CN102185144A - Metal oxide/graphene composite material and preparation method thereof - Google Patents

Metal oxide/graphene composite material and preparation method thereof Download PDF

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Publication number
CN102185144A
CN102185144A CN2011100837281A CN201110083728A CN102185144A CN 102185144 A CN102185144 A CN 102185144A CN 2011100837281 A CN2011100837281 A CN 2011100837281A CN 201110083728 A CN201110083728 A CN 201110083728A CN 102185144 A CN102185144 A CN 102185144A
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metal oxide
composite material
graphene composite
metal
graphene
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谢健
刘双宇
宋文涛
郑云肖
曹高劭
赵新兵
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Zhejiang University ZJU
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Zhejiang University ZJU
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract

The invention discloses a metal oxide/graphene composite material, which consists of a nanometer metal oxide and graphene, wherein the metal oxide is an oxide of a metal from IIIA group, IVA group or VA group. Because of the dispersing and loading effects of the graphene, the metal oxide in the composite material can be distributed uniformly and is small in particle size, and the stability and the cyclical stability of the metal oxide in the process of charging and discharging can be effectively improved. The invention also discloses a one-step low-temperature preparation method of the composite material, which has the advantages of simple process, low cost, short cycle, low energy consumption and the like, and is suitable for large-scale industrial production.

Description

Metal oxide/graphene composite material and preparation method thereof
Technical field
The present invention relates to the lithium ion battery field of compound material, be specifically related to a kind of metal oxide/graphene composite material and preparation method thereof.
Background technology
Lithium ion battery has advantages such as operating voltage height, energy density is big, security performance is good, therefore is used widely in portable type electronic products such as digital camera, mobile phone and notebook computer, also has application prospect for electric bicycle and electric automobile.Present commercial lithium ion battery generally adopts the carbon back negative material, though this material stability is higher, theoretical capacity only has 372mAhg -1
Compare with material with carbon element, some metal oxide has the high theoretical capacity, as the theoretical capacity of SnO up to 870mAhg -1This quasi-metal oxides has a general character: reversible alloying can take place and take off alloying reaction in contained metal with lithium metal, and this reaction provides reversible capacity, and the Li that forms 2O no longer decomposes as matrix, and its course of reaction can be write as:
M xO y+(nx+2y)Li→x?Li nM+y?Li 2O
Though this reaction can provide higher capacity, because alloying and to take off in the alloying process change in volume bigger causes the rapid decay of capacity.At present, effectively slow down capacity fast the method for decay generally be metal oxide and other basis material to be carried out compound, comparatively ideal basis material is a material with carbon element.In various material with carbon elements, Graphene is very desirable basis material because of its high conductivity, high mechanical strength, big specific area agent and porosity.
Summary of the invention
The invention provides a kind of electrochemical stability and cyclical stability good metal oxide/graphene composite material.
The invention provides a kind of preparation method of metal oxide/graphene composite material, this method technology is simple, and energy consumption is low, cost is low, is suitable for large-scale industrial production.
The present invention finds metal oxide and Graphene is compound, can be used to improve the chemical property, particularly cyclical stability of metal oxide.
A kind of metal oxide/graphene composite material is made up of nanosize metal oxide and Graphene (G), and described metal oxide is the oxide of IIIA family metal, the oxide of IVA family metal or the oxide of VA family metal.
Described metal oxide can be selected Bi for use 2O 3, Sb 2O 3, Sb 2O 5, In 2O 3, SnO, SnO 2, PbO or Pb 3O 4
In order further to improve the application performance of composite material, the weight percentage of Graphene is preferably 0.5%～10% in the described composite material.
The preparation method of described metal oxide/graphene composite material may further comprise the steps:
1) compound that will contain IIIA family metal, IVA family metal or VA family metal is dissolved in deionized water or the organic solvent, obtains the solution that concentration is 0.01mol/L～0.1mol/L, adds graphene oxide (GO) again, obtains mixed solution;
The addition of described GO is 1%～20% of a metal oxide theoretical weight;
2) the reducing agent hydrazine hydrate will be added in the mixed solution of step 1), every milligram of GO adds hydrazine hydrate 1 μ L～10 μ L, add alkaline conditioner again the pH value is transferred to 8～12, be warming up to 100 ℃～250 ℃ then, react after 4 hours～48 hours and be cooled to room temperature, collect solid product, through deionized water and the washing of absolute ethyl alcohol alternate repetition, drying obtains metal oxide/graphene composite material.
In order to reach better invention effect, preferably:
Add surfactant in the mixed liquor of step 1), the molal quantity of described surfactant is 0～2: 1 with the ratio of the theoretical molar number of transition metal oxide.
Described surfactant is softex kw (CTAB), dodecyl sodium sulfate (SDS) or polyvinylpyrrolidone (PVP).When described surfactant was polyvinylpyrrolidone, its molal quantity converted with the molecular weight of N-vinylpyrrolidone monomer.
The compound of the described IIIA of containing family metal, IVA family metal or VA family metal is chloride, nitrate, sulfate, oxalates or acetate.Described IIIA family metal is In; Described IVA family metal is Sn or Pb; Described VA family metal is Bi or Sb.
Described organic solvent is ethanol, methyl alcohol, ethylene glycol, 1-butanols, N, dinethylformamide, pyridine, ethylenediamine, benzene or toluene.
Described alkaline conditioner is ammoniacal liquor, sodium hydrate aqueous solution or potassium hydroxide aqueous solution.
Described metal oxide/graphene composite material can be used as ion cathode material lithium.
Compared with prior art, the present invention has following advantage:
1, the present invention adopts one-step method to prepare metal oxide/graphene composite material at low temperature, has that technology is simple, cost is low, the cycle is short, low power consumption and other advantages, is fit to large-scale industrial production.
2, owing to the dispersion and the carrying effect of Graphene, the metal oxide granularity is little in the gained composite material, and diameter is about 10～40 nanometers, and it is more even to distribute, and can effectively improve its stability and cyclical stability in charge and discharge process.
Description of drawings
Fig. 1 is embodiment 3 gained SnO 2The X ray diffracting spectrum of/graphene composite material, all diffraction maximums can be classified as SnO among Fig. 1 2Diffraction maximum, do not find among Fig. 1 the diffraction maximum of Graphene to show that graphene layer is by SnO 2Uniform particles is disperseed;
Fig. 2 is embodiment 3 gained SnO 2The transmission electron microscope photo of/graphene composite material.
Embodiment
Embodiment 1
With Bi (NO 3) 35H 2O is a raw material, with Bi (NO 3) 35H 2O is dissolved in the deionized water, is mixed with 80 milliliters of Bi (NO 3) 3Concentration is the solution of 0.04mol/L, adds 30 milligrams of GO again and makes mixed solution; It is 100 milliliters autoclave (compactedness 80% that mixed solution is placed capacity, percent by volume) in, add 0.3 gram surfactant PVP (its molal quantity converts with the molecular weight of N-vinylpyrrolidone monomer) and 100 μ L hydrazine hydrates, the NaOH aqueous solution with 6mol/L transfers to 10 with the pH value again, then reactor is sealed, reacted 12 hours down at 190 ℃, naturally cool to room temperature; Collect solid reaction product, through deionized water and the washing of absolute ethyl alcohol alternate repetition, drying obtains the 0.75g composite material with product, and wherein, the weight percentage of Graphene is 1.3%.
The X ray diffracting spectrum of the composite material of gained and transmission electron microscope photo show that the composite material of gained is Bi 2O 3/ graphene composite material, wherein Bi 2O 3Particle size is nanoscale, and diameter is about 10 nanometers～20 nanometers, and it is more even to distribute.
Constant current charge-discharge (current density 40mAg -1, voltage range 0.05～1.5V) test shows is with pure nanometer Bi 2O 3Compare gained Bi 2O 3The electrochemistry cyclical stability of/graphene composite material in charge and discharge process obviously improves.
Embodiment 2
With SbCl 3Be raw material, with SbCl 3Be dissolved in the deionized water, be mixed with the solution of 0.02mol/L, add 15 milligrams of GO again and make mixed solution; It is 100 milliliters autoclave (compactedness 80% that 80 milliliters of mixed solutions are placed capacity, percent by volume) in, add 0.2 gram surfactant SDS and 60 μ L hydrazine hydrates, with 25wt% ammoniacal liquor the pH value is transferred to 9 again, then reactor is sealed, reacted 8 hours down at 180 ℃, naturally cool to room temperature; Collect solid reaction product, through deionized water and the washing of absolute ethyl alcohol alternate repetition, drying obtains 0.2g Sb with product 2O 3/ graphene composite material, wherein, the weight percentage of Graphene is 3.2%.
The X ray diffracting spectrum of the composite material of gained and transmission electron microscope photo show that the composite material of gained is Sb 2O 3/ graphene composite material, wherein Sb 2O 3Particle size is nanoscale, and diameter is about 15 nanometers～20 nanometers, and it is more even to distribute.
Constant current charge-discharge (current density 40mAg -1, voltage range 0.05～1.5V) test shows is with pure nanometer Sb 2O 3Compare gained Sb 2O 3The electrochemistry cyclical stability of/graphene composite material in charge and discharge process obviously improves.
Embodiment 3
With SnCl 45H 2O is a raw material, is dissolved in being mixed with SnCl in the ethanol 4Concentration is the solution of 0.01mol/L, adds 10 milligrams of GO again and makes mixed solution; It is 100 milliliters autoclave (compactedness 80% that 80 milliliters of mixed solutions are placed capacity, percent by volume) in, add 0.1 gram surfactant SDS and 30 μ L hydrazine hydrates, KOH with 6mol/L transfers to 8 with the pH value again, then reactor is sealed, reacted 4 hours down at 200 ℃, naturally cool to room temperature; Collect solid reaction product, through deionized water and the washing of absolute ethyl alcohol alternate repetition, drying obtains 0.11g SnO with product 2/ graphene composite material, wherein, the weight percentage of Graphene is 4.1%.
The X ray diffracting spectrum of the composite material of gained and transmission electron microscope photo show that respectively as Fig. 1 and Fig. 2 the composite material of gained is SnO 2/ graphene composite material, wherein SnO 2Particle size is nanoscale, and diameter is about 10 nanometers～20 nanometers, and it is more even to distribute.
Constant current charge-discharge (current density 40mAg -1, voltage range 0.05～1.5V) test shows is with pure nano SnO 2Compare gained SnO 2The electrochemistry cyclical stability of/graphene composite material in charge and discharge process obviously improves.
Embodiment 4
With SnCl 22H 2O is a raw material, is dissolved in deionized water and is mixed with SnCl 2Concentration is the solution of 0.03mol/L, adds 20 milligrams of GO again and makes mixed solution; It is in 100 milliliters the autoclave (compactedness 80%, percent by volume) that 80 milliliters of mixed solutions are placed capacity, adds 40 μ L hydrazine hydrates, with 25wt% ammoniacal liquor the pH value is transferred to 11 again, with the reactor sealing, reacted 4 hours down then, naturally cool to room temperature at 180 ℃; Collect solid reaction product, through deionized water and the washing of absolute ethyl alcohol alternate repetition, drying obtains 0.33g SnO/ graphene composite material wherein with product, and the weight percentage of Graphene is 2.7%.
The X ray diffracting spectrum of the composite material of gained and transmission electron microscope photo show that the composite material of gained is the SnO/ graphene composite material, and wherein the SnO particle size is nanoscale, and diameter is about 15 nanometers～25 nanometers, and it is more even to distribute.
Constant current charge-discharge (current density 40mAg -1, voltage range 0.05～1.5V) test shows is compared with pure nano SnO, and the electrochemistry cyclical stability of gained SnO/ graphene composite material in charge and discharge process obviously improves.
Embodiment 5
With Pb (CH 3COO) 23H 2O is a raw material, is dissolved in ethylene glycol and is mixed with Pb (CH 3COO) 2Concentration is the solution of 0.05mol/L, adds 20 milligrams of GO again and makes mixed solution; It is in 100 milliliters the autoclave (compactedness 80%, percent by volume) that 80 milliliters of mixed solutions are placed capacity, adds 70 μ L hydrazine hydrates, NaOH with 6mol/L transfers to 9 with the pH value again, with the reactor sealing, reacted 24 hours down then, naturally cool to room temperature at 200 ℃; Collect solid reaction product, through deionized water and the washing of absolute ethyl alcohol alternate repetition, drying obtains 0.85g Pb with product 3O 4/ graphene composite material wherein, the weight percentage of Graphene is 0.9%.
The X ray diffracting spectrum of the composite material of gained and transmission electron microscope photo show that the composite material of gained is Pb 3O 4/ graphene composite material, wherein Pb 3O 4Particle size is nanoscale, and diameter is about 15 nanometers～25 nanometers, and it is more even to distribute.
Constant current charge-discharge (current density 40mAg -1, voltage range 0.05～1.5V) test shows is with pure nanometer Pb 3O 4Compare gained Pb 3O 4The electrochemistry cyclical stability of/graphene composite material in charge and discharge process obviously improves.

Claims (10)

1. a metal oxide/graphene composite material is made up of nanosize metal oxide and Graphene, and described metal oxide is the oxide of IIIA family metal, the oxide of IVA family metal or the oxide of VA family metal.
2. metal oxide/graphene composite material according to claim 1 is characterized in that, described metal oxide is Bi 2O 3, Sb 2O 3, Sb 2O 5, In 2O 3, SnO, SnO 2, PbO or Pb 3O 4
3. metal oxide/graphene composite material according to claim 1 and 2 is characterized in that, the weight percentage of Graphene is 0.5%～10% in the described composite material.
4. the preparation method of metal oxide/graphene composite material according to claim 1 may further comprise the steps:
1) compound that will contain IIIA family metal, IVA family metal or VA family metal is dissolved in deionized water or the organic solvent, obtains the solution that concentration is 0.01mol/L～0.1mol/L, adds GO again, obtains mixed solution;
The addition of described GO is 1%～20% of a metal oxide theoretical weight;
2) the reducing agent hydrazine hydrate will be added in the mixed solution of step 1), every milligram of GO adds hydrazine hydrate 1 μ L～10 μ L, add alkaline conditioner again the pH value is transferred to 8～12, be warming up to 100 ℃～250 ℃ then, react after 4 hours～48 hours and be cooled to room temperature, collect solid product, through deionized water and the washing of absolute ethyl alcohol alternate repetition, drying obtains metal oxide/graphene composite material.
5. the preparation method of metal oxide/graphene composite material according to claim 4, it is characterized in that, add surfactant in the mixed liquor of step 1), the molal quantity of described surfactant is 0～2: 1 with the ratio of the theoretical molar number of transition metal oxide.
6. the preparation method of metal oxide/graphene composite material according to claim 5 is characterized in that, described surfactant is softex kw, dodecyl sodium sulfate or polyvinylpyrrolidone.
7. the preparation method of metal oxide/graphene composite material according to claim 4 is characterized in that, the compound of the described IIIA of containing family metal, IVA family metal or VA family metal is chloride, nitrate, sulfate, oxalates or acetate.
8. according to the preparation method of claim 4 or 7 described metal oxide/graphene composite materials, it is characterized in that described IIIA family metal is In; Described IVA family metal is Sn or Pb; Described VA family metal is Bi or Sb.
9. the preparation method of metal oxide/graphene composite material according to claim 4 is characterized in that, described organic solvent is ethanol, methyl alcohol, ethylene glycol, 1-butanols, N, dinethylformamide, pyridine, ethylenediamine, benzene or toluene;
Described alkaline conditioner is ammoniacal liquor, sodium hydrate aqueous solution or potassium hydroxide aqueous solution.
According to claim 1,2 or 3 described metal oxide/graphene composite materials as the application in the ion cathode material lithium.
CN2011100837281A 2011-04-02 2011-04-02 Metal oxide/graphene composite material and preparation method thereof Pending CN102185144A (en)

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CN102633256A (en) * 2012-04-16 2012-08-15 中国科学院上海硅酸盐研究所 Preparation method of graphene colloid dispersion solution
CN102903891A (en) * 2012-10-12 2013-01-30 上海中聚佳华电池科技有限公司 Negative material SnOxS2-x/graphene composite for lithium ion battery and preparation method thereof
CN103050687A (en) * 2012-12-26 2013-04-17 上海锦众信息科技有限公司 Preparation method of positive lead paste for power battery
CN103606656A (en) * 2013-12-02 2014-02-26 华南师范大学 Preparation method of lead oxide/graphene nanocomposite material for lead carbon super battery
CN103691418A (en) * 2013-12-21 2014-04-02 海安县吉程机械有限公司 Preparation of mesoporous indium sesquioxide/reduced oxidized graphene compound photocatalyst
CN103811763A (en) * 2012-11-13 2014-05-21 海洋王照明科技股份有限公司 Graphene-bismuth oxide composite material as well as preparation method thereof, lead carbon battery cathode diachylon as well as preparation method thereof and lead carbon battery cathode plate
CN103904312A (en) * 2014-04-15 2014-07-02 山东省科学院能源研究所 Preparation method of tin oxide-graphene composite carbon film
CN103904313A (en) * 2014-04-15 2014-07-02 山东省科学院能源研究所 Preparation method and application of tin oxide-aza graphene aerosol composite material
CN103934014A (en) * 2014-04-25 2014-07-23 苏州大学 Method for preparing nitrogen-doped indium oxide nanorod/graphene oxide composite photocatalyst
CN104600275A (en) * 2015-01-20 2015-05-06 鲁东大学 Method for preparing graphene-based hollow tin dioxide lithium ion battery negative electrode material
CN105428634A (en) * 2015-12-25 2016-03-23 浙江大学 Lithium ion battery negative electrode material and preparation method of lithium sulfide battery
CN106252632A (en) * 2016-09-18 2016-12-21 陕西科技大学 A kind of carbon fiber and the preparation method of stibium oxide composite
CN106410128A (en) * 2016-07-18 2017-02-15 苏州大学 Preparation method of graphene-bismuth oxide composite material for lithium ion battery negative electrode
CN106916337A (en) * 2015-12-27 2017-07-04 黄国波 Antimony oxide loads bromination Graphene fire retardant
CN110212165A (en) * 2019-06-24 2019-09-06 陕西科技大学 A kind of carbon cloth base flexibility sodium-ion battery cathode Sb2O5The preparation method of/GO/ carbon cloth electrode material
CN110357221A (en) * 2019-07-09 2019-10-22 中南大学 A kind of C@Bi/rGO Electro Sorb composite active material and its preparation and application
CN110364706A (en) * 2019-06-27 2019-10-22 华南理工大学 A kind of antimony oxide base negative electrode material and preparation method thereof with high reversible capacity
CN111799452A (en) * 2020-06-29 2020-10-20 安徽师范大学 Ultrathin porous bismuth oxide nanosheet loaded graphene composite material and preparation method thereof, lithium ion battery cathode and battery

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CN101924211A (en) * 2010-08-19 2010-12-22 北京科技大学 Graphene/silicon lithium ion battery cathode material and preparation method thereof
CN101969113A (en) * 2010-09-21 2011-02-09 上海大学 Preparation method of graphene-base tin dioxide composite anode material for lithium ion batteries

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CN101478043A (en) * 2009-01-08 2009-07-08 上海交通大学 Negative pole material for lithium ionic cell and preparation process thereof
CN101800302A (en) * 2010-04-15 2010-08-11 上海交通大学 Graphene nanometer sheet-cobaltous oxide composite negative electrode material of lithium ion battery and preparation method thereof
CN101924211A (en) * 2010-08-19 2010-12-22 北京科技大学 Graphene/silicon lithium ion battery cathode material and preparation method thereof
CN101969113A (en) * 2010-09-21 2011-02-09 上海大学 Preparation method of graphene-base tin dioxide composite anode material for lithium ion batteries

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CN102633256A (en) * 2012-04-16 2012-08-15 中国科学院上海硅酸盐研究所 Preparation method of graphene colloid dispersion solution
CN102903891A (en) * 2012-10-12 2013-01-30 上海中聚佳华电池科技有限公司 Negative material SnOxS2-x/graphene composite for lithium ion battery and preparation method thereof
CN102903891B (en) * 2012-10-12 2014-11-19 上海中聚佳华电池科技有限公司 Negative material SnOxS2-x/graphene composite for lithium ion battery and preparation method thereof
CN103811763A (en) * 2012-11-13 2014-05-21 海洋王照明科技股份有限公司 Graphene-bismuth oxide composite material as well as preparation method thereof, lead carbon battery cathode diachylon as well as preparation method thereof and lead carbon battery cathode plate
CN103050687A (en) * 2012-12-26 2013-04-17 上海锦众信息科技有限公司 Preparation method of positive lead paste for power battery
CN103606656A (en) * 2013-12-02 2014-02-26 华南师范大学 Preparation method of lead oxide/graphene nanocomposite material for lead carbon super battery
CN103606656B (en) * 2013-12-02 2016-07-20 华南师范大学 A kind of preparation method of the lead oxide/graphene nanocomposite material for plumbous charcoal superbattery
CN103691418A (en) * 2013-12-21 2014-04-02 海安县吉程机械有限公司 Preparation of mesoporous indium sesquioxide/reduced oxidized graphene compound photocatalyst
CN103904312A (en) * 2014-04-15 2014-07-02 山东省科学院能源研究所 Preparation method of tin oxide-graphene composite carbon film
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CN103904313B (en) * 2014-04-15 2016-01-20 山东省科学院能源研究所 The preparation method of a kind of tin oxide-nitrogen-doped graphene aerosol composite material and application thereof
CN103904312B (en) * 2014-04-15 2016-06-29 山东省科学院能源研究所 A kind of preparation method of stannum oxide-Graphene compound carbon film
CN103934014A (en) * 2014-04-25 2014-07-23 苏州大学 Method for preparing nitrogen-doped indium oxide nanorod/graphene oxide composite photocatalyst
CN104600275A (en) * 2015-01-20 2015-05-06 鲁东大学 Method for preparing graphene-based hollow tin dioxide lithium ion battery negative electrode material
CN105428634A (en) * 2015-12-25 2016-03-23 浙江大学 Lithium ion battery negative electrode material and preparation method of lithium sulfide battery
CN105428634B (en) * 2015-12-25 2018-01-05 浙江大学 A kind of preparation method of lithium ion battery negative material and its lithium sulphide battery
CN106916337A (en) * 2015-12-27 2017-07-04 黄国波 Antimony oxide loads bromination Graphene fire retardant
CN106410128A (en) * 2016-07-18 2017-02-15 苏州大学 Preparation method of graphene-bismuth oxide composite material for lithium ion battery negative electrode
CN106252632A (en) * 2016-09-18 2016-12-21 陕西科技大学 A kind of carbon fiber and the preparation method of stibium oxide composite
CN110212165A (en) * 2019-06-24 2019-09-06 陕西科技大学 A kind of carbon cloth base flexibility sodium-ion battery cathode Sb2O5The preparation method of/GO/ carbon cloth electrode material
CN110212165B (en) * 2019-06-24 2020-10-27 陕西科技大学 Sb2O5Preparation method of/GO/carbon cloth sodium ion battery cathode material
CN110364706A (en) * 2019-06-27 2019-10-22 华南理工大学 A kind of antimony oxide base negative electrode material and preparation method thereof with high reversible capacity
CN110357221A (en) * 2019-07-09 2019-10-22 中南大学 A kind of C@Bi/rGO Electro Sorb composite active material and its preparation and application
CN111799452A (en) * 2020-06-29 2020-10-20 安徽师范大学 Ultrathin porous bismuth oxide nanosheet loaded graphene composite material and preparation method thereof, lithium ion battery cathode and battery

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Application publication date: 20110914