CN106099076B - A kind of flower-shaped nitrogen-doped carbon cladding bismuth structural composite material and its preparation method and application - Google Patents

A kind of flower-shaped nitrogen-doped carbon cladding bismuth structural composite material and its preparation method and application Download PDF

Info

Publication number
CN106099076B
CN106099076B CN201610701833.XA CN201610701833A CN106099076B CN 106099076 B CN106099076 B CN 106099076B CN 201610701833 A CN201610701833 A CN 201610701833A CN 106099076 B CN106099076 B CN 106099076B
Authority
CN
China
Prior art keywords
bismuth
composite material
flower
doped carbon
nitrogen
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.)
Active
Application number
CN201610701833.XA
Other languages
Chinese (zh)
Other versions
CN106099076A (en
Inventor
兰金叻
秦成杰
杨小平
于运花
于礼玮
殷全帅
韩嘉豪
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.)
Beijing University of Chemical Technology
Original Assignee
Beijing University of Chemical Technology
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 Beijing University of Chemical Technology filed Critical Beijing University of Chemical Technology
Priority to CN201610701833.XA priority Critical patent/CN106099076B/en
Publication of CN106099076A publication Critical patent/CN106099076A/en
Application granted granted Critical
Publication of CN106099076B publication Critical patent/CN106099076B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention relates to a kind of flower-shaped nitrogen-doped carbons to coat bismuth structural composite material and its preparation method and application, and which solve the not high technical problems of existing lithium ion battery negative material capacity and cyclical stability, have the following structure：The amorphous carbon of N doping is uniformly coated on flower-shaped bismuth nano grain surface；The composite material diameter 200nm~600nm, 100~300nm of thickness, it is 10~20nm that carbon-coating, which coats thickness,.The present invention discloses preparation method simultaneously.The present invention can be used for the preparation field of lithium ion battery negative material.

Description

A kind of flower-shaped nitrogen-doped carbon cladding bismuth structural composite material and its preparation method and application
Technical field
The present invention relates to lithium ion battery electrode material preparation field, and in particular to a kind of flower-shaped nitrogen-doped carbon cladding bismuth structure Composite material and preparation method and application.
Background technology
Lithium ion battery is widely paid close attention to because many advantages are possessed, its application field also expands constantly Greatly, from mobile phone, digital camera, laptop electric vehicle till now and military use product.
Currently, commercial lithium ion battery negative material is mainly graphited carbon material.There are theoretical capacities for carbon material It is low, first charge-discharge efficiency is low, organic solvent many deficiencies such as embedded altogether, and start to restrict the hair of entire lithium ion battery Exhibition.But with the continuous development of society, requirement of each field to capacity of lithium ion battery and charge-discharge velocity is constantly carrying Height because it directly affect electronic product miniaturization and some large-scale instrument stand-by power supplies high-rate charge-discharge capability and The problems such as cruising ability, so the development of high performance lithium ion battery is for portable electronic device, electric vehicle and other one A little storage devices are particularly important.Researcher while improving carbon material performance as possible, also begin to exploitation it is new, may be used as Negative electrode of lithium ion battery, the more superior material of performance.
In recent years, researcher has carried out extensive research to lithium ion battery negative material.Currently, bismuth metal material Research start to cause the attention of researcher.The mass theory capacity of bismuth is 386mA h/g, slightly above carbon material, but It is it with higher volume capacity 3765mAh/cm-3.Mainly there are pattern control and carbon for the research method of bismuth material at present Cladding, such as document (Su D, Dou S, Wang G.Bismuth:A new anode for the Na-ion battery.Nano Energy,2015,12:The nanocomposite for 88-95.) preparing bismuth and graphene is used for sodium-ion battery cathode, Under the current density of 40mA/g, higher reversible specific capacity can be kept, is 561mAh/g, but capacity and cyclical stability are also There can be further raising.
Invention content
The present invention is exactly to be asked to solve existing lithium ion battery negative material capacity and the not high technology of cyclical stability Topic provides a kind of flower-shaped nitrogen-doped carbon cladding bismuth structural composite material and preparation method thereof with outstanding multiplying power and cycle performance And application.
For this purpose, the present invention provides a kind of flower-shaped nitrogen-doped carbon cladding bismuth structural composite material, have the following structure：It is compound Material has the following structure：The amorphous carbon of N doping is uniformly coated on flower-shaped bismuth nano grain surface；The bismuth nanometer Hole is equipped between grain；The composite material diameter 200nm~600nm, 100~300nm of thickness, carbon-coating coat thickness be 10~ 20nm。
Present invention simultaneously provides the preparation methods that a kind of flower-shaped nitrogen-doped carbon coats bismuth structural composite material comprising as follows Step：(1) claim the Na of 0.3~0.7 mass parts2CO3After being dissolved in the water of 50~90 mass parts, 1.2~2 mass parts are added Bismuth citrate stir evenly, at 150~180 DEG C carry out 20~30h of hydro-thermal reaction, clean and dry after being cooled to room temperature To the presoma of bismuth；(2) salt acid for adjusting pH will be used extremely after being mixed with buffer solution by the aqueous solution of gained presoma in step (1) 8.0~9.0, the reaction of 50~200 mass parts Dopamine hydrochlorides is added, the reaction time is 8~56h, obtains poly-dopamine cladding Forerunner's composite material, filtration washing collecting reaction product；(3) poly-dopamine obtained in step (2) cladding presoma is multiple Condensation material 2~4h of carburizing reagent at 600~800 DEG C in nitrogen atmosphere, you can obtain flower-shaped nitrogen-doped carbon cladding bismuth structure Composite material.
Preferably, the buffer substance being added in the buffer solution is disodium hydrogen phosphate or trishydroxymethylaminomethane.
Present invention simultaneously provides flower-shaped nitrogen-doped carbon cladding bismuth structural composite materials to prepare lithium ion battery negative material In application.
The flower-shaped presoma for the bismuth that the present invention is synthesized using hydro-thermal method, using dopamine as carbon source, is existed as template by dopamine Auto polymerization in buffer solution is uniformly coated on the surface of flower-shaped presoma, then high temperature cabonization, and the presoma of internal bismuth turns CO is generated while turning to bismuth oxide2Gas causes to generate hole between Bismuth oxide particles, and at the same time bismuth oxide and carbon are in height Temperature is lower to occur carbothermic reduction reaction, ultimately forms flower-shaped nitrogen-doped carbon cladding bismuth structural composite material.In prepared composite material, Carbon-coating is coated with to improve the electronic conductivity energy of bismuth, can effectively improve the high rate performance of the material；Bismuth active material it Between hole, can the effectively volume expansion that is generated during repeated charge of padded coaming, it is ensured that the Gao Xun of composite material Ring stability, and the transmission range of lithium ion can be shortened.
Flower-shaped nitrogen-doped carbon cladding bismuth structural composite material prepared by the present invention can as lithium ion battery negative material To show outstanding chemical property.Carbon-coating is conducive to improve the electronic conductivity energy of bismuth, can effectively improve the material High rate performance；Gap in carbonization process between bismuth active material, can effectively padded coaming produced during repeated charge Raw volume expansion, it is ensured that the high circulation stability of composite material, and the transmission range of lithium ion can be shortened.
Description of the drawings
Fig. 1 is the stereoscan photograph of 1 product of embodiment；
Fig. 2 is the XRD curves of 1 product of embodiment；
Fig. 3 is that embodiment 1 is prepared, and there is flower-shaped nitrogen-doped carbon to coat bismuth structural composite material as lithium cell cathode material High rate performance figure.
Specific implementation mode
It elaborates below to the embodiment of the present invention, the present embodiment is carried out lower based on the technical solution of the present invention Implement, gives detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following implementation Example.
Embodiment 1
Claim 0.3g Na2CO31.2g bismuth citrates are added after being dissolved in 50mL water to stir evenly, water is carried out at 150 DEG C Thermal response 30h cleans and dries to obtain the presoma of bismuth after being cooled to room temperature.Again by the aqueous solution of presoma and trihydroxy methyl ammonia With salt acid for adjusting pH to 8.0~9.0 after methylmethane mixing, the reaction of 50mg Dopamine hydrochlorides is added, reaction time 56h is obtained Forerunner's composite material, filtration washing collecting reaction product are coated to poly-dopamine.Obtained poly-dopamine is coated into presoma Composite material carburizing reagent 2h at 800 DEG C in nitrogen atmosphere, you can obtain flower-shaped nitrogen-doped carbon cladding bismuth structure composite material Material.
The stereoscan photograph of product is as shown in Figure 1, the XRD curves of product are as shown in Figure 2.Fig. 3 is that the multiplying power of material is filled Discharge test figure.As can be seen from Figure 3 with the increase of current density, capacity decline is slower, illustrates this Material has preferable rate charge-discharge performance.And the circulation volume several times under each multiplying power keeps stablizing, when electric current is close When degree returns to low range, capacity can be very good to restore, it was demonstrated that this material has good cyclical stability.
Embodiment 2
Claim 0.5g Na2CO31.6g bismuth citrates are added after being dissolved in 70mL water to stir evenly, water is carried out at 180 DEG C Thermal response 20h cleans and dries to obtain the presoma of bismuth after being cooled to room temperature.Again by the aqueous solution of presoma and trihydroxy methyl ammonia With salt acid for adjusting pH to 8.0~9.0 after methylmethane mixing, the reaction of 125mg Dopamine hydrochlorides is added, reaction time 40h is obtained Forerunner's composite material, filtration washing collecting reaction product are coated to poly-dopamine.Obtained poly-dopamine is coated into presoma Composite material carburizing reagent 3h at 700 DEG C in nitrogen atmosphere, you can obtain flower-shaped nitrogen-doped carbon cladding bismuth structure composite material Material.
Electro-chemical test part is with embodiment 1, the prepared materials show experiment knot almost the same with embodiment 1 Fruit.
Embodiment 3
Claim 0.7g Na2CO32g bismuth citrates are added after being dissolved in 90mL water to stir evenly, hydro-thermal is carried out at 170 DEG C 25h is reacted, cleans and dry to obtain the presoma of bismuth after being cooled to room temperature.Again by the aqueous solution of presoma and trihydroxy methyl amino With salt acid for adjusting pH to 8.0~9.0 after methane blended, the reaction of 200mg Dopamine hydrochlorides is added, reaction time 8h is obtained Poly-dopamine coats forerunner's composite material, filtration washing collecting reaction product.Obtained poly-dopamine cladding presoma is answered Condensation material carburizing reagent 4h at 600 DEG C in nitrogen atmosphere, you can obtain flower-shaped nitrogen-doped carbon cladding bismuth structural composite material.
Electro-chemical test part is with embodiment 1, the prepared materials show experiment knot almost the same with embodiment 1 Fruit.

Claims (4)

1. a kind of flower-shaped nitrogen-doped carbon coats bismuth structural composite material, it is characterized in that the composite material has the following structure：Nitrogen The amorphous carbon of doping is uniformly coated on flower-shaped bismuth nano grain surface；Hole is equipped between the bismuth nano particle；It is described Composite material diameter 200nm~600nm, 100~300nm of thickness, it is 10~20nm that carbon-coating, which coats thickness,.
2. a kind of preparation method of flower-shaped nitrogen-doped carbon cladding bismuth structural composite material, it is characterized in that including the following steps：
(1) claim the Na of 0.3~0.7 mass parts2CO3After being dissolved in the water of 50~90 mass parts, 1.2~2 mass parts are added Bismuth citrate stirs evenly, and 20~30h of hydro-thermal reaction is carried out at 150~180 DEG C, is cleaned after being cooled to room temperature and dries to obtain The presoma of bismuth；
(2) salt acid for adjusting pH will be used to 8.0~9.0 after being mixed with buffer solution by the aqueous solution of gained presoma in the step (1), The reaction of 50~200 mass parts Dopamine hydrochlorides is added, the reaction time is 8~56h, obtains poly-dopamine cladding forerunner's bluk recombination Material, filtration washing collecting reaction product；
(3) by the poly-dopamine obtained in step (2) coat forerunner's composite material in nitrogen atmosphere at 600~800 DEG C 2~4h of carburizing reagent, you can obtain flower-shaped nitrogen-doped carbon cladding bismuth structural composite material.
3. the preparation method of flower-shaped nitrogen-doped carbon cladding bismuth structural composite material according to claim 2, it is characterised in that The buffer substance being added in the buffer solution is disodium hydrogen phosphate or trishydroxymethylaminomethane.
4. flower-shaped nitrogen-doped carbon cladding bismuth structural composite material as described in claim 1 is preparing lithium ion battery negative material In application.
CN201610701833.XA 2016-08-22 2016-08-22 A kind of flower-shaped nitrogen-doped carbon cladding bismuth structural composite material and its preparation method and application Active CN106099076B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610701833.XA CN106099076B (en) 2016-08-22 2016-08-22 A kind of flower-shaped nitrogen-doped carbon cladding bismuth structural composite material and its preparation method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610701833.XA CN106099076B (en) 2016-08-22 2016-08-22 A kind of flower-shaped nitrogen-doped carbon cladding bismuth structural composite material and its preparation method and application

Publications (2)

Publication Number Publication Date
CN106099076A CN106099076A (en) 2016-11-09
CN106099076B true CN106099076B (en) 2018-09-21

Family

ID=57225498

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610701833.XA Active CN106099076B (en) 2016-08-22 2016-08-22 A kind of flower-shaped nitrogen-doped carbon cladding bismuth structural composite material and its preparation method and application

Country Status (1)

Country Link
CN (1) CN106099076B (en)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107146915B (en) * 2017-04-10 2019-08-27 中山大学 A kind of preparation method of porous bismuth-carbon composite
CN108281628B (en) * 2018-01-05 2020-08-04 武汉理工大学 Zinc-cobalt sulfide/nitrogen-doped carbon composite material and preparation method and application thereof
CN108689715B (en) * 2018-04-18 2021-01-15 山东国瓷功能材料股份有限公司 Aluminum nitride powder and preparation method thereof
CN108899557B (en) * 2018-06-07 2020-11-06 上海交通大学 Nitrogen-doped flower-type carbon nano material with through-type mesopores and preparation method
CN108832110A (en) * 2018-06-26 2018-11-16 华南师范大学 A kind of compound ZIF-8 negative electrode material of height ratio capacity bismuth nanoparticle and its preparation method and application
CN111044645A (en) * 2020-01-10 2020-04-21 福州大学 Preparation method and application of magnetic flower-like nano material
CN111769272A (en) * 2020-07-28 2020-10-13 广西师范大学 Bi @ C hollow nanosphere composite material and preparation method and application thereof
CN112542577B (en) * 2020-12-03 2022-09-09 济南大学 Nano bismuth/nitrogen-doped carbon foam nanosheet two-dimensional composite material and preparation method and application thereof
CN112599743B (en) * 2020-12-15 2022-06-07 西安交通大学 Carbon-coated nickel cobaltate multi-dimensional assembled microsphere negative electrode material and preparation method thereof
CN112844351A (en) * 2021-01-08 2021-05-28 杭州神起科技有限公司 Flower-shaped Fe-doped TiO2Preparation method and application of porous carbon-loaded composite material
CN113363434B (en) * 2021-05-12 2022-06-14 中国科学院过程工程研究所 Multi-core multi-shell hollow material for encapsulating nano particles and preparation method and application thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102212880A (en) * 2010-04-08 2011-10-12 中国检验检疫科学研究院 Elementary substance Bi nano-structured material and preparation method and application thereof
CN103708551A (en) * 2013-12-26 2014-04-09 湛江师范学院 Preparation method of bismuth oxycarbonate flower-like microsphere thermally synthesized by ethylene glycol-water mixed solvent
CN104229881A (en) * 2014-09-24 2014-12-24 浙江大学 Preparation method of bismuth subcarbonate microflowers and product
CN105024056A (en) * 2015-06-05 2015-11-04 中南大学 Bismuth/nitrogen-doped carbon-sphere composite anode material for sodium ion battery and preparation method thereof
CN105312086A (en) * 2014-08-04 2016-02-10 西北大学 Preparation method for carbon-coated bismuth nano composite material
CN105552393A (en) * 2016-01-22 2016-05-04 中南大学 Bi-functional catalyst for alkaline water system metal/air battery and preparation method thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101817555B (en) * 2010-03-25 2012-06-27 山东大学 Bismuthyl carbonate micro flowery material with graded structure and preparation method thereof
CN105664980B (en) * 2016-02-24 2018-04-17 江苏大学 A kind of Preparation method and use of pine needle charcoal load flower BiOCl composite photo-catalysts

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102212880A (en) * 2010-04-08 2011-10-12 中国检验检疫科学研究院 Elementary substance Bi nano-structured material and preparation method and application thereof
CN103708551A (en) * 2013-12-26 2014-04-09 湛江师范学院 Preparation method of bismuth oxycarbonate flower-like microsphere thermally synthesized by ethylene glycol-water mixed solvent
CN105312086A (en) * 2014-08-04 2016-02-10 西北大学 Preparation method for carbon-coated bismuth nano composite material
CN104229881A (en) * 2014-09-24 2014-12-24 浙江大学 Preparation method of bismuth subcarbonate microflowers and product
CN105024056A (en) * 2015-06-05 2015-11-04 中南大学 Bismuth/nitrogen-doped carbon-sphere composite anode material for sodium ion battery and preparation method thereof
CN105552393A (en) * 2016-01-22 2016-05-04 中南大学 Bi-functional catalyst for alkaline water system metal/air battery and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"N掺杂Bi2O2CO3/氧化石墨烯结构的合成及其可见光催化性能研究";董兴安 等;《人工晶体学报》;20150630;第44卷(第6期);全文 *

Also Published As

Publication number Publication date
CN106099076A (en) 2016-11-09

Similar Documents

Publication Publication Date Title
CN106099076B (en) A kind of flower-shaped nitrogen-doped carbon cladding bismuth structural composite material and its preparation method and application
CN105742602B (en) A kind of sodium-ion battery cathode Sn/MoS2/ C composite and preparation method thereof
CN105355870B (en) Expanded graphite and nanometer silicon composite material and preparation method thereof, electrode slice, battery
CN105742635B (en) A kind of tin ash/graphene/carbon composite material and preparation method thereof
Li et al. Building a Ni 3 S 2 nanotube array and investigating its application as an electrode for lithium ion batteries
CN105720251B (en) A kind of sodium-ion battery antimony trisulfide based composites and preparation method thereof
CN106654215B (en) Biological micromolecule and graphene composite material functional membrane and preparation method thereof
CN104051729B (en) NiFe for cathode of lithium battery2o4the preparation method of/graphene composite material
CN103326007B (en) The preparation method of three-dimensional graphite thiazolinyl tin dioxide composite material and application thereof
CN106410150A (en) MoO2-MoS2 negative electrode material of sodium-ion battery with core-shell structure and preparation method of MoO2-MoS2 negative electrode material
CN106914244B (en) A kind of graphene-based metallic compound nano array material preparation and application
CN104966824A (en) Nitrogen-doped porous carbon sphere and cobaltous oxide nano-composite anode material based on chitosan and derivatives thereof and preparation method thereof
CN106099069A (en) A kind of sodium-ion battery negative pole SnS/C composite and preparation method thereof
CN109285994A (en) The preparation method of lithium ion battery silicon-carbon cathode material
CN104835964A (en) Three-dimensional macroporous graphene, carbon nano tube and molybdenum disulfide composite material, and preparation method and application of composite material
CN105826527A (en) Porous silicon-carbon composite material and preparation method and application thereof
CN108390014A (en) The preparation method of foamed nickel supported different-shape cobalt black nano material
CN108658119B (en) Method for preparing copper sulfide nanosheet and compound thereof by low-temperature vulcanization technology and application
CN107680821B (en) A kind of double-metal hydroxide@nickel molybdate@graphene nanocomposite material, preparation method and applications
CN105428612B (en) A kind of nanometer MoO2‑MoSe2@SFC lithium ion battery negative materials and preparation method thereof
CN106876682A (en) A kind of manganese oxide with loose structure/nickel micron ball and its preparation and application
CN105280897A (en) Preparation method for C/ZnO/Cu composite material of anode material of lithium ion battery
CN108492996A (en) A kind of preparation method of fluorine, nitrogen co-doped class graphene film layer material
CN106450193A (en) Nickel sulfide/graphene composite material and preparation method and application thereof
CN104953105B (en) A kind of lithium ion battery SnOxThe preparation method of/carbon nano tube compound material

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant