CN106450559A - Method for preparing new electrodes through recovering of waste ion batteries - Google Patents

Method for preparing new electrodes through recovering of waste ion batteries Download PDF

Info

Publication number
CN106450559A
CN106450559A CN201611114126.7A CN201611114126A CN106450559A CN 106450559 A CN106450559 A CN 106450559A CN 201611114126 A CN201611114126 A CN 201611114126A CN 106450559 A CN106450559 A CN 106450559A
Authority
CN
China
Prior art keywords
lithium
cobalt
waste
added
ion batteries
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
Application number
CN201611114126.7A
Other languages
Chinese (zh)
Inventor
吴进波
吴昱铮
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.)
Tianjin Huaqing Baisheng Energy Co Ltd
Original Assignee
Tianjin Huaqing Baisheng Energy Co Ltd
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 Tianjin Huaqing Baisheng Energy Co Ltd filed Critical Tianjin Huaqing Baisheng Energy Co Ltd
Priority to CN201611114126.7A priority Critical patent/CN106450559A/en
Publication of CN106450559A publication Critical patent/CN106450559A/en
Pending legal-status Critical Current

Links

Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/54Reclaiming serviceable parts of waste accumulators
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/84Recycling of batteries or fuel cells

Abstract

The invention relates to a method for preparing new electrodes through recovering of waste ion batteries. Firstly, waste lithium-ion batteries are discharged and manually dissembled, an anode material is obtained, calcined, added to water and stirred with an electric stirrer, screening and drying are performed, lithium cobalt oxide powder is obtained and subjected to ball milling, a mixed solution of natural organic acid and hydrogen peroxide is added, an ammonium oxalate solution is added after the reaction, a cobalt oxalate precipitate is obtained, lithium salt powder is added, the mixture is evenly ground, and lithium cobalt oxide powder which can be directly used as an electrode material is obtained after roasting. The waste lithium-ion batteries are recovered, the novel lithium cobalt oxide electrode is prepared and synthesized from the waste lithium cobalt oxide material, the natural organic acid raw material is used during preparation, secondary pollution caused by waste liquor treatment is avoided, used instruments are simple, the operation is convenient, environmental pollution caused by waste batteries can be reduced, and recycling of the lithium-ion batteries is realized.

Description

A kind of method that new electrode is prepared in recovery from useless ion battery
Technical field
The present invention relates to battery recycling field, more particularly, to a kind of reclaim the side preparing new electrode from useless ion battery Method.
Background technology
With it, lithium ion battery, since realizing commercialization, has had that energy density is big, light weight, a life-span length and without memory Plurality of advantages be widely used.Because the service life of lithium ion battery is 2~3 years, therefore all can produce every year and give up in a large number The lithium battery abandoned, and in lithium ion battery, contain cobalt 5~20%, lithium 5~7%, nickel 5~10%.Wherein, cobalt is a kind of rare money Source, mainly for the manufacture of heat strong alloy, permanent magnet, developing rapidly recently as secondary cell, cobalt is in battery industry Consumption also substantially increases.Cobalt acid lithium synthesis is relatively simple, and electrochemical properties are stable, are widely used in the positive pole material of lithium ion battery Material, no matter from cost-effective, environmental conservation, or world fossil resource reasonable using with the aspects such as exploitation from the point of view of, lithium ion The recovery of battery and cycling and reutilization are respectively provided with important theory significance and practical value.From waste lithium ion high efficiente callback Electrode material has important economic implications.
Content of the invention
Present invention seek to address that the deficiencies in the prior art, and provide a kind of recovery from useless ion battery to prepare new electrode Method.
The present invention for achieving the above object, employs the following technical solutions:A kind of recovery from useless ion battery prepares newly electricity The method of pole is it is characterised in that its step is as follows:
(1) carry out in sodium hydrate aqueous solution used Li ion cell being put into 0.1~1.0mol/L at the electric discharge of 1~3h Reason, is disassembled using manual, is obtained positive electrode,
(2) positive electrode obtaining is dried, calcines 3~6h at 500~700 DEG C with Muffle furnace, heating rate is 5 DEG C/min, it is incubated 1h, naturally cool to room temperature;
(3) take out the positive electrode through roasting, be added to the water and stir 15~30min with motor stirrer, add water The mass ratio of quality and positive electrode be 1:40, in whipping process the temperature of water be 20~50 DEG C, mixing speed be 100~ 200r/min;
(4) after stopping stirring, the mixture in container is sieved with the screen cloth of 10~20 mesh, oversize is aluminium foil, Siftage is the solution containing positive active material;Oversize aluminium foil water cleans 1~3 time, obtains aluminium foil through spontaneously drying;Sieve Lower thing carries out sucking filtration, and in filter, thing water cleans 1~3 time, then after spontaneously drying, obtains cobalt acid lithium powder;
(5) cobalt acid lithium being carried out with ball milling 1~5h to particle diameter using ball mill is 0.01~1.0mm;
(6) natural organic acidss of 125g/L are added in cobalt acid lithium powder, solid-to-liquid ratio is 20~30:1, it is simultaneously introduced quality Fraction is the mixed solution of 30% hydrogen peroxide, and solid-to-liquid ratio is 10~40:1g/L, reaction temperature is 80~100 DEG C, and reaction is being stirred Carry out it is ensured that cobalt acid lithium and solution are fully contacted under the conditions of mixing, after the completion of reaction, be filtrated to get the filtrate containing cobalt and lithium;
(7) add ammonium oxalate solution in the filtrate containing cobalt, lithium ion is not reacted with oxalate, thus obtains oxalic acid Cobalt precipitates;
(8) press the mol ratio 1 of cobalt and lithium:1~1.05 adds lithium salts powder in cobalt oxalate precipitation, after grinding uniformly, Roasting 6~8h at 800~850 DEG C, obtains the cobalt acid lithium powder that can use directly as electrode material.
Particularly, the natural organic acidss in described step (4) are one of citric acid, malic acid.
Particularly, the lithium salts in described step (6) is one of lithium nitrate, lithium carbonate.
The invention has the beneficial effects as follows:The present invention reclaims to waste and old lithium ion battery, and waste and old lithium ion battery is entered After the programs such as row electric eliminating, fractionation, pulverizing, calcining, ball milling, obtain waste and old cobalt acid lithium material, then prepare synthesis as raw material New cobalt acid lithium electrode, employs natural organic acidss raw material in preparation, it is to avoid the secondary pollution that liquid waste processing causes, instrument Simply, easy to operate, the environmental pollution that old and useless battery causes can not only be reduced, and achieve the circulation of lithium ion battery again Make profits use.
Specific embodiment
With reference to embodiment, the invention will be further described:
Embodiment 1
A kind of method that new electrode is prepared in recovery from useless ion battery, its step is as follows:
(1) carry out the discharge process of 1h in sodium hydrate aqueous solution used Li ion cell being put into 0.1mol/L, adopt Disassembled by hand, obtained positive electrode,
(2) positive electrode obtaining is dried, calcines 6h at 500 DEG C with Muffle furnace, heating rate is 5 DEG C/min, protects Warm 1h, naturally cools to room temperature;
(3) take out the positive electrode through roasting, be added to the water and stir 15min with motor stirrer, add the matter of water Amount is 1 with the mass ratio of positive electrode:40, in whipping process, the temperature of water is 20 DEG C, and mixing speed is 100r/min;
(4) after stopping stirring, the mixture in container is sieved with the screen cloth of 10 mesh, oversize is aluminium foil, under sieve Thing is the solution containing positive active material;Oversize aluminium foil water cleans 1 time, obtains aluminium foil through spontaneously drying;Siftage enters Row sucking filtration, in filter, thing water cleans 1 time, then after spontaneously drying, obtains cobalt acid lithium powder;
(5) using ball mill, cobalt acid lithium being carried out with ball milling 1h is 1.0mm to particle diameter;
(6) add the citric acid of 125g/L in cobalt acid lithium powder, solid-to-liquid ratio is 20:1, being simultaneously introduced mass fraction is The mixed solution of 30% hydrogen peroxide, solid-to-liquid ratio is 10:1g/L, reaction temperature is 80 DEG C, and reaction is carried out under agitation, protects Card cobalt acid lithium and solution are fully contacted, and after the completion of reaction, are filtrated to get the filtrate containing cobalt and lithium;
(7) add ammonium oxalate solution in the filtrate containing cobalt, lithium ion is not reacted with oxalate, thus obtains oxalic acid Cobalt precipitates;
(8) press the mol ratio 1 of cobalt and lithium:1 adds lithium carbonate powder in cobalt oxalate precipitation, after grinding uniformly, at 800 DEG C Lower roasting 6h, obtains the cobalt acid lithium powder that can use directly as electrode material.
Embodiment 2
A kind of method that new electrode is prepared in recovery from useless ion battery, its step is as follows:
(1) carry out the discharge process of 3h in sodium hydrate aqueous solution used Li ion cell being put into 1.0mol/L, adopt Disassembled by hand, obtained positive electrode,
(2) positive electrode obtaining is dried, calcines 3h at 700 DEG C with Muffle furnace, heating rate is 5 DEG C/min, protects Warm 1h, naturally cools to room temperature;
(3) take out the positive electrode through roasting, be added to the water and stir 30min with motor stirrer, add the matter of water Amount is 1 with the mass ratio of positive electrode:40, in whipping process, the temperature of water is 50 DEG C, and mixing speed is 200r/min,
(4) after stopping stirring, the mixture in container is sieved with the screen cloth of 20 mesh, oversize is aluminium foil, under sieve Thing is the solution containing positive active material;Oversize aluminium foil water cleans 3 times, obtains aluminium foil through spontaneously drying;Siftage enters Row sucking filtration, in filter, thing water cleans 3 times, then after spontaneously drying, obtains cobalt acid lithium powder;
(5) using ball mill, cobalt acid lithium being carried out with ball milling 5h is 0.01mm to particle diameter;
(6) add the malic acid of 125g/L in cobalt acid lithium powder, solid-to-liquid ratio is 30:1, being simultaneously introduced mass fraction is The mixed solution of 30% hydrogen peroxide, solid-to-liquid ratio is 40:1g/L, reaction temperature is 100 DEG C, and reaction is carried out under agitation, Ensure that cobalt acid lithium and solution are fully contacted, after the completion of reaction, be filtrated to get the filtrate containing cobalt and lithium;
(7) add ammonium oxalate solution in the filtrate containing cobalt, lithium ion is not reacted with oxalate, thus obtains oxalic acid Cobalt precipitates;
(8) press the mol ratio 1 of cobalt and lithium:1.05 add nitric acid lithium powder in cobalt oxalate precipitation, after grinding uniformly, Roasting 8h at 850 DEG C, obtains the cobalt acid lithium powder that can use directly as electrode material.
Above the present invention is exemplarily described it is clear that the present invention implements is not subject to the restrictions described above, As long as employing method of the present invention design and the various improvement that carry out of technical scheme, or not improved directly apply to other fields Close, all within protection scope of the present invention.

Claims (3)

1. a kind of recovery from useless ion battery prepares the method for new electrode it is characterised in that its step is as follows:
(1) carry out the discharge process of 1~3h in sodium hydrate aqueous solution used Li ion cell being put into 0.1~1.0mol/L, Disassembled using manual, obtained positive electrode,
(2) by obtain positive electrode be dried, calcine 3~6h at 500 DEG C~700 DEG C with Muffle furnace, heating rate for 5 DEG C/ Min, is incubated 1h, naturally cools to room temperature;
(3) take out the positive electrode through roasting, be added to the water and stir 15~30min with motor stirrer, add the matter of water Amount is 1 with the mass ratio of positive electrode:40, in whipping process, the temperature of water is 20~50 DEG C, and mixing speed is 100~200r/ min;
(4) after stopping stirring, the mixture in container is sieved with the screen cloth of 10~20 mesh, oversize is aluminium foil, under sieve Thing is the solution containing positive active material;Oversize aluminium foil water cleans 1~3 time, obtains aluminium foil through spontaneously drying;Siftage Carry out sucking filtration, in filter, thing water cleans 1~3 time, then after spontaneously drying, obtain cobalt acid lithium powder;
(5) cobalt acid lithium being carried out with ball milling 1~5h to particle diameter using ball mill is 0.01~1.0mm;
(6) natural organic acidss of 125g/L are added in cobalt acid lithium powder, solid-to-liquid ratio is 20~30:1, it is simultaneously introduced mass fraction The mixed solution of the hydrogen peroxide for 30%, solid-to-liquid ratio is 10~40:1g/L, reaction temperature is 80~100 DEG C, and reaction is in stirring bar Carry out it is ensured that cobalt acid lithium and solution are fully contacted under part, after the completion of reaction, be filtrated to get the filtrate containing cobalt and lithium;
(7) add ammonium oxalate solution in the filtrate containing cobalt, lithium ion is not reacted with oxalate, thus obtains cobalt oxalate and sink Form sediment;
(8) press the mol ratio 1 of cobalt and lithium:1~1.05 adds lithium salts powder in cobalt oxalate precipitation, after grinding uniformly, 800~ Roasting 6~8h at 850 DEG C, obtains the cobalt acid lithium powder that can use directly as electrode material.
2. a kind of method preparing new electrode that reclaims from useless ion battery according to claim 1 is it is characterised in that institute Stating the natural organic acidss in step (4) is one of citric acid, malic acid.
3. a kind of method preparing new electrode that reclaims from useless ion battery according to claim 1 is it is characterised in that institute Stating the lithium salts in step (6) is one of lithium nitrate, lithium carbonate.
CN201611114126.7A 2016-12-07 2016-12-07 Method for preparing new electrodes through recovering of waste ion batteries Pending CN106450559A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201611114126.7A CN106450559A (en) 2016-12-07 2016-12-07 Method for preparing new electrodes through recovering of waste ion batteries

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201611114126.7A CN106450559A (en) 2016-12-07 2016-12-07 Method for preparing new electrodes through recovering of waste ion batteries

Publications (1)

Publication Number Publication Date
CN106450559A true CN106450559A (en) 2017-02-22

Family

ID=58216691

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201611114126.7A Pending CN106450559A (en) 2016-12-07 2016-12-07 Method for preparing new electrodes through recovering of waste ion batteries

Country Status (1)

Country Link
CN (1) CN106450559A (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107275706A (en) * 2017-06-19 2017-10-20 上海第二工业大学 A kind of technique of use mechanical activation method Call Provision and lithium from waste and old cobalt acid lithium battery
CN112142589A (en) * 2020-09-27 2020-12-29 厦门理工学院 Method for synthesizing cobalt oxalate dihydrate from leaching solution of positive active material of waste lithium battery
CN114400395A (en) * 2022-02-22 2022-04-26 楚能新能源股份有限公司 Method for preparing lithium cobalt phosphate by recycling waste lithium cobalt oxide
ES2924113A1 (en) * 2021-03-16 2022-10-04 Asociacion De Investig De Las Industrias Ceramicas A I C E METHOD FOR THE RECOVERY OF ACTIVE CATHODE MATERIAL FROM SPENT LITHIUM-ION RECHARGEABLE BATTERIES (Machine-translation by Google Translate, not legally binding)
WO2024055510A1 (en) * 2022-09-15 2024-03-21 广东邦普循环科技有限公司 Method for preparing lithium iron phosphate from nickel-rion alloy and use thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103474718A (en) * 2013-08-27 2013-12-25 华中科技大学武昌分校 Method for recovering cobalt from lithium battery anode material
CN103985920A (en) * 2014-06-05 2014-08-13 兰州理工大学 Method for separating lithium cobalt oxide and aluminum foil on scrapped lithium ion battery positive pole piece
CN104103870A (en) * 2014-07-30 2014-10-15 兰州理工大学 Method for recovering cobalt lithium aluminum from positive pole plate of scrap lithium ion battery
CN104466292A (en) * 2014-12-30 2015-03-25 兰州理工大学 Method for recovering cobalt lithium metal from waste lithium ion battery of lithium cobalt oxide positive material
CN105886777A (en) * 2016-05-16 2016-08-24 兰州理工大学 Method for synergistically treating acid-making exhaust gas and wasted lithium cobalt oxide and recovering cobalt lithium
CN105907977A (en) * 2016-07-08 2016-08-31 长沙理工大学 Method for recycling lithium cobalt oxides from waste lithium-ion batteries

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103474718A (en) * 2013-08-27 2013-12-25 华中科技大学武昌分校 Method for recovering cobalt from lithium battery anode material
CN103985920A (en) * 2014-06-05 2014-08-13 兰州理工大学 Method for separating lithium cobalt oxide and aluminum foil on scrapped lithium ion battery positive pole piece
CN104103870A (en) * 2014-07-30 2014-10-15 兰州理工大学 Method for recovering cobalt lithium aluminum from positive pole plate of scrap lithium ion battery
CN104466292A (en) * 2014-12-30 2015-03-25 兰州理工大学 Method for recovering cobalt lithium metal from waste lithium ion battery of lithium cobalt oxide positive material
CN105886777A (en) * 2016-05-16 2016-08-24 兰州理工大学 Method for synergistically treating acid-making exhaust gas and wasted lithium cobalt oxide and recovering cobalt lithium
CN105907977A (en) * 2016-07-08 2016-08-31 长沙理工大学 Method for recycling lithium cobalt oxides from waste lithium-ion batteries

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107275706A (en) * 2017-06-19 2017-10-20 上海第二工业大学 A kind of technique of use mechanical activation method Call Provision and lithium from waste and old cobalt acid lithium battery
CN112142589A (en) * 2020-09-27 2020-12-29 厦门理工学院 Method for synthesizing cobalt oxalate dihydrate from leaching solution of positive active material of waste lithium battery
CN112142589B (en) * 2020-09-27 2023-04-28 厦门理工学院 Method for synthesizing cobalt oxalate dihydrate from leaching solution of waste lithium battery anode active material
ES2924113A1 (en) * 2021-03-16 2022-10-04 Asociacion De Investig De Las Industrias Ceramicas A I C E METHOD FOR THE RECOVERY OF ACTIVE CATHODE MATERIAL FROM SPENT LITHIUM-ION RECHARGEABLE BATTERIES (Machine-translation by Google Translate, not legally binding)
CN114400395A (en) * 2022-02-22 2022-04-26 楚能新能源股份有限公司 Method for preparing lithium cobalt phosphate by recycling waste lithium cobalt oxide
CN114400395B (en) * 2022-02-22 2023-08-25 楚能新能源股份有限公司 Method for preparing lithium cobalt phosphate by recycling waste lithium cobalt oxide
WO2024055510A1 (en) * 2022-09-15 2024-03-21 广东邦普循环科技有限公司 Method for preparing lithium iron phosphate from nickel-rion alloy and use thereof

Similar Documents

Publication Publication Date Title
CN106450559A (en) Method for preparing new electrodes through recovering of waste ion batteries
CN102891345B (en) Method for recycling lithium chloride from waste lithium iron phosphate
CN101609888B (en) Method for preparing battery level lithium carbonate by using lithium chloride solution
CN104466295B (en) The renovation process of positive electrode active materials in nickle cobalt lithium manganate used Li ion cell
CN104466292B (en) The method of Call Provision lithium metal from the used Li ion cell of lithium cobaltate cathode material
CN107653378A (en) The recovery method of valuable metal in a kind of waste and old nickel cobalt manganese lithium ion battery
CN102903985B (en) Method for recycling lithium carbonate from lithium iron phosphate waste material
CN107699692A (en) A kind of recovery and the method for regenerating waste used anode material for lithium-ion batteries
CN109088115A (en) Waste lithium ion cell anode closed matereial cycle prepares tertiary cathode material method
CN106450547A (en) Method for recycling iron phosphate and lithium carbonate from lithium iron phosphate waste
CN102820468B (en) Preparation process of cobaltosic oxide for continuous production of batteries
CN105742744B (en) A kind of method that lithium is extracted in the waste liquid containing lithium produced from waste and old lithium ion battery removal process
CN105990617A (en) Method for recycling and regenerating waste lithium ion battery electrode materials
CN101205080B (en) Method for preparing high-quality red lead by lead slime of lead-acid batteries
CN104134791A (en) High-voltage mono-crystal lithium nickel cobalt manganese oxide anode material and preparation method thereof
CN104538696A (en) Method for recycling metal from waste lithium ion battery with Ni-Co lithium manganite positive electrode materials
CN102285673A (en) Method for recovering lithium and iron from lithium iron phosphate power battery for electromobile
CN104538695A (en) Method for recycling metal in waste LiMn1-x-yNixCoyO2 battery and preparing LiMn1-x-yNixCoyO2
CN104577104B (en) Regeneration method of positive material lithium manganate waste of lithium ion battery
CN104466294A (en) Method for recycling metal from waste Ni-Co lithium manganate battery
CN105895983A (en) Method for preparing high-purity PbO by cycle wet method
CN104485493A (en) Repair and regeneration method for lithium cobaltate positive active material in waste lithium ion battery
CN110092398A (en) A kind of method of waste and old lithium ion battery baking tail gases resource utilization
CN107285394A (en) A kind of precursor for ternary anode material and preparation method thereof
CN110395767A (en) A method of chemical manganese bioxide is prepared using electrolytic manganese anode mud

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20170222