CN111204751A - Three-dimensional graphene macroscopic material and preparation method and application thereof - Google Patents

Three-dimensional graphene macroscopic material and preparation method and application thereof Download PDF

Info

Publication number
CN111204751A
CN111204751A CN201911152133.XA CN201911152133A CN111204751A CN 111204751 A CN111204751 A CN 111204751A CN 201911152133 A CN201911152133 A CN 201911152133A CN 111204751 A CN111204751 A CN 111204751A
Authority
CN
China
Prior art keywords
graphene
heteropolyacid
dimensional
preparation
composite
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
CN201911152133.XA
Other languages
Chinese (zh)
Inventor
吴忠帅
孙承林
王森
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.)
Dalian Institute of Chemical Physics of CAS
Original Assignee
Dalian Institute of Chemical Physics of CAS
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 Dalian Institute of Chemical Physics of CAS filed Critical Dalian Institute of Chemical Physics of CAS
Priority to CN201911152133.XA priority Critical patent/CN111204751A/en
Publication of CN111204751A publication Critical patent/CN111204751A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/194—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00—Structure or properties of graphene
    • C01B2204/20—Graphene characterized by its properties
    • C01B2204/22—Electronic properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00—Structure or properties of graphene
    • C01B2204/20—Graphene characterized by its properties
    • C01B2204/32—Size or surface area

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Inorganic Chemistry (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The invention discloses a three-dimensional graphene macroscopic body material and a preparation method and application thereof, and specifically comprises the following steps: uniformly mixing graphene oxide and heteropoly acid solution, then adding hydrazine hydrate, uniformly mixing, and standing at room temperature to obtain the graphene macroscopic body with the three-dimensional cross-linked porous network. Compared with the prior art, the preparation method of the three-dimensional graphene macroscopic material only needs room temperature and does not need heating; the method is simple and convenient to operate, convenient and quick, low in energy consumption and high in efficiency, and is a method capable of preparing the three-dimensional graphene macroscopic body in a large scale.

Description

Three-dimensional graphene macroscopic material and preparation method and application thereof
Technical Field
The invention belongs to the field of nano materials, and particularly relates to a method for quickly preparing a graphene/heteropoly acid composite three-dimensional graphene macroscopic body at room temperature.
Background
The three-dimensional graphene macroscopic material has the characteristics of low density, porosity, high specific surface area and the like, can be used as an excellent electrode, adsorption and heat dissipation material, and has wide application prospect. At present, methods for constructing a three-dimensional graphene macroscopic body mainly include a template method and a self-assembly method. The template method mainly uses a chemical vapor deposition method, and the surface of the three-dimensional graphene macroscopic body prepared by the method is always strong in hydrophobicity and very limited in application; in addition, the chemical vapor deposition method has high preparation cost and is difficult to realize large-scale preparation. The self-assembly method mainly comprises a sol-gel method, a hydrothermal/solvothermal method, chemical reduction self-assembly and the like, but the reaction temperature of the existing self-assembly process is mostly higher than 90 ℃, the energy consumption is high, a hydrothermal kettle is needed, the large-scale production is not easy, and the practical application of the self-assembly method is greatly limited. Therefore, the development of a method which is simple in process, low in energy consumption and capable of preparing the high-performance three-dimensional graphene macroscopic material in a large scale can greatly promote the development and practical application of the three-dimensional graphene macroscopic material in the fields of electrode materials and the like.
Disclosure of Invention
In order to overcome the defect that the macroscopical preparation method of the three-dimensional graphene is embodied, the invention aims to develop a method for quickly, efficiently and massively preparing a macroscopical three-dimensional graphene body at room temperature.
The invention provides a graphene/heteropoly acid composite three-dimensional graphene macroscopic body material, wherein the graphene/heteropoly acid composite three-dimensional graphene macroscopic body consists of graphene and heteropoly acid, and the density of the graphene/heteropoly acid composite three-dimensional graphene macroscopic body is 0.02-1.5g/cm3The content of heteropoly acid is 5-30 wt%, and the specific surface area is 100-800cm2The electrical conductivity is 10-100S/m.
The invention provides a preparation method of a graphene/heteropoly acid composite three-dimensional graphene macroscopic material, which specifically comprises the following steps:
(1) uniformly mixing graphene oxide and a heteropoly acid aqueous solution to obtain a mixed solution; wherein the mass ratio of the graphene oxide to the heteropoly acid is 0.1-20: 1. The lateral dimension of the graphene oxide is 0.5-200 μm, and the preferable range is 1-100 μm; the concentration of the graphene oxide is 0.1-20mg/mL, and the preferable range is 0.5-10 mg/mL.
(2) Uniformly dispersing hydrazine hydrate in the mixed solution obtained in the step (1), and standing at room temperature to obtain graphene/heteropoly acid composite three-dimensional graphene hydrogel;
(3) and (3) drying the graphene/heteropoly acid composite three-dimensional graphene hydrogel obtained in the step (2) to obtain the three-dimensional graphene macroscopic material.
The three-dimensional graphene macroscopic body is a graphene/heteropoly acid composite three-dimensional graphene macroscopic body.
The heteropoly acid in the step (1) comprises one or more of phosphomolybdic acid, silicomolybdic acid, germanium molybdic acid, phosphotungstic acid, silicotungstic acid, germanium tungstic acid and the like.
The concentration of the heteropoly acid in the step (1) is 0.1-50mmol/L, and the preferable range is 0.5-30 mmol/L.
The mixing time of the graphene oxide and the heteropoly acid solution in the step (1) is 0.5-5h, and the preferred range is 1-3 h.
The mass ratio of hydrazine hydrate to heteropoly acid in the step (2) is 0.5-5: 1.
The preparation temperature of the graphene oxide/heteropoly acid composite three-dimensional graphene macroscopic body in the step (2) is 10-35 ℃. The preferred range is 20-30 ℃.
And (3) adding hydrazine hydrate in the step (2) into the mixed solution obtained in the step (1), uniformly mixing, and standing for 0.1-20 h.
And (3) drying the three-dimensional graphene macroscopic body in the step (3) in a drying mode including room temperature drying, forced air drying, vacuum drying and freeze drying.
The graphene/heteropoly acid composite three-dimensional graphene macroscopic material disclosed by the invention is used as an electrode material of a super capacitor, an organic solvent and an adsorbent of heavy metal.
The three-dimensional graphene macroscopic body is a graphene/heteropoly acid composite three-dimensional graphene macroscopic body and is prepared by taking a graphene oxide solution and a heteropoly acid solution as raw materials.
The invention has the following advantages:
1. the invention provides a method for quickly, efficiently and massively preparing a three-dimensional graphene macroscopic body at room temperature, which is simple to operate, low in energy consumption and high in efficiency, and has no special requirements on containers and equipment (heating and reaction kettles are not needed) in the preparation process;
2. the three-dimensional graphene macroscopic body consists of graphene and heteropoly acid, and the graphene and the heteropoly acid are connected through chemical bonds, so that the three-dimensional graphene macroscopic body has better stability;
3. heteropoly acid with excellent electrochemical performance and catalytic performance is introduced into the graphene, so that the application field of the graphene assembly is widened.
Drawings
Fig. 1 is a photograph of a graphene/heteropoly acid three-dimensional macroscopic material prepared in example 1 of the present invention.
Fig. 2 is a scanning electron microscope image of a graphene/heteropoly acid three-dimensional graphene macroscopic body prepared in example 2 of the present invention.
Detailed Description
The method of the present invention will be described in detail with reference to specific examples, which are carried out on the premise of the technical solution of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1
Uniformly mixing 10mL of graphene oxide with the concentration of 5mg/mL and the transverse dimension of 10-50 μm with 5mL of 5mmol/L phosphomolybdic acid solution, then adding 100 μ L of 80% hydrazine hydrate, uniformly mixing, and standing at 20 ℃ for 2h to obtain the three-dimensional graphene macroscopic body hydrogel (as shown in figure 1). Obtaining a compact three-dimensional graphene macroscopic body through vacuum drying, wherein the mass density is 1.25g/cm3Specific surface area of 58cm2The specific mass capacity of the material is 360F/g.
Example 2
Uniformly mixing 8mL of graphene oxide with the concentration of 0.1mg/mL and the transverse dimension of 1-50 μm with 5mL of phosphotungstic acid solution with the transverse dimension of 0.1mmol/L, then adding 10 μ L of 50% hydrazine hydrate, uniformly mixing, and standing at 25 ℃ for 0.1h to obtain the three-dimensional graphene macroscopic body hydrogel. Drying at room temperature to obtain compact three-dimensional graphene macroscopic body with mass density of 1.5g/cm3The specific surface area is 380cm2The specific mass capacity of the electrode material is 230F/g.
Example 3
Uniformly mixing 20mL of graphene oxide with the concentration of 20mg/mL and the transverse dimension of 10-50 μm with 1mL of phosphomolybdic acid solution with the transverse dimension of 50mmol/L, then adding 200 μ L of 80% hydrazine hydrate, uniformly mixing, and standing at 25 ℃ for 20h to obtain the three-dimensional graphene macroscopic body hydrogel. Freeze drying to obtain three-dimensional graphene macroscopic body aerogel (shown as figure 2), with mass density of 1.5g/cm3The specific surface area is 0.03cm2The specific conductivity is 1000S/m, and the specific adsorption capacity is 130 times of the volume of the adsorbent applied to the organic solvent.
Example 4
30mL of the oxidized stone with the concentration of 20mg/mL and the transverse dimension of 50-200 mu mUniformly mixing the graphene with 1mL of 25mmol/L silicomolybdic acid solution, then adding 100 mu L of 60% hydrazine hydrate, uniformly mixing, and standing at 27 ℃ for 8h to obtain the three-dimensional graphene macroscopic body. Obtaining the three-dimensional graphene macroscopic body aerogel through air blast drying, wherein the mass density is 0.45g/cm3The specific surface area is 0.03cm2The specific surface area per gram (mg/g) and the conductivity is 750S/m, and the specific surface area per gram (mg/g) is 450mg/g when the adsorbent is applied to an adsorbent for heavy metal lead ions.

Claims (13)

1.一种石墨烯/杂多酸复合三维石墨烯宏观体材料，其特征在于：石墨烯/杂多酸复合三维石墨烯宏观体由石墨烯和杂多酸组成，密度为0.02-1.5g/cm3，杂多酸含量为5-30wt％，比表面积为10-800cm2/g，电导率为10-1000S/m。1. a graphene/heteropolyacid composite three-dimensional graphene macroscopic body material, is characterized in that: graphene/heteropolyacid composite three-dimensional graphene macroscopic body is made up of Graphene and heteropolyacid, and density is 0.02-1.5g/ cm 3 , the content of the heteropoly acid is 5-30 wt %, the specific surface area is 10-800 cm 2 /g, and the electrical conductivity is 10-1000 S/m. 2.一种石墨烯/杂多酸复合三维石墨烯宏观体材料的制备方法，其特征在于：具体包括以下步骤：2. a preparation method of graphene/heteropolyacid composite three-dimensional graphene macroscopic body material, is characterized in that: specifically comprises the following steps: (1)将氧化石墨烯与杂多酸水溶液混合均匀得到混合溶液；(1) evenly mixing graphene oxide and heteropolyacid aqueous solution to obtain a mixed solution; (2)将水合肼均匀分散于步骤(1)所得的混合溶液中，室温下静置得到石墨烯/杂多酸复合三维石墨烯水凝胶；(2) uniformly dispersing hydrazine hydrate in the mixed solution obtained in step (1), and standing at room temperature to obtain a graphene/heteropolyacid composite three-dimensional graphene hydrogel; (3)将步骤(2)得到的石墨烯/杂多酸复合三维石墨烯水凝胶经干燥后得到三维石墨烯宏观体材料。(3) drying the graphene/heteropolyacid composite three-dimensional graphene hydrogel obtained in step (2) to obtain a three-dimensional graphene macroscopic bulk material. 3.根据权利要求2所述的石墨烯/杂多酸复合三维石墨烯宏观体材料的制备方法，其特征在于：所述三维石墨烯宏观体为石墨烯/杂多酸复合三维石墨烯宏观体。3. the preparation method of graphene/heteropolyacid composite three-dimensional graphene macroscopic body material according to claim 2, it is characterized in that: described three-dimensional graphene macroscopic body is graphene/heteropolyacid composite three-dimensional graphene macroscopic body . 4.根据权利要求2所述的石墨烯/杂多酸复合三维石墨烯宏观体材料的制备方法，其特征在于：所述步骤(1)中氧化石墨烯与杂多酸的质量比为0.1-20:1。4. the preparation method of graphene/heteropolyacid composite three-dimensional graphene macroscopic body material according to claim 2, is characterized in that: in described step (1), the mass ratio of graphene oxide and heteropolyacid is 0.1- 20:1. 5.根据权利要求2所述的石墨烯/杂多酸复合三维石墨烯宏观体材料的制备方法，其特征在于：所述步骤(1)中氧化石墨烯的横向尺寸为0.5-200μm，浓度为0.1-20mg/mL。5. the preparation method of graphene/heteropolyacid composite three-dimensional graphene macroscopic body material according to claim 2, is characterized in that: in described step (1), the lateral dimension of graphene oxide is 0.5-200 μm, and the concentration is 0.1-20 mg/mL. 6.根据权利要求2所述的石墨烯/杂多酸复合三维石墨烯宏观体材料的制备方法，其特征在于：所述步骤(1)中杂多酸包括磷钼酸、硅钼酸、锗钼酸、磷钨酸、硅钨酸、锗钨酸等其中的一种或多种。6. the preparation method of graphene/heteropolyacid composite three-dimensional graphene macroscopic body material according to claim 2, is characterized in that: in described step (1), heteropolyacid comprises phosphomolybdic acid, silico-molybdic acid, germanium One or more of molybdic acid, phosphotungstic acid, silicotungstic acid, germanium tungstic acid, etc. 7.根据权利要求2所述的石墨烯/杂多酸复合三维石墨烯宏观体材料的制备方法，其特征在于：所述步骤(1)中杂多酸的浓度为0.1-50mmol/L。7. the preparation method of graphene/heteropolyacid composite three-dimensional graphene macroscopic body material according to claim 2, is characterized in that: in described step (1), the concentration of heteropolyacid is 0.1-50mmol/L. 8.根据权利要求2所述的石墨烯/杂多酸复合三维石墨烯宏观体的制备方法，其特征在于：所述步骤(1)中氧化石墨烯与杂多酸溶液的混合时间为0.5-5h。8. the preparation method of graphene/heteropolyacid composite three-dimensional graphene macro body according to claim 2, is characterized in that: in described step (1), the mixing time of graphene oxide and heteropolyacid solution is 0.5- 5h. 9.根据权利要求2所述的石墨烯/杂多酸复合三维石墨烯宏观体的制备方法，其特征在于：所述步骤(2)中水合肼与杂多酸的质量比为0.5-5:1。9. the preparation method of graphene/heteropolyacid composite three-dimensional graphene macro body according to claim 2, is characterized in that: in described step (2), the mass ratio of hydrazine hydrate and heteropolyacid is 0.5-5: 1. 10.根据权利要求2所述的石墨烯/杂多酸复合三维石墨烯宏观体的制备方法，其特征在于：所述步骤(2)中氧化石墨烯/杂多酸复合三维石墨烯宏观体的制备温度为10-35℃。10. the preparation method of graphene/heteropolyacid composite three-dimensional graphene macroscopic body according to claim 2, is characterized in that: in described step (2), graphene oxide/heteropolyacid composite three-dimensional graphene macroscopic body The preparation temperature is 10-35°C. 11.根据权利要求2所述的石墨烯/杂多酸复合三维石墨烯宏观体的制备方法，其特征在于：所述步骤(2)中水合肼加入步骤(1)所得的混合溶液中混合均匀后静置时间为0.1-20h。11. the preparation method of graphene/heteropolyacid composite three-dimensional graphene macro-body according to claim 2, is characterized in that: in the described step (2), hydrazine hydrate is added in the mixed solution obtained in step (1) to mix well The post-resting time is 0.1-20h. 12.根据权利要求2所述的石墨烯/杂多酸复合三维石墨烯宏观体的制备方法，其特征在于：所述步骤(3)中三维石墨烯宏观体的干燥方式包括室温干燥，鼓风干燥，真空干燥和冷冻干燥。12. the preparation method of graphene/heteropolyacid composite three-dimensional graphene macro-body according to claim 2, is characterized in that: in described step (3), the drying mode of three-dimensional graphene macro-body comprises room temperature drying, blasting Drying, vacuum drying and freeze drying. 13.一种权利要求1所述的石墨烯/杂多酸复合三维石墨烯宏观体材料的应用，其特征在于：石墨烯/杂多酸复合三维石墨烯宏观体材料作为超级电容器的电极材料、有机溶剂和重金属的吸附剂。13. an application of graphene/heteropolyacid composite three-dimensional graphene macroscopic body material according to claim 1, is characterized in that: graphene/heteropolyacid composite three-dimensional graphene macroscopic body material is used as the electrode material of supercapacitor, Sorbent for organic solvents and heavy metals.
CN201911152133.XA 2019-11-22 2019-11-22 Three-dimensional graphene macroscopic material and preparation method and application thereof Pending CN111204751A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911152133.XA CN111204751A (en) 2019-11-22 2019-11-22 Three-dimensional graphene macroscopic material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911152133.XA CN111204751A (en) 2019-11-22 2019-11-22 Three-dimensional graphene macroscopic material and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN111204751A true CN111204751A (en) 2020-05-29

Family

ID=70787081

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911152133.XA Pending CN111204751A (en) 2019-11-22 2019-11-22 Three-dimensional graphene macroscopic material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN111204751A (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20130074904A (en) * 2011-12-27 2013-07-05 한국화학연구원 Catalyst for preparing levulinic acid or esters thereof from biomass and method for preparing levulinic acid or esters thereof using the catalyst
CN104347877A (en) * 2013-07-31 2015-02-11 北京海特远舟新能源科技有限公司 A nanometer level graphene-based composite material and a preparing method thereof
CN105870430A (en) * 2016-06-20 2016-08-17 扬州大学 Method for preparing three-dimensional graphene-phosphotungstate
KR101667205B1 (en) * 2015-04-17 2016-10-18 서울대학교산학협력단 Method for manufacturing cross-linked graphene-based film
CN107615428A (en) * 2015-11-27 2018-01-19 积水化学工业株式会社 Capacitor electrode material and capacitor

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20130074904A (en) * 2011-12-27 2013-07-05 한국화학연구원 Catalyst for preparing levulinic acid or esters thereof from biomass and method for preparing levulinic acid or esters thereof using the catalyst
CN104347877A (en) * 2013-07-31 2015-02-11 北京海特远舟新能源科技有限公司 A nanometer level graphene-based composite material and a preparing method thereof
KR101667205B1 (en) * 2015-04-17 2016-10-18 서울대학교산학협력단 Method for manufacturing cross-linked graphene-based film
CN107615428A (en) * 2015-11-27 2018-01-19 积水化学工业株式会社 Capacitor electrode material and capacitor
US20180366279A1 (en) * 2015-11-27 2018-12-20 Sekisui Chemical Co., Ltd. Capacitor electrode material and capacitor
CN105870430A (en) * 2016-06-20 2016-08-17 扬州大学 Method for preparing three-dimensional graphene-phosphotungstate

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
HUAXUE CAI ET AL.: "A novel SPEEK/PW11V/rGO hybrid film for proton conduction", 《JOURNAL OF NON-CRYSTALLINE SOLIDS》 *
周智佳等: "杂多酸盐-石墨烯吸附降解甲基紫废水的性能", 《广州化工》 *
孙永明: ""分级结构MoO2/石墨烯纳米复合材料的构筑及其储锂性能研究"", 《中国博士学位论文全文数据库工程科技Ⅰ辑》 *

Similar Documents

Publication Publication Date Title
CN107994225B (en) Porous silicon-carbon composite negative electrode material, preparation method thereof and lithium ion battery
CN106654278B (en) Novel carbon sphere and preparation method and application thereof
CN105170097B (en) A kind of TiO2Nuclear-shell structured nano-composite materials of/ZIF 8 and preparation method thereof
CN112053861B (en) In-situ preparation method of three-dimensional conductive MOF @ MXene composite electrode
CN109671576A (en) Carbon nano tube-MXene composite three-dimensional porous carbon material and preparation method thereof
CN104401969B (en) A kind of constant pressure and dry prepares the method for Graphene microsphere
CN106215817B (en) Preparation method of graphene hydrogel with adjustable internal structure
CN106492761A (en) A kind of preparation method of magnetic hydrogel microsphere
CN103159891B (en) Magnetic amino-modified superhighly-crosslinked resin and preparation method thereof
CN104909351A (en) Nitrogen-doped mesoporous carbon sphere nanomaterial and preparation method thereof
CN106365142A (en) Preparation method of high-specific-surface-area high-electric-conductivity graphene compound carbon aerogel based on chemical crosslinking
CN112007618A (en) Amidoxime group-containing three-dimensional cyclodextrin/graphene aerogel composite adsorption material and preparation method and application thereof
CN104587918A (en) Silver nano-particle modified carbon ball/graphene composite aero-gel material as well as preparation method and application of material
CN104157883A (en) Preparation method of anode of direct methanol fuel cell
CN108975863A (en) Graphene-carbon nano tube composite aerogel based on hydrogen bubble template
CN111977641A (en) A kind of graphene aerogel microsphere with gradient pore structure and preparation method and application thereof
CN103832997A (en) Graphene/carbon black composite material, preparation method and application thereof
CN112086642B (en) A kind of graphitized carbon-coated porous carbon ball with high specific surface area and its preparation method and application
CN103638988B (en) Magnetic mesoporous material, and preparation method and application of magnetic mesoporous material
CN108155392A (en) A kind of preparation method of redox graphene load Pd-M nano-composite catalysts
CN109449012A (en) A kind of preparation method of carboxylic carbon nano-tube/graphene aerogel/nickel foam combination electrode material
CN106395802A (en) Method for preparing graphene porous membrane
CN103523871B (en) Preparation method of mesoporous carbon electrode for electric adsorption desalination
CN110317005B (en) Preparation method of graphene electrode material with three-dimensional hierarchical pore structure
CN108408723A (en) Coal base stratification carbon nano-material based on soft template method and preparation method thereof

Legal Events

Date Code Title Description
PB01 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

Application publication date: 20200529

RJ01 Rejection of invention patent application after publication