN100459250C CN 100459250 C CN100459250 C CN 100459250C CN B2007101757396 A CNB2007101757396 A CN B2007101757396A CN 200710175739 A CN200710175739 A CN 200710175739A CN 100459250 C CN100459250 C CN 100459250C
Authority
CN
China
Prior art keywords
anode material
doping
solid oxide
oxide fuel
anode
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CNB2007101757396A
Other languages
Chinese (zh)
Other versions
CN101123308A (en
Inventor
赵海雷
高峰
李雪
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Science and Technology Beijing USTB
Original Assignee
University of Science and Technology Beijing USTB
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by University of Science and Technology Beijing USTB filed Critical University of Science and Technology Beijing USTB
Priority to CNB2007101757396A priority Critical patent/CN100459250C/en
Publication of CN101123308A publication Critical patent/CN101123308A/en
Application granted granted Critical
Publication of CN100459250C publication Critical patent/CN100459250C/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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

Landscapes

  • Fuel Cell (AREA)

Abstract

A vacancy doping anode material for solid oxide fuel cell belongs to the fuel cell field. The invention is characterized in that place A of the perovskite-type SrTiO3 is the vacancy doping of Y, the molecular formula after the vacancy doping is (Y0.08Sr0.92)1-xTiO3-triangle, wherein, x is equal to 0.005 subtracting 0.07, and the place A is doped with transition element Yttrium. The vacancy doping anode material prepared by the invention can be used in solid oxide fuel cell, and has the advantages of stable performance, good chemical compatibility with electrolyte YSZ and LSGM. Meanwhile, the invention has the high electronic conductivity and the ionic conductivity, the total conductivity increases by 6.38 percent to 22.7 percent and the ionic conductivity increases by two orders of magnitude by comparing to the data of Y0.08Sr0.92TiO3-triangle without vacancy doping material at 800 DEG C, thereby promoting the working performance of SOFC and advancing the practical utilization process of SOFC.

Description

A kind of lack phase adulated anode material that is used for Solid Oxide Fuel Cell
Technical field
The invention belongs to fuel cell field, be specifically related to that vacantly mix in the high A position of a kind of stable performance, conductivity, cubic perovskite type strontium titanates anode of solid oxide fuel cell material.
Technical background
The research and development of fuel cell is considered to the generation technology of the efficient pollution-free of 21 century first-selection as one of technology of greatly developing and promote in the 21 century world wide.Solid Oxide Fuel Cell (SOFC) is a third generation fuel cell, is solid-state energy conversion, has the strong and advantages of environment protection of conversion efficiency height, suitability of fuel, is to have one of green energy resource of development potentiality most.
The performance of anode material is the key factor that influences solid-oxide fuel battery performance, anode not only will provide the place for the electrochemical oxidation reactions of fuel, also to play catalytic action to the carrying out of fuel oxidation reaction, electronics and the gas of also wanting transfer reaction to produce simultaneously.In addition, because the operating ambient temperature height of anode material, it not only contacts with fuel, but also with reaction impurities and the ever-increasing oxidation product of concentration, and electrolyte, some other parts of batteries such as connector contact, according to document A.Atkinson, S.Barnett, R.J.Gorte, et al.Advanced anodes forhigh-temperature fuel cells.Nature Materials, 2004 (3): 17～27 report, when the antianode material is selected, must consider its action function and operational environment simultaneously, this just requires generally must have as the material of SOFC anode:
1. high electronics and ionic conductivity make electrolyte pass the ion of coming and arrive conversion zone smoothly, and the electronics that reaction produces passes to external loop smoothly and produces electric current.
2. good catalytic activity and enough surface areas are with the carrying out of the electrochemical oxidation reactions that promotes fuel;
3. the suitable porosity makes fuel gas can be penetrated into electrode-electrolyte interface place continuously and participates in reaction, and the steam of generation and other accessory substance are taken away, simultaneously the not serious again structural strength that influences anode;
4. with the chemical compatibility of contacted material, thermal expansion matching;
5. good chemical stability, structure and mutually stability.
SOFC the most frequently used anode at present is Ni/YSZ, generally uses pure hydrogen to do fuel.But because the hydrogen manufacturing problem is not solved at present at all, the cost of hydrogen fuel is too high, so use hydrocarbon gas to do the trend that fuel is the SOFC development.According to document Y.Matsuzaki, I.Yasuda.The poisoning effect of sulfur-containingimpurity gas on a SOFC anode:Part I.Dependence on temperature, time, and impurityconcentration.Solid State Ionics, 2000,132:261～269 reports: if use hydrocarbon gas to do fuel, the Ni/YSZ anode just problems such as carbon laydown, sulfur poisoning may occur, and this will influence the catalytic activity of anode and the stable work in work of battery.Therefore, research and development are urgent and necessary to the anode material that hydrocarbon fuel has adaptability.
ABO 3The SrTiO of type perovskite structure 3In very wide partial pressure of oxygen and temperature range, can keep the stable of structure and performance, doping by A, B bit element, can improve the electronic conductance and the ionic conductance of material, and can improve the catalytic activity of material, thereby become one of outstanding candidate of SOFC anode material.The SrTiO of stoichiometric proportion 3Conductivity is very low, can not be directly used in anode material.But it has very strong doping ability in A, B position, thereby can be by mixing to its modification the SrTiO of doping 3Show the character of mixed conductor, electrochemical reaction can take place on entire electrode, and this will reduce the concentration polarization of battery.Simultaneously, SrTiO 3Be full ceramic component, at high temperature have structural stability and the chemical stability higher than Ni/YSZ.The SrTiO that mixes 3Can with multiple electrolyte compatibility, physics and chemical reaction can not take place.In recent years, SrTiO 3The base anode material has caused people's very big interest.But the battery performance by this anode material assembling is desirable not enough, and power output is on the low side, and performance degradation is more serious, and its structure and performance await further to improve.How to improve SrTiO by the selection of doped chemical kind and the control of doping 3Conductivity, become SrTiO 3Key point as SOFC anode material practicability.
According to document S.Hui, A.Petric.Evaluation of yttrium-doped SrTiO 3As anode for solidoxide fuel cells, Journal of European Ceramic Society, 2002 (22): 1673～1681 report: Y doping SrTiO 3In very wide partial pressure of oxygen scope (1～10 -20Atm) shown stability of structure and high conductivity, thermal coefficient of expansion and YSZ and LSGM coupling is 58mW/cm as the monocell maximum power density of anode assembling 900 ℃ the time 2O.A.Marina, N.L.Canfield, J.W.Stevenson.Thermal, electrical, andelectrocatalytical properties of lanthanum-doped strontium titanate, Solid State Ionics, 2002 (149): 21～28 reports: La doping SrTiO 3Conductivity be subjected to the influence of doping and partial pressure of oxygen bigger, the physics of this material and stable chemical performance in redox reaction; D.P.Fagg, V.V.Khaton, A.V.Kovalevsky, et al.The stability and mixed conductivity in La and Fe doped SrTiO 3In the search for potentialSOFC anode materials, Journal of European Ceramic Society, 2001 (21): 1831～1835. and D.P.Fagg, V.V.Khaton, JR Frade, et al.Stability and mixed ionic-electronic conductivity of (Sr, La) (Ti, Fe) O 3-δPerovskites, Solid State Ionics, 2003 (156): 45～57 reports: La mixes, make material in hydrogen stability and all improve a lot with the chemical compatibility of YSZ, electronic conductance increases; But lead and the electronic conductance reduction at air intermediate ion electricity, transference number of ions reduces.Ionic conductance and electronic conductance increase along with the increase of Fe doping.The increase of the sublattice defective of A position and B position sublattice cation concn increases the material coefficient of thermal expansion coefficient, and reproducibility strengthens; And the generation in room, A position can suppress the reaction of material and YSZ.Document XueLi, Hailei Zhao, et al.Synthesis and properties of Y-doped SrTiO 3As an anode material forSOFCs, Journal of Power Sources, 2007 (166): 47-52 is to the Y SrTiO that mixes 3Ion and electronic conductivity, thermal circulation performance, thermal stability, catalytic activity, battery performance etc. all study, reach a conclusion, when the doping of Y is 8mol%, every performance of material is best, but, the ionic conductance of this material and electronic conductance are still on the low side, and this will cause bigger anode polarization phenomenon in the battery operation process.In order further to improve the conductivity of anode material, need SrTiO 3Anode performance is further improved.
Summary of the invention
The objective of the invention is to overcome stoichiometric proportion doping SrTiO 3The defective that anode material electronic conductance or ionic conductivity are on the low side, a kind of stable performance, Solid Oxide Fuel Cell anode material (Y that conductivity is high are prepared in research 0.08Sr 0.92) 1-xTiO 3-δ, promptly at Ca-Ti ore type SrTiO 3The omission of carrying out Y of A position mix, can improve the electronic conductivity and the ionic conductivity of anode greatly, reduce the polarization resistance of anode material, improve the operating characteristic of anode material, with electrolyte YSZ, LSGM good chemical compatibility is arranged, thereby improve the SOFC service behaviour, promote the practicalization of SOFC.
The invention is characterized in: Ca-Ti ore type SrTiO 3The A position be that the omission of Y is mixed, the molecular formula after vacant the doping is: (Y 0.08Sr 0.92) 1-xTiO 3-δ, x=0.005-0.07 wherein, the transition elements of mixing in described A position is a yttrium.
The present invention can be used for the anode material of Solid Oxide Fuel Cell, and stable performance has good chemical compatibility with electrolyte YSZ, LSGM.Electronic conductivity and ionic conductivity height are under 800 ℃, with the material Y that does not have vacant doping 0.08Sr 0.92TiO 3-δData compare, the total conductivity of material has improved 6.38% to 22.7%; Ionic conductivity has improved 2 orders of magnitude.
Material provided by the invention can prepare as follows:
A, with raw material with Y 2O 3Or Y (NO 3) 3Or Y 2(CO 3) 3, SrCO 3Or SrO or Sr (NO 3) 2, TiO 2Or TiCl 4Or butyl titanate is according to (Y 0.08Sr 0.92) 1-xTiO 3-δ(x=0.005-0.07) chemical ratios preparation.
B, the vacant SrTiO that mixes in above-mentioned A position 3Material adopts solid phase method, hydro thermal method and citric acid method synthetic powder in 1000-1500 ℃, reducing atmosphere.
C, with the doping SrTiO of synthetic A position omission 3After powder wet-milling or the dry grinding, sieve (100-200 order), the vacant doping SrTiO in preparation A position 3The anode fine powder.
D, in the A position vacant doping SrTiO 3Add the inflammable substance of 10-50 volume % in the anode fine powder, inflammable substance comprises carbon dust, starch, corn flour, resin, and dry-pressing or half-dried molded then in 1100-1600 ℃ of temperature lower calcination 2-16 hour, can prepare the porous anode block again; Or with the vacant doping SrTiO in A position 3The anode powder in add entry, soluble starch and ethyl cellulose and make slurry, adopt silk screen print method that it is coated in the fine and close YSZ or the LaGaO of doping equably 3The vacant doping SrTiO in A position of porous through 1100-1600 ℃ of temperature lower calcination 2-16 hour, is made in the electrolyte sheet surface 3Anode film.
The invention has the advantages that, to Ca-Ti ore type SrTiO 3The omission doping of Y is carried out in the A position of material, and then causes the increase and the Ti of oxygen vacancy concentration 3+The increase of concentration, with respect to non-vacant the doping, the total conductivity of material and ionic conductivity all improve greatly, for (Y 0.08Sr 0.92) 1-xTiO 3-δ(x=0.05) sample, the total conductivity under 800 ℃ is 73.15S/cm, ionic conductivity is 0.013S/cm, forms mixed conductor material a kind of perovskite structure, high conductivity.As shown in Figure 1, the x-ray diffraction pattern of the material of A position omission 0.06 occurs without any impurity, and material shows as pure perovskite structure.
Description of drawings
Fig. 1 is the synthetic (Y of solid reaction process of the present invention 0.08Sr 0.92) 1-xTiO 3-δXRD figure during powder x=0.06, synthesis temperature are 1500 ℃.
(the Y that Fig. 2 synthesizes for the present invention 0.08Sr 0.92) 1-xTiO 3-δThe temperature variant curve of conductivity of (x=0,0.01) sample, sintering temperature is 1500 ℃.
(the Y that Fig. 3 synthesizes for the present invention 0.08Sr 0.92) 1-xTiO 3-δThe temperature variant curve of ionic conductivity of (x=0,0.05) sample, sintering temperature is 1500 ℃.
Embodiment
Embodiment 1:
With Y 2O 3, SrCO 3, TiO 2Be raw material, according to (Y 0.08Sr 0.92) 0.99TiO 3-δThe element ratio preparating mixture, be medium with alcohol, ball milling is 6 hours in the agate ball ball grinder, after mixing, dries in baking oven.The powder grinding of oven dry is sieved in (100 order), and the powder after sieving is contained in the alumina crucible at 5%H 2In/Ar the atmosphere, 1300 ℃ of insulations were synthesized in 10 hours.Synthetic powder is sieved in (100 order), add the carbon dust of 40 volume %, 2 volume %PVA solution mix dry-pressing formedly, and the sample that makes is incubated 5 hours down at 1500 ℃, make the porous anode material.Total conductivity during 1000 ℃ of materials is 59.8S/cm, and ionic conductivity is 1.6 * 10 -2S/cm, as shown in Figure 2, vacant 0.01 o'clock, material all was higher than not vacant sample in conductivity at each temperature.Under 1000 ℃ of conditions with YSZ, La 0.8Sr 0.2Ga 0.8Mg 0.2O 3Electrolyte does not have chemical reaction.
Embodiment 2:
With Y (NO 3) 3, Sr (NO 3) 2, TiCl 4Be raw material, according to (Y 0.08Sr 0.92) 0.95TiO 3-δThe element ratio preparating mixture, make solvent with the potassium hydroxide solution of 1mol/L, be reflected in the autoclave of sealing and carry out, autoclave is warming up to 150 ℃ of insulation 30min.Behind the autoclave natural cooling, with the washing of precipitate drying, the powder that obtains synthesizing.With synthetic powder sieve (160 order), get the 1g powder, add the soluble starch of 10% mass fraction and the ethyl cellulose of 1% mass fraction, add the 1ml deionized water at last, mix the back and be coated in the electrolyte YSZ surface of the densification that high temperature burns till with silk screen print method equably, be incubated 10 hours down at 1550 ℃, make the porous anode thin-film material.Total conductivity during 1000 ℃ of materials is 50.1S/cm, and ionic conductivity is 2.38 * 10 -2S/cm, as shown in Figure 3, vacant 0.05 o'clock, material all was higher than not vacant sample in conductivity at each temperature.Under 1000 ℃ of conditions with YSZ, La 0.8Sr 0.2Ga 0.8Mg 0.2O 3Electrolyte does not have chemical reaction.
Embodiment 3:
By (Y 0.08Sr 0.92) 0.97TiO 3-δStoichiometric proportion take by weighing butyl titanate (chemical pure), Y 2(CO 3) 3(analyzing pure) and SrCO 3(analyzing pure).Earlier butyl titanate and ethylenediamine tetra-acetic acid (EDTA analyzes pure) are mixed, wherein the mol ratio of EDTA and titanium ion is 1: 1, and the back that is dissolved in water to clarification, adds Y 80 ℃ of stirring in water bath again 2(CO 3) 3And SrCO 3In the mol ratio of citric acid (analyzing pure) and titanium ion is that 4: 1 ratio adds citric acid, regulates the pH value to 8-9 with ammoniacal liquor, obtains light yellow vitreosol through adding thermal agitation.Colloidal sol obtains clear gel after the drying in baking oven, gel obtains porous spongy coking product through the heating coking.With obtaining elementary powder after the grinding of coking product is presoma.In 500-600 ℃ of temperature range, elementary powder is heat-treated, obtain synthetic powder.Synthetic powder is sieved in (100 order), add the carbon dust of 40 volume %, 2 volume %PVA solution mix dry-pressing formedly, and the sample that makes is incubated 5 hours down at 1500 ℃, make the porous anode material.Under 1000 ℃ of conditions with YSZ, La 0.8Sr 0.2Ga 0.8Mg 0.2O 3Electrolyte does not have chemical reaction.

Claims (2)

1, a kind of lack phase adulated anode material that is used for Solid Oxide Fuel Cell is characterized in that, Ca-Ti ore type SrTiO 3The A position be that the omission of yttrium is mixed, the molecular formula after vacant the doping is: (Y 0.08Sr 0.92) 1-xTiO 3-δ, x=0.005-0.07 wherein.
2, the purposes of the described lack phase adulated anode material of claim 1, this material is used for Solid Oxide Fuel Cell.
CNB2007101757396A 2007-10-11 2007-10-11 A lack phase adulated anode material for solid oxide fuel battery Expired - Fee Related CN100459250C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNB2007101757396A CN100459250C (en) 2007-10-11 2007-10-11 A lack phase adulated anode material for solid oxide fuel battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNB2007101757396A CN100459250C (en) 2007-10-11 2007-10-11 A lack phase adulated anode material for solid oxide fuel battery

Publications (2)

Publication Number Publication Date
CN101123308A CN101123308A (en) 2008-02-13
CN100459250C true CN100459250C (en) 2009-02-04

Family

ID=39085539

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB2007101757396A Expired - Fee Related CN100459250C (en) 2007-10-11 2007-10-11 A lack phase adulated anode material for solid oxide fuel battery

Country Status (1)

Country Link
CN (1) CN100459250C (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8952295B2 (en) * 2008-06-18 2015-02-10 Lincoln Global, Inc. Welding wire with perovskite coating
CN105908211B (en) * 2016-05-05 2017-12-26 东北林业大学 A kind of preparation of electrolytic cell device, electrolytic cell of high-temperature electrolysis water hydrogen manufacturing stable operation and the application method of electrolytic cell device
CN108774749A (en) * 2018-06-22 2018-11-09 西北工业大学 The preparation method of strontium titanate monocrystal surface metalation
CN110061245A (en) * 2019-04-11 2019-07-26 武汉大学 The preparation method of solid oxide cell electrode material
CN110357614B (en) * 2019-07-25 2021-12-10 哈尔滨理工大学 Room-temperature paraelectric-ferroelectric adjustable ceramic material and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1672284A (en) * 2002-08-01 2005-09-21 圣安德鲁斯大学董事会 Perovskite-based fuel cell electrode and membrane
US20050250000A1 (en) * 2004-05-07 2005-11-10 Battelle Memorial Institute Novel composite solid oxide fuel cell anode based on ceria and strontium titanate

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1672284A (en) * 2002-08-01 2005-09-21 圣安德鲁斯大学董事会 Perovskite-based fuel cell electrode and membrane
US20050250000A1 (en) * 2004-05-07 2005-11-10 Battelle Memorial Institute Novel composite solid oxide fuel cell anode based on ceria and strontium titanate

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Evaluation of yttrium-doped SrTiO3 as an anode for solidoxide fuel cells. Shiqiang Hui, Anthony Petric.Journal of the European Ceramic Society,Vol.22 No.9. 2002
Evaluation of yttrium-doped SrTiO3 as an anode for solidoxide fuel cells. Shiqiang Hui, Anthony Petric.Journal of the European Ceramic Society,Vol.22 No.9. 2002 *

Also Published As

Publication number Publication date
CN101123308A (en) 2008-02-13

Similar Documents

Publication Publication Date Title
Nguyen et al. Preparation and evaluation of BaZr0. 1Ce0. 7Y0. 1Yb0. 1O3− δ (BZCYYb) electrolyte and BZCYYb-based solid oxide fuel cells
CN110581283B (en) Bismuth-doped solid oxide cell fuel electrode material and preparation method and application thereof
Huang et al. Investigation of La2NiO4+ δ-based cathodes for SDC–carbonate composite electrolyte intermediate temperature fuel cells
Gao et al. Infiltrated Pr2NiO4 as promising bi-electrode for symmetrical solid oxide fuel cells
CN104916850B (en) Cathode of solid oxide fuel cell material and have its composite cathode material and preparation method thereof and battery composite cathode preparation method
CN100583516C (en) A cathode material for A and B adulterated SrTiO3 solid oxide fuel battery
Flores et al. Advances in the development of titanates for anodes in SOFC
CN101599546A (en) A kind of cathode material for solid-oxide fuel cell and application
Wang et al. A novel CO2-tolerant Ba0. 5Sr0. 5Co0. 8Fe0. 1Ta0. 1O3-δ cathode with high performance for proton-conducting solid oxide fuel cells
CN108649235A (en) A kind of A laminated perovskite type electrode material and preparation method thereof
CN102942364A (en) Zinc oxide-carbonate co-doped cerium barium zirconate proton conductor material and preparation method thereof
CN100459250C (en) A lack phase adulated anode material for solid oxide fuel battery
Jafari et al. Enhancement of an IT-SOFC cathode by introducing YSZ: Electrical and electrochemical properties of La0. 6Ca0. 4Fe0. 8Ni0. 2O3-δ-YSZ composites
Fu et al. Performance of Pd-impregnated Sr1. 9FeNb0. 9Mo0. 1O6-δ double perovskites as symmetrical electrodes for direct hydrocarbon solid oxide fuel cells
CN100502117C (en) B-position omission perovskite anode material used for solid-oxide fuel battery
Miao et al. Optimizing strontium titanate anode in solid oxide fuel cells by ytterbium doping
CN115044928A (en) Proton conductor type solid oxide electrochemical cell oxygen electrode material and preparation method thereof
Devi et al. Solid oxide fuel cell materials: a review
CN101299460A (en) Anode material lacking A bit for solid-oxide fuel battery
Yang et al. Sr-substituted SmBa0. 75Ca0. 25CoFeO5+ δ as a cathode for intermediate-temperature solid oxide fuel cells
Zhang et al. An intermediate temperature fuel cell based on composite electrolyte of carbonate and doped barium cerate with SrFe0. 7Mn0. 2Mo0. 1O3− δ cathode
Afzal et al. Lanthanum-doped calcium manganite (La0. 1Ca0. 9MnO3) cathode for advanced solid oxide fuel cell (SOFC)
CN116014159A (en) Oxygen electrode material of solid oxide battery, preparation method and application
CN115650312A (en) Proton conductor reversible battery air electrode, preparation method and application
JP3573519B2 (en) Single cell of solid oxide fuel cell and method of manufacturing the same

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: 20090204

Termination date: 20111011