CN104096832A - High-activity hollow-out silver powder and preparation method thereof - Google Patents
High-activity hollow-out silver powder and preparation method thereof Download PDFInfo
- Publication number
- CN104096832A CN104096832A CN201310116387.2A CN201310116387A CN104096832A CN 104096832 A CN104096832 A CN 104096832A CN 201310116387 A CN201310116387 A CN 201310116387A CN 104096832 A CN104096832 A CN 104096832A
- Authority
- CN
- China
- Prior art keywords
- silver powder
- resin
- hollow out
- silver
- preparation
- 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.)
- Pending
Links
Landscapes
- Powder Metallurgy (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention relates to high-activity hollow-out silver powder and a preparation method thereof and belongs to the field of preparation for high-activity silver powder. The silver powder particles are of hollow-out sphere-like shapes; the diameters of the particles are 35-150 micrometers; the specific area of the particles is not smaller than 25 square meters/gram. The silver powder disclosed by the invention is hollow-out sphere-like powder; in addition, a large quantity of nano holes exist in each particle; the inside of each particle is of a three-dimensional mesh structure; the holes are mutually communicated; by using a prepared silver oxide anode, the effective reaction area of the electrode can be effectively increased, the electric current density is reduced, further the polarization of the electrode is reduced and output performances (current and voltage) of a battery are improved; the voltage of the battery and the utilization rate of active substances are improved; in addition, under the condition that the porosity is ensured, compared with the traditional silver powder, the high-activity silver powder has the advantages that the thickness of the pressed silver oxide electrode is thinner under the condition of equal quantity, further the mass transfer efficiency is improved and the utilization rate of anode active substances is improved.
Description
Technical field
The present invention relates to a kind of high activity hollow out silver powder and preparation method thereof, belong to high activity silver powder preparation field.
Background technology
At present the direction of research high activity silver powder is mainly the specific area that increases silver powder, as makes the powder of hollow sphere and nano-scale, or improves the surface-active etc. of silver powder.The silver powder specific area of these research preparations increases to 20 meters squared per gram than the specific area of traditional silver powder 2 meters squared per gram, but is making after cell positive material, and the electrical performance indexes of battery does not have corresponding raising.Increase although main cause is specific area, activity uprises, and makes that to have quite a lot of micropore after silver oxide electrode be independently, the concentration gradient of reactant and product is large, the concentration polarization being caused by mass transfer is large, causes anode electrode current potential seriously to reduce, the utilization of positive active material.
Summary of the invention
The object of this invention is to provide the preparation method of a kind of hollow out silver powder of high-specific surface area and the hollow out silver powder of described high-specific surface area.According to the feature of the required silver powder of anode, the present invention adopts unique technology of preparing, as carrier, utilizes the framework of large empty resin with macroreticular resin, through reduction, decomposes, and obtains the powder of an engraved structure.From Electronic Speculum, can find out, its powder granule is a class ball-type, and size is at 30～150 microns.
Above-mentioned purpose of the present invention reaches by the following technical programs:
A kind of high activity hollow out silver powder, the class that is shaped as hollow out of this silver powder particles is spherical, and the diameter of particle is 35 microns～150 microns, specific area >=25 meters squared per gram.
A preparation method for high activity hollow out silver powder, comprises the steps:
(1) compound concentration is the liquor argenti nitratis ophthalmicus of 20 grams per liter～250 grams per liters, and macroreticular resin is packed in organic glass column, adopts the mode of chromes, and the flow velocity of liquor argenti nitratis ophthalmicus is 50～350 ml/min, obtains silver nitrate resin;
(2) step (1) is prepared to silver nitrate resin and be heated to 30 DEG C～75 DEG C, add ammoniacal liquor, adjust pH is 8～10, then adds hydrazine hydrate, and silver nitrate resin is reduced to silver resin, spends ion-cleaning, obtains pH value and be 7 silver resin, then filters, dry;
(3) step (2) is prepared to dry silver resin and put into thermal decomposition furnace, heat up with 2 DEG C/point～60 DEG C of/point of programming rates, passing into air speed is 0.1 liter/min～50 liters/min, is warming up to 350 DEG C～750 DEG C, is incubated 100 points～450 points, carries out thermal decomposition; Then be naturally cooled to below 250 DEG C, pulverize, sieve, obtain hollow out silver powder.
In step (1), macroreticular resin comprises styrene-divinylbenzene resin, styrene-methyl methacrylate, Styrene And Chloroalkyl Acrylates methyl esters, styrene-trimethyl acrylic acid glyceride, styrene-dimethacrylate ethanol ester, polytrifluorochloroethylene, polytetrafluoroethylene (PTFE), polyethylene, polyacrylonitrile and polyurethane resin.The particle size range of described resin is at 0.01～1.25 millimeter, and preferably 0.1～1.10 millimeter, the average pore size of resin exists
, specific area is in 600～1000 meters squared per gram.
In step (1), preferably concentration 30 grams per liter～150 grams per liters of liquor argenti nitratis ophthalmicus, preferably the flow velocity of liquor argenti nitratis ophthalmicus is 70～200 ml/min.
In step (2), preferably silver nitrate resin heating-up temperature is 35 DEG C～75 DEG C; Baking temperature is 30 DEG C～200 DEG C, and be 2～30 hours drying time; Preferably baking temperature is 50 DEG C～80 DEG C, and be preferably 5～10 hours drying time.
In step (3), preferably programming rate is 8 DEG C/point～45 DEG C/point, and preferably air speed is 3 liters/min～25 liters/min, and preferably heat decomposition temperature is 400 DEG C～600 DEG C, preferably 150～350 points of thermal decomposition times.
Show by S-4800 field emission scanning electron microscope measurement result: the silver powder that the present invention obtains is hollow out, and each particle is a hollow out spheroid, and inside is a three-dimensional network structure, between cavity, communicates with each other.The particle size range of hollow out silver powder is between 30～150 microns.
With full-automatic specific surface and voidage analyzer (SB-091A) detection, between specific area 25～55 meters squared per gram of hollow out silver powder.
There is a large amount of nano-voids in the inside of each particle of hollow out silver powder that the present invention obtains, each particle is a hollow out spheroid, and inside is a three-dimensional network structure, between cavity, communicates with each other, and specific area can be up to 50 meters squared per gram.The silver oxide positive pole that this high activity hollow out silver powder is made, can make each cavity effectively link, be conducive to infiltration and the diffusion of reactant and product, greatly reduce the concentration polarization of silver oxide positive pole, improve positive electrode potential, in changing into, the conversion ratio (changing into silver oxide) of silver also increases, thereby the capacitance of silver oxide positive pole is improved.
And the specific area of this high activity hollow out silver powder is greater than 25 meters squared per gram, the silver oxide positive pole of making, can improve the effecting reaction area of electrode, reduces current density, thereby reduces electrode polarization, improves the output performance (electric current and voltage) of battery.Improve the utilization rate of cell voltage and active material, high activity silver powder is in the situation that ensureing porosity, compared with traditional silver powder in addition, in equivalent situation, be pressed into silver oxide electrode thickness thinner, further improve mass-transfer efficiency, improved the utilization rate of positive active material.
The present invention is described further for the drawings and Examples of passing through below, but do not mean that limiting the scope of the invention.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of silver powder of the present invention.
Fig. 2 is the scanning electron microscope (SEM) photograph of silver powder individual particle of the present invention.
Fig. 3 is the scanning electron microscope (SEM) photograph of silver powder particles of the present invention part.
Detailed description of the invention
Embodiment 1
(1) silver nitrate is mixed with to the solution that concentration is 65 grams per liters, (average pore size of resin exists macroreticular resin for styrene-divinylbenzene resin, 0.35 millimeter of average grain diameter
specific area is in 650 meters squared per gram) pack into
in lucite post, adopt the mode of chromes, the flow velocity charging by the above-mentioned liquor argenti nitratis ophthalmicus preparing with 75 ml/min, the solution receiving with 10% sodium chloride solution inspection, adularescent precipitation starts, and receives solution and recycles.Obtain thus silver nitrate resin transfer in bucket, carry out reduction experiment.
(2) bucket that step (1) obtains silver nitrate resin will be housed and put into 65 DEG C of hot baths, stir silver nitrate resin, when the temperature that is heated to silver nitrate resin is 30 DEG C, under stirring, add 70 milliliters of ammoniacal liquor, when silver nitrate resin system reaches pH=8, add 180 milliliters of hydrazine hydrates, continue to stir 30 minutes, place more than 1 hour, silver reduction completely, obtains silver resin.Spend ion-cleaning, obtain pH value and be 7 silver resin, then filter, filtration is obtained to silver resin and put into dish.In baking oven, dry 22 hours, 50 DEG C of oven temperatures.
(3) dried silver resin is put into crucible, then put in thermal decomposition furnace, set 12 DEG C/min of programming rate, pass into air capacity 11L/min, be warming up to 510 DEG C, be incubated 200 minutes, stop heating.Naturally be cooled to 250 DEG C of silver in taking-up crucible, through pulverizing, 180 mesh sieve screenings, obtain specific area 33m
2/ g high activity hollow out silver powder, the class that is shaped as hollow out of this silver powder particles is spherical, and the average grain diameter of particle is 75 microns.
Embodiment 2
(1) silver nitrate being mixed with to concentration is 220 grams per liter solution, by macroreticular resin (styrene-methyl methacrylate, specific area 750m
2/ g, average pore size
, 0.64 millimeter of average grain diameter) pack into
in lucite post, adopt the mode of chromes, the flow velocity of liquor argenti nitratis ophthalmicus is 300 ml/min, obtains silver nitrate resin.
(2) step (1) is obtained silver nitrate resin be heated to 60 DEG C time, under stirring, add ammoniacal liquor, in the time that silver nitrate resin system reaches pH=8, add 180 milliliters of hydrazine hydrates, continue to stir 30 minutes, place more than 1 hour, silver reduction completely, obtains silver resin.Spend ion-cleaning, obtain pH value and be 7 silver resin, then filter, filtration is obtained to silver resin and put into dish.In baking oven, dry 12 hours, 100 DEG C of oven temperatures.
(3) dried silver resin is put into crucible, then put in thermal decomposition furnace, set 18 DEG C/min of programming rate, pass into air capacity 8L/min, be warming up to 550 DEG C, be incubated 150 minutes, stop heating.Naturally be cooled to 250 DEG C of silver in taking-up crucible, through pulverizing, 180 mesh sieve screenings, obtain specific area 37m
2/ g high activity hollow out silver powder, the class that is shaped as hollow out of this silver powder particles is spherical, and the average grain diameter of particle is 65 microns.
Embodiment 3
(1) silver nitrate being mixed with to concentration is 120 grams per liter solution, by macroreticular resin (styrene-dimethacrylate ethanol ester, specific area 950m
2/ g, aperture
0.75 millimeter of average grain diameter) pack into
in lucite post, adopt the mode of chromes, the flow velocity of liquor argenti nitratis ophthalmicus is 200 ml/min, obtains silver nitrate resin.
(2) step (1) is obtained silver nitrate resin be heated to 70 DEG C time, under stirring, add ammoniacal liquor, when silver nitrate resin system reaches pH=8, add 180 milliliters of hydrazine hydrates, continue to stir 30 minutes, place more than 1 hour, silver reduction completely, obtains silver resin.Spend ion-cleaning, obtain pH value and be 7 silver resin, then filter, filtration is obtained to silver resin and put into dish.In baking oven, dry 3 hours, 180 DEG C of oven temperatures.
(3) dried silver resin is put into crucible, then put in thermal decomposition furnace, set 22 DEG C/min of programming rate, pass into air capacity 5L/min, be warming up to 450 DEG C, be incubated 250 minutes, stop heating.Naturally be cooled to 250 DEG C of silver in taking-up crucible, through pulverizing, 180 mesh sieve screenings, obtain specific area 32m
2/ g high activity hollow out silver powder, the class that is shaped as hollow out of this silver powder particles is spherical, and the average grain diameter of particle is 58 microns.
Embodiment 4
(1) silver nitrate being mixed with to concentration is 30 grams per liter solution, by macroreticular resin (styrene-trimethyl acrylic acid glyceride, specific area 550m
2/ g, aperture
, 0.45 millimeter of average grain diameter) pack into
in lucite post, adopt the mode of chromes, the flow velocity of liquor argenti nitratis ophthalmicus is 150 ml/min, obtains silver nitrate resin.
(2) step (1) is obtained silver nitrate resin be heated to 45 DEG C time, under stirring, add ammoniacal liquor, when silver nitrate resin system reaches pH=8, add 180 milliliters of hydrazine hydrates, continue to stir 30 minutes, place more than 1 hour, silver reduction completely, obtains silver resin.Spend ion-cleaning, obtain pH value and be 7 silver resin, then filter, filtration is obtained to silver resin and put into dish.In baking oven, dry 6 hours, 150 DEG C of oven temperatures.
(3) dried silver resin is put into crucible, then put in thermal decomposition furnace, set 42 DEG C/min of programming rate, pass into air capacity 0.5L/min, be warming up to 350 DEG C, be incubated 400 minutes, stop heating.Naturally be cooled to 250 DEG C of silver in taking-up crucible, through pulverizing, 180 mesh sieve screenings, obtain specific area 32m
2/ g high activity hollow out silver powder, the class that is shaped as hollow out of this silver powder particles is spherical, and the average grain diameter of particle is 58 microns.
Adopt S-4800 field emission scanning electron microscope, full-automatic specific surface and voidage analyzer (SB-091A) to detect the silver powder of embodiment 1-4 gained, as shown in Figure 1, Figure 2 and Figure 3, be respectively scanning electron microscope (SEM) photograph, the scanning electron microscope (SEM) photograph of silver powder individual particle and the scanning electron microscope (SEM) photograph of silver powder particles part of embodiment 1 gained silver powder.Measurement result shows: the silver powder that the present invention obtains is the class spherical powder of hollow out, be that each particle is a hollow out spheroid, and there is a large amount of nano-voids in the inside of each particle, inside is a three-dimensional network structure, between cavity, communicate with each other, the diameter range of this silver powder particles is between 35 microns～150 microns, and specific area is more than or equal to 25 meters squared per gram.
Claims (10)
1. a high activity hollow out silver powder, is characterized in that: the class that is shaped as hollow out of this silver powder particles is spherical, and the diameter of particle is 35 microns～150 microns, specific area >=25 meters squared per gram.
2. a preparation method for high activity hollow out silver powder, comprises the steps:
(1) silver nitrate being mixed with to concentration is 20 grams per liter～250 grams per liter solution, and macroreticular resin is packed in organic glass column, adopts the mode of chromes, and the flow velocity of liquor argenti nitratis ophthalmicus is 50～350 ml/min, obtains silver nitrate resin;
(2) the silver nitrate resin of gained is heated to 30 DEG C～75 DEG C, adds ammoniacal liquor, adjust pH is 8～10, then adds hydrazine hydrate, and silver nitrate resin is reduced to silver resin, spends ion-cleaning, obtains pH value and be 7 silver resin, then filters, dry;
(3) dry silver resin is put into thermal decomposition furnace, heat up with 2 DEG C/point～60 DEG C of/point of programming rates, passing into air speed is 0.1 liter/min～50 liters/min, is warming up to 350 DEG C～750 DEG C, is incubated 100 points～450 points, carries out thermal decomposition; Then be naturally cooled to below 250 DEG C, pulverize, sieve, obtain hollow out silver powder.
3. the preparation method of high activity hollow out silver powder according to claim 2, is characterized in that: described macroreticular resin is styrene-divinylbenzene resin, styrene-methyl methacrylate, Styrene And Chloroalkyl Acrylates methyl esters, styrene-trimethyl acrylic acid glyceride, styrene-dimethacrylate ethanol ester, polytrifluorochloroethylene, polytetrafluoroethylene (PTFE), polyethylene, polyacrylonitrile and/or polyurethane resin.
4. the preparation method of high activity hollow out silver powder according to claim 3, is characterized in that: the particle diameter of described macroreticular resin is 0.01～1.25 millimeter, and the average pore size of resin is
, specific area is 600～1000 meters squared per gram.
5. the preparation method of high activity hollow out silver powder according to claim 4, is characterized in that: the particle diameter of described macroreticular resin is 0.1～1.10 millimeter.
6. the preparation method of high activity hollow out silver powder according to claim 2, is characterized in that: the concentration of described liquor argenti nitratis ophthalmicus is 30 grams per liter～150 grams per liters, and the flow velocity of described liquor argenti nitratis ophthalmicus is 70～200 ml/min.
7. the preparation method of high activity hollow out silver powder according to claim 2, is characterized in that: described baking temperature is 30 DEG C～200 DEG C, and be 2～30 hours drying time.
8. the preparation method of high activity hollow out silver powder according to claim 7, is characterized in that: described baking temperature is 50 DEG C～80 DEG C, and be 5～10 hours described drying time.
9. the preparation method of high activity hollow out silver powder according to claim 2, is characterized in that: described programming rate is 8 DEG C/point～45 DEG C/point, and described air speed is 3 liters/min～25 liters/min.
10. the preparation method of high activity hollow out silver powder according to claim 2, is characterized in that: described heat decomposition temperature is 400 DEG C～600 DEG C, and thermal decomposition time is 150～350 points.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310116387.2A CN104096832A (en) | 2013-04-03 | 2013-04-03 | High-activity hollow-out silver powder and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310116387.2A CN104096832A (en) | 2013-04-03 | 2013-04-03 | High-activity hollow-out silver powder and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104096832A true CN104096832A (en) | 2014-10-15 |
Family
ID=51665596
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310116387.2A Pending CN104096832A (en) | 2013-04-03 | 2013-04-03 | High-activity hollow-out silver powder and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104096832A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110842213A (en) * | 2019-11-12 | 2020-02-28 | 广东羚光新材料股份有限公司 | High-activity silver powder and preparation method and application thereof |
| CN111432959A (en) * | 2017-12-15 | 2020-07-17 | 同和电子科技有限公司 | Spherical silver powder |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4882232A (en) * | 1984-01-25 | 1989-11-21 | Sorapec Societe De Researche Et D'applications Electrtochimiques | Porous metal structure and method of manufacturing of said structure |
| US5312580A (en) * | 1992-05-12 | 1994-05-17 | Erickson Diane S | Methods of manufacturing porous metal alloy fuel cell components |
| CN1133895A (en) * | 1995-01-12 | 1996-10-23 | 住友电气工业株式会社 | Process for preparing metallic porous body, electrode substrate for battery and process for preparing the same |
| CN101318225A (en) * | 2008-07-14 | 2008-12-10 | 西北有色金属研究院 | Method of preparing metal stephanoporate spherical aluminum powder |
| CN101391304A (en) * | 2008-11-07 | 2009-03-25 | 中南大学 | Preparation method of porous aluminum powder with high specific surface area |
| CN102473925A (en) * | 2010-03-26 | 2012-05-23 | 住友电气工业株式会社 | Porous metal body manufacturing method and porous aluminum body, battery electrode material using metal porous body or porous aluminum body, and electrode material for electric double layer capacitor |
-
2013
- 2013-04-03 CN CN201310116387.2A patent/CN104096832A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4882232A (en) * | 1984-01-25 | 1989-11-21 | Sorapec Societe De Researche Et D'applications Electrtochimiques | Porous metal structure and method of manufacturing of said structure |
| US5312580A (en) * | 1992-05-12 | 1994-05-17 | Erickson Diane S | Methods of manufacturing porous metal alloy fuel cell components |
| CN1133895A (en) * | 1995-01-12 | 1996-10-23 | 住友电气工业株式会社 | Process for preparing metallic porous body, electrode substrate for battery and process for preparing the same |
| CN101318225A (en) * | 2008-07-14 | 2008-12-10 | 西北有色金属研究院 | Method of preparing metal stephanoporate spherical aluminum powder |
| CN101391304A (en) * | 2008-11-07 | 2009-03-25 | 中南大学 | Preparation method of porous aluminum powder with high specific surface area |
| CN102473925A (en) * | 2010-03-26 | 2012-05-23 | 住友电气工业株式会社 | Porous metal body manufacturing method and porous aluminum body, battery electrode material using metal porous body or porous aluminum body, and electrode material for electric double layer capacitor |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111432959A (en) * | 2017-12-15 | 2020-07-17 | 同和电子科技有限公司 | Spherical silver powder |
| CN110842213A (en) * | 2019-11-12 | 2020-02-28 | 广东羚光新材料股份有限公司 | High-activity silver powder and preparation method and application thereof |
| CN110842213B (en) * | 2019-11-12 | 2022-05-27 | 广东羚光新材料股份有限公司 | High-activity silver powder and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liang et al. | A deep reduction and partial oxidation strategy for fabrication of mesoporous Si anode for lithium ion batteries | |
| CN105060351B (en) | Flower-like cobaltosic oxide material composed of nanoparticles and preparation method thereof | |
| CN106684342B (en) | Silico-carbo nanotube microballoon, its lithium metal compound and preparation method and application | |
| CN104810509B (en) | Ferroso-ferric oxide/graphene three dimensional composite structure and its preparation method and application | |
| CN106711419B (en) | The porous composite lithium ion battery cathode material of the NiO/C of core-shell structure copolymer shape | |
| CN107768659A (en) | A kind of preparation method of the sulfur electrode material of loose structure | |
| CN102585517B (en) | Hollow polyphosphazenes microsphere with magnetic particles embedded in casing layer and preparation method thereof | |
| CN110838583B (en) | Carbon nanotube/M-phase vanadium dioxide composite structure, preparation method thereof and application thereof in water-based zinc ion battery | |
| CN108946824B (en) | Preparation method of large-particle-size cobaltosic oxide | |
| CN103570083B (en) | A kind of preparation method of lithium ion battery anode material nickel cobalt aluminium spherical precursor | |
| CN105680013A (en) | Preparation method for silicon/graphite/carbon composite negative electrode material of lithium ion battery | |
| CN104577049A (en) | Hierarchical pore structure silicon-based negative electrode material for lithium battery and preparation method of hierarchical pore structure silicon-based negative electrode material | |
| CN104300133B (en) | A kind of lithium titanate material of CNT cladding and preparation method thereof | |
| CN103934471A (en) | Method for preparing graphene carrying tin-nickel nano-alloy particle composite material | |
| CN103346323A (en) | Preparation method of carbon-coated lithium iron phosphate material with polystyrene microspheres and polyethylene glycol as carbon sources | |
| CN105110384B (en) | Porous cobaltosic oxide and preparation method thereof | |
| CN114195132B (en) | Preparation method of nano germanium/three-dimensional porous graphene composite material and application of nano germanium/three-dimensional porous graphene composite material to lithium ion battery negative electrode | |
| CN112341630B (en) | Method for continuously preparing nano metal-organic framework material by using supergravity technology | |
| CN104096832A (en) | High-activity hollow-out silver powder and preparation method thereof | |
| CN108134052A (en) | High-volume silicon-carbon negative electrode material and preparation method thereof used in a kind of power battery | |
| CN106699550A (en) | Preparation method of nano Cu-CuBTC type metal organic framework material | |
| CN106450255B (en) | A kind of NiTiO of sodium-ion battery3/ C negative electrode material, preparation and application | |
| CN106825553B (en) | A kind of preparation method of cobalt-nitrogen-carbon nucleocapsid hybrid hollow porous carbon ball | |
| CN108598384A (en) | A kind of preparation method of composite aerogel negative material | |
| CN105271443A (en) | Method for preparing flaky nano CoO or Co3O4 through assistant microwave heating |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20141015 |