CN110316723A - A kind of preparation method and supercapacitor of the porous graphene for supercapacitor - Google Patents
A kind of preparation method and supercapacitor of the porous graphene for supercapacitor Download PDFInfo
- Publication number
- CN110316723A CN110316723A CN201810273067.0A CN201810273067A CN110316723A CN 110316723 A CN110316723 A CN 110316723A CN 201810273067 A CN201810273067 A CN 201810273067A CN 110316723 A CN110316723 A CN 110316723A
- Authority
- CN
- China
- Prior art keywords
- preparation
- graphene
- graphene oxide
- present
- porous graphene
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 156
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 148
- 238000002360 preparation method Methods 0.000 title claims abstract description 50
- 239000000017 hydrogel Substances 0.000 claims abstract description 37
- 239000003513 alkali Substances 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 230000001681 protective effect Effects 0.000 claims abstract description 7
- 239000012298 atmosphere Substances 0.000 claims abstract description 6
- 238000013021 overheating Methods 0.000 claims abstract description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 33
- 238000010438 heat treatment Methods 0.000 claims description 19
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000005554 pickling Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 238000012545 processing Methods 0.000 abstract description 8
- 230000009467 reduction Effects 0.000 abstract description 8
- 230000004913 activation Effects 0.000 abstract description 7
- 238000005530 etching Methods 0.000 abstract description 7
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000010808 liquid waste Substances 0.000 abstract description 3
- 238000000034 method Methods 0.000 description 20
- 239000002994 raw material Substances 0.000 description 13
- 239000003990 capacitor Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000005030 aluminium foil Substances 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- -1 graphite alkenes Chemical class 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000004080 punching Methods 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical group [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- WNEYXFDRCSFJCU-UHFFFAOYSA-N propan-1-amine;hydrate Chemical compound [OH-].CCC[NH3+] WNEYXFDRCSFJCU-UHFFFAOYSA-N 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- 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
-
- 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
- Y02E60/13—Energy storage using capacitors
Abstract
The present invention provides a kind of preparation methods of porous graphene, include the following steps, after first mixing graphene oxide hydrogel and aqueous slkali, obtain mixture;Then under protective atmosphere, the mixture that above-mentioned steps are obtained obtains porous graphene after Overheating Treatment.The graphene oxide and alkali that the present invention uses low cost is initial feeds, subsequent preparation is carried out based on the graphene oxide hydrogel with 3D pattern, reaction condition is mild, greatly reduce the preparation cost of porous graphene, and hydrogel can absorb aqueous slkali, make mixing more evenly, the more conducively etching and reduction of alkali, effective solution graphene oxide and the dry-mixed non-uniform problem of alkali;And it is easily processed by sample after activation, liquid waste processing is simple, does not pollute to environment, is suitble to large-scale industrial production, has extensive prospects for commercial application.
Description
Technical field
The invention belongs to technical field of graphene, are related to the preparation method more particularly to a kind of use of a kind of porous graphene
In the preparation method and supercapacitor of the porous graphene of supercapacitor.
Background technique
Graphene (Graphene) is a kind of new material of individual layer laminated structure being made of carbon atom.It is one kind by carbon
Atom forms the flat film that hexangle type is in honeycomb lattice, the two-dimensional material of only one carbon atom thickness with sp2 hybridized orbit.
As a kind of two dimensional crystal of only one layer of atomic thickness being made of carbon atom, it is at present into most thin in application field
Material and most tough material;Graphene has huge theoretical specific surface area simultaneously, and physicochemical properties are stablized, can be in senior engineer
Make to keep good structural stability under voltage and high current fast charging and discharging;Graphene also has excellent electric conductivity, can be with
Internal resistance is reduced, the cyclical stability of supercapacitor is improved;In addition, graphene be almost it is fully transparent, only absorb 2.3%
Light.And it is very fine and close, even the smallest gas atom (helium atom) can not also penetrate.These features are very suitable to it
As the raw material of transparent electron product, such as transparent touch display screen, luminescent screen and solar panel.Just because of graphene
With above-mentioned many excellent physical chemical property, in energy storage material, environmental project, sensing sensitive aspect is widely used,
Referred to as " dark fund " or " king of new material ", and potential application prospect is vast, and it is burnt to have become global concern at present
The excellent properties of point and research hotspot, especially graphene are to develop high-performance, multifunctional polymer nanocomposite reality
Great prospect.
Since Geim in 2004 etc. prepares graphene using micromechanics stripping method for the first time, graphene is just because it has height
The excellent performance such as electric conductivity, high-specific surface area, high intensity and high electron mobility, causes the extensive concern of people, in turn
Also promote the fast development of graphene preparation technology.Due to the property such as unique two dimensional crystal structure and excellent photo-thermal power electricity
Matter, graphene show huge potentiality in supercapacitor field.Currently, graphene preparation method has developed many kinds.
Wherein graphite oxide reduction method is the best approach for preparing graphene at present in the potentiality for closely having industrialized production at present
One of.This method is easy to operate, preparation cost is low, can prepare graphene on a large scale, can satisfy large-scale production
Business needs, and the further research and development for graphite alkenes material and its derivative provides effective antecedent basis.
Among these, porous graphene is important in graphite alkenes material one, refers to have on two-dimentional basal plane and receive
The carbon material of meter level hole, porous graphene not only remains the advantageous property of graphene, but also compares inert graphene table
Face, it is various sizes of that the hole that the presence in hole promotes the raising of matter transportation efficiency, especially atomic level can play screening
The effect of ion/molecular.Importantly, the introducing in hole also effectively opens the band gap of graphene, graphene is promoted
In the application of field of electronic devices, thus also become the research hotspot of graphene defect functionalization in recent years.
Although however, disclose the preparation method of the porous graphene of many high-specific surface areas in existing technical literature,
But usually all method is complicated, at high cost, can not be suitable for actual production, when more important is carrying out space application, it is also necessary to again
Secondary to build macroscopical 3D structure, not only difficulty is big, but also will affect the performance of original graphene.
Therefore, the preparation method for how finding a kind of porous graphene, solves the above problems, it has also become many in field to grind
Study carefully personnel and enterprise widely one of focus.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that providing a kind of preparation method of porous graphene, especially
It is a kind of preparation method of microcosmic porous graphene, porous graphene provided by the invention has 3D macro morphology, higher
Specific surface area and lower oxygen content, and preparation that can in a mild condition quickly, inexpensive, it is environmentally protective, it is suitable for industry
Change mass production application.
The present invention provides a kind of preparation methods of porous graphene, comprising the following steps:
A after) mixing graphene oxide hydrogel and aqueous slkali, mixture is obtained;
B) under protective atmosphere, the mixture that above-mentioned steps are obtained obtains porous graphene after Overheating Treatment.
Preferably, the alkali includes potassium hydroxide, sodium hydroxide, concentrated ammonia liquor, urea, sodium carbonate and tetrapropylammonium hydroxide
One of or it is a variety of;
The mass ratio of the graphene oxide hydrogel and the alkali is 1:(4~8).
Preferably, the step A) specifically:
After graphene oxide absorbed aqueous slkali, mixture is obtained;
The concentration of the aqueous slkali is 1~4mol/L.
Preferably, the graphene oxide hydrogel is formed by graphene oxide aqueous dispersion liquid after hydro-thermal reaction
3D shape graphene oxide hydrogel.
Preferably, the concentration of the graphene oxide aqueous dispersion liquid is 8 ‰~9 ‰;
The temperature of the hydro-thermal reaction is 120~180 DEG C;
The time of the hydro-thermal reaction is 12~16h;
It further include rinsing step after the hydro-thermal reaction.
It preferably, further include vacuum drying step after the mixing;
The vacuum drying temperature is 80~120 DEG C.
Preferably, the time of the heat treatment is 45~75min;
The temperature of the heat treatment is 800~900 DEG C;
The heating rate of the heat treatment is 5~15 DEG C/min.
It preferably, further include washing and/or drying steps after the heat treatment;
The mass concentration of the spent pickling acid is 1%~10%.
Preferably, the specific surface area of the porous graphene is 1200~1500m2/g;
The oxygen content of the porous graphene is less than or equal to 0.3%;
In the porous graphene, the ratio of the quantity of micropore and middle hole number is 1:(3~5);
The aperture of the micropore is less than or equal to 2nm;
The aperture of the mesoporous is 2~50nm.
The present invention provides a kind of supercapacitors, which is characterized in that comprising described in above-mentioned technical proposal any one
Porous graphene prepared by preparation method.
The present invention provides a kind of preparation methods of porous graphene, include the following steps, first by graphene oxide water
After gel and aqueous slkali mixing, mixture is obtained;Then under protective atmosphere, the mixture that above-mentioned steps are obtained is through overheating
After processing, porous graphene is obtained.Compared with prior art, the present invention existed for existing porous graphene preparation method
Journey is complicated, problem at high cost;And when carrying out space application, it is also necessary to macroscopical 3D structure is built again, not only difficulty is big, and
And it also will affect the defect of the performance of original graphene;And graphene directly prepares 3D carbon material, and is generally faced with and is difficult to advise
The problems such as modelling preparation, higher cost.
The graphene oxide for using low cost and alkali of the invention is initial feeds, with the oxidation with 3D pattern
Subsequent preparation is carried out based on graphene hydrogel, reaction condition is mild, greatly reduces the preparation cost of porous graphene, more
Important is hydrogels can absorb aqueous slkali, makes mixing more evenly, the more conducively etching and reduction of alkali, effective solution oxygen
Graphite alkene and the dry-mixed non-uniform problem of alkali;And it is easily processed by sample after activation, liquid waste processing is simple, not to environment
It pollutes, is very suitable to large-scale industrial production, there is extensive prospects for commercial application.
The experimental results showed that porous graphene specific surface area prepared by the present invention reaches 1500m2/ g, oxygen content be less than etc.
In 3%, the button capacitor prepared using commercialized preparation method, capacitor can reach 31.5F/g.
Detailed description of the invention
Fig. 1 is the appearance photo of 3D porous graphene prepared by the embodiment of the present invention 1;
Fig. 2 is the nitrogen adsorption desorption curve graph of 3D porous graphene prepared by the embodiment of the present invention 1;
Fig. 3 is the graph of pore diameter distribution of 3D porous graphene prepared by the embodiment of the present invention 1;
Fig. 4 is the SEM scanning electron microscope (SEM) photograph of porous graphene prepared by the embodiment of the present invention 1;
Fig. 5 is the specific capacitance cyclic curve figure of button capacitor prepared by the embodiment of the present invention 1.
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described below with reference to embodiment, still
It should be appreciated that these descriptions are intended merely to further illustrate the features and advantages of the present invention, rather than to invention claim
Limitation.
All raw materials of the present invention, are not particularly limited its source, buying on the market or according to those skilled in the art
The preparation of conventional method known to member.
All raw materials of the present invention, are not particularly limited its purity, and present invention preferably employs analyze the preparation of pure or graphene
The purity requirement of field routine.
All raw materials of the present invention, the trade mark and abbreviation belong to this field routine trade mark and abbreviation, each trade mark and abbreviation
In the field of its associated uses be it is explicit, those skilled in the art according to the trade mark, abbreviation and corresponding purposes,
It can be commercially available from city's mid-sales or conventional method is prepared.
The present invention provides a kind of preparation methods of porous graphene, comprising the following steps:
A after) mixing graphene oxide hydrogel and aqueous slkali, mixture is obtained;
B) under protective atmosphere, the mixture that above-mentioned steps are obtained obtains porous graphene after Overheating Treatment.
After the present invention first mixes graphene oxide hydrogel and aqueous slkali, mixture is obtained.
The specific pattern of the graphene oxide hydrogel is not particularly limited in the present invention, ripe with those skilled in the art
The conventional structure and pattern for the graphene oxide hydrogel known, those skilled in the art can according to practical situations,
Raw material condition and product requirement are selected and are adjusted, and graphene oxide hydrogel of the present invention is preferably three macroscopically
Material is tieed up, the graphene oxide hydrogel is preferably 3D material, can have the pattern of specific three dimensional.
The source of the graphene oxide hydrogel is not particularly limited in the present invention, with well known to those skilled in the art
Prepared by the preparation method of graphene oxide hydrogel or commercially available purchase, those skilled in the art can be according to actual production feelings
Condition, raw material condition and product requirement are selected and are adjusted, and graphene oxide hydrogel of the present invention is preferably by oxidation stone
Black alkene aqueous dispersion liquid (aqueous solution) forms graphene oxide hydrogel, i.e. 3D shape graphene oxide water after hydro-thermal reaction
Gel.
The parameter of the graphene oxide aqueous dispersion liquid is not particularly limited in the present invention, ripe with those skilled in the art
The conventional parameter for the graphene oxide water solution known, those skilled in the art can be according to practical conditions, raw material feelings
Condition and product requirement are selected and are adjusted, and the present invention is to further increase the specific surface area and electrical property of subsequent product, institute
The concentration for stating graphene oxide aqueous dispersion liquid is preferably 8 ‰~9 ‰, more preferably 8.2 ‰~8.8 ‰, more preferably 8.4 ‰
~8.6 ‰.
The parameter of the hydro-thermal reaction is not particularly limited in the present invention, with preparation well known to those skilled in the art oxidation
The conventional parameter of graphene hydrogel, those skilled in the art can be according to practical condition, raw material condition and productions
Product require to be selected and adjusted, and the temperature of hydro-thermal reaction of the present invention is preferably 120~180 DEG C, more preferably 130~
170 DEG C, more preferably 140~160 DEG C.The time of the hydro-thermal reaction is preferably 12~16h, more preferable 13~15h, more preferably
For 13.5~14.5h.
The present invention is to improve the practicability of preparation method, complete process route, and it is also preferable to include leaching after the hydro-thermal reaction
Wash step.The design parameter of the rinsing step is not particularly limited in the present invention, and those skilled in the art can be according to reality
The condition of production, product requirement and quality requirement are selected and are adjusted, elution of the present invention preferably repeatedly elution.
The selection of the alkali is not particularly limited in the present invention, with well known to those skilled in the art for etching and restoring
Graphene oxide routinely use alkali, those skilled in the art can be according to practical condition, product requirement and quality
It is required that selected and adjusted, alkali of the present invention preferably include potassium hydroxide, sodium hydroxide, concentrated ammonia liquor, urea, sodium carbonate and
One of tetrapropylammonium hydroxide is a variety of, more preferably potassium hydroxide, sodium hydroxide, concentrated ammonia liquor, urea, sodium carbonate or four
Propyl ammonium hydroxide, most preferably potassium hydroxide.
The concentration of the aqueous slkali is not particularly limited in the present invention, with the normal of aqueous slkali well known to those skilled in the art
Advise parameter, those skilled in the art can be selected according to practical condition, raw material condition and product requirement and
Adjustment, the present invention is to further increase the effect of etching and reduction, guarantees the specific surface area and electrical property of subsequent product, the alkali
The concentration of solution is preferably 1~4mol/L, more preferably 1.5~3.5mol/L, more preferably 2~3mol/L.
The dosage of the alkali is not particularly limited in the present invention, those skilled in the art can according to practical condition,
Raw material condition and product requirement are selected and are adjusted, and the present invention is to further increase the effect of etching and reduction, after guarantee
The mass ratio of the specific surface area and electrical property of continuous product, the graphene oxide hydrogel and the alkali is preferably 1:(4~8),
More preferably 1:(4.5~7.5), more preferably 1:(5~7), more preferably 1:(5.5~6.5).
The mixed mode is not particularly limited in the present invention, and those skilled in the art can be according to actual production feelings
Condition, product requirement and quality requirement are selected and are adjusted, and the present invention is to further increase the effect of etching and reduction, are guaranteed
The specific surface area and electrical property of subsequent product, the mixed mode preferably impregnate, i.e., the described step A) be particularly preferred as by
After graphene oxide absorbed aqueous slkali, mixture is obtained, the specific can be that graphene oxide hydrogel is dipped in alkali
After absorbing in solution, mixture is obtained.
The present invention is to improve the practicability of preparation method, and complete process route, it is dry that it is also preferable to include vacuum after the mixing
Dry step.The design parameter of the vacuum drying step is not particularly limited in the present invention, and those skilled in the art can basis
Practical condition, product requirement and quality requirement are selected and are adjusted, and vacuum drying temperature of the present invention is preferred
It is 80~120 DEG C, more preferably 85~115 DEG C, more preferably 90~110 DEG C, is specifically as follows 120 DEG C.
Then under protective atmosphere, the mixture that above-mentioned steps are obtained obtains porous the present invention after Overheating Treatment
Graphene.
The design parameter of the heat treatment is not particularly limited in the present invention, with similar side well known to those skilled in the art
The conventional parameter of method thermal reduction processing, those skilled in the art can be according to practical condition, product requirement and matter
Amount requires to be selected and adjusted, and the time of heat treatment of the present invention is preferably 45~75min, more preferably 50~70min,
More preferably 55~65min, most preferably 60min.The temperature of the heat treatment is preferably 800~900 DEG C, more preferably 820
~880 DEG C, more preferably 840~860 DEG C, are specifically as follows 800 DEG C.The heating rate of the heat treatment is preferably 5~15 DEG C/
Min, more preferably 7~13 DEG C/min, more preferably 9~11 DEG C/min, are specifically as follows 10 DEG C/min.
The present invention is to improve the practicability of preparation method, and complete process route, it is also preferable to include washings after the heat treatment
And/or drying steps.The washing and/or dry detailed process is not particularly limited in the present invention, those skilled in the art
It can be selected and be adjusted according to practical condition, product requirement and quality requirement, it is of the present invention to wash and/or do
It is dry to be preferably a step washing and drying steps, more preferably washing and/or pickling, re-dry, more preferably successively washed,
Pickling and suction filtration washing, re-dry.The mass concentration of spent pickling acid of the present invention is preferably 1%~10%, and more preferably 3%
~8%, more preferably 5%~6%.
Porous graphene has been prepared by above-mentioned steps in the present invention, especially with the microcosmic porous graphite of 3D pattern
Alkene, the specific surface area of porous graphene of the present invention are preferably 1200~1500m2/ g, more preferably 1250~1450m2/ g,
More preferably 1300~1400m2/g.The oxygen content of the porous graphene can be less than or equal to 0.3%, more preferably less than or equal to
0.25%, more preferably less than or equal to 0.2%.
Micropore and mesoporous are preferably comprised in porous graphene of the present invention.The quantity of micropore of the present invention and middle hole count
The ratio of amount is preferably 1:(3~5), more preferably 1:(3.3~4.7), more preferably 1:(3.5~4.5), more preferably 1:
(3.7~4.3).The aperture of micropore of the present invention is preferably smaller than equal to 2nm, more preferably less than or equal to 1.8nm, more preferably less than
Equal to 1.5nm.The aperture of mesoporous of the present invention is preferably 2~50nm, more preferably 5~45nm, more preferably 10~40nm,
More preferably 20~30nm.
The present invention also provides a kind of supercapacitors, preparation-obtained made comprising above-mentioned technical proposal any one
Standby porous graphene.
The structure and composition of the supercapacitor is not particularly limited in the present invention, with well known to those skilled in the art
The conventional structure and composition of supercapacitor, those skilled in the art can according to practical condition, raw material condition with
And product requirement is selected and is adjusted.
The preparation method for the porous graphene that above-mentioned steps of the present invention provide, using the graphene oxide and KOH of low cost
For initial feed, freeze-dried formed of graphene oxide is had into 3D pattern hydrogel, low energy consumption is easy prepare with scale, then
Subsequent preparation is carried out based on this, and reaction condition is mild, greatly reduces the preparation cost of porous graphene, and hydrogel
KOH solution can be absorbed, makes mixing more evenly, more conducively KOH etching and reduction, effective solution graphene oxide and hydrogen-oxygen
Change the dry-mixed non-uniform problem of potassium;And it is easily processed by sample after activation, liquid waste processing is simple, does not cause dirt to environment
Dye, is very suitable to large-scale industrial production, has extensive prospects for commercial application.
And graphene oxide hydrogel is prepared by hydro-thermal method using graphene oxide as raw material in the present invention, then leads to
It crosses alkali activation high-temperature process and porous graphene is prepared, before being compared by porous graphene specific surface area prepared by the method
It is enhanced, activates, carbonization improves the compacted density of graphene, effective solution graphene volume energy density
Low disadvantage.
The experimental results showed that porous graphene specific surface area prepared by the present invention reaches 1500m2/ g, oxygen content be less than etc.
In 3%, the button capacitor prepared using commercialized preparation method, capacitor can reach 31.5F/g.
In order to further illustrate the present invention, with reference to embodiments to a kind of preparation of porous graphene provided by the invention
Method is described in detail, but it is to be understood that and these embodiments are to be implemented under the premise of the technical scheme of the present invention,
The detailed implementation method and specific operation process are given, only to further illustrate the features and advantages of the present invention, without
It is limiting to the claimed invention, protection scope of the present invention is also not necessarily limited to following embodiments.
Embodiment 1
The preparation of hydrogel: the graphene oxide solution that 100ml concentration is 8mg/ml is ultrasonically treated 0.5h, is packed into
In the water heating kettle of 200ml, 16h is reacted under conditions of 180 DEG C, reaction end is eluted 3 times with pure water, obtains 3D graphene oxide water
Gel.(EDS indicates that C content is 75%)
Alkaline soak: the hydrogel of synthesis is dipped into the 200mlKOH aqueous solution of 2M, and it is extra that processing is removed for 24 hours
KOH aqueous solution is dried in vacuo for 24 hours at 120 DEG C.
The activation of carbon alkali mixture: the sample after drying is put into nickel pot, is sent into high-temperature process in tube furnace, N2Atmosphere
Under, 800 DEG C are risen to the rate of 10 DEG C/min, and reaction 1h is kept at 800 DEG C;Gained sample is washed, pickling: water
Ph7~8 are washed till, pickling stirs 2h in 5% HCl, and in filtering and washing to neutrality, it is more that 120 DEG C of vacuum drying obtain 3D for 24 hours
Hole graphene.
It is the appearance photo of 3D porous graphene prepared by the embodiment of the present invention 1 referring to Fig. 1, Fig. 1.
The 3D porous graphene prepared to the embodiment of the present invention 1 characterizes.
Referring to fig. 2, Fig. 2 is the nitrogen adsorption desorption curve graph of 3D porous graphene prepared by the embodiment of the present invention 1.
As shown in Figure 2, N2Adsorption desorption curve exist more apparent lag loop, illustrate prepared by the present invention porous
There are a large amount of mesoporous for graphene.
It is the graph of pore diameter distribution of 3D porous graphene prepared by the embodiment of the present invention 1 referring to Fig. 3, Fig. 3.
From the figure 3, it may be seen that the distribution in aperture, is distributed at mesoporous more, this is corresponding with our subsequent BET results, mesoporous
Presence improve the specific surface area and specific capacity of graphene.
EDS detection and BET detection are carried out to porous graphene prepared by the embodiment of the present invention 1.
Referring to table 1, table 1 is graphene oxide raw material, 3D graphene oxide hydrogel and the 3D in the embodiment of the present invention
The EDS energy spectrum analysis data of porous graphene.
Table 1
Referring to table 2, table 2 is the BET testing result of porous graphene prepared by the embodiment of the present invention 1.Table 2
As shown in Table 2, BET shows that the specific surface area of sample is 1517.49m2/g。
The porous graphene prepared to the embodiment of the present invention 1 characterizes.
Referring to fig. 4, Fig. 4 is the SEM scanning electron microscope (SEM) photograph of porous graphene prepared by the embodiment of the present invention 1.
As shown in Figure 4, it is activated by alkali, after handling our hydrogel, there are certain pleats for graphene surface
Wrinkle (a) and hole (b), increases the specific surface area of graphene, provides more active sites to subsequent electrolyte.
Performance detection is carried out to porous graphene prepared by the embodiment of the present invention 1.
Supercapacitor is prepared using porous graphene prepared by the embodiment of the present invention 1, briefly steps are as follows:
This active carbon is mixed into homogenate with CMC with binder SBR, is uniformly coated on aluminium foil, through drying, is rolled, punching
After be assembled into button capacitor (organic system, 2.7V).
The supercapacitor prepared to the embodiment of the present invention 1 detects, the results showed that, quality specific capacitance is 31.5F/g.
It is the specific capacitance cyclic curve figure of button capacitor prepared by the embodiment of the present invention 1 referring to Fig. 5, Fig. 5.
As shown in Figure 5, the embodiment of the present invention 1 prepare button capacitor 10000 times circulation after, specific capacitance conservation rate according to
78% can so be reached.
Embodiment 2
The preparation of hydrogel: the graphene oxide solution that 100ml concentration is 8mg/ml is ultrasonically treated 0.5h, is packed into
In the water heating kettle of 200ml, 16h is reacted under conditions of 180 DEG C, reaction end is eluted 3 times with pure water.(EDS indicates that C content is
75%)
Alkaline soak: the hydrogel of synthesis is dipped into the 200mlKOH aqueous solution of 3M, and it is extra that processing is removed for 24 hours
KOH aqueous solution is dried in vacuo for 24 hours at 120 DEG C.
The activation of carbon alkali mixture: the sample after drying is put into nickel pot, is sent into high-temperature process in tube furnace, N2Atmosphere
Under, 800 DEG C are risen to the rate of 10 DEG C/min, and reaction 1h is kept at 800 DEG C;Gained sample is washed, pickling: water
It is washed till ph7-8, pickling stirs 2h in 5% HCl, and in filtering and washing to neutrality, it is more that 120 DEG C of vacuum drying obtain 3D for 24 hours
Hole graphene.
BET detection is carried out to porous graphene prepared by the embodiment of the present invention 2, the results showed that, BET shows the ratio table of sample
Area is 1375.56m2/g。
Supercapacitor is prepared using porous graphene prepared by the embodiment of the present invention 2, briefly steps are as follows:
This active carbon is mixed into homogenate with CMC with binder SBR, is uniformly coated on aluminium foil, through drying, is rolled, punching
After be assembled into button capacitor (organic system, 2.7V).
The supercapacitor prepared to the embodiment of the present invention 2 detects, the results showed that, quality specific capacitance is 28.7F/g.
Embodiment 3
The preparation of hydrogel: the graphene oxide solution that 100ml concentration is 8mg/ml is ultrasonically treated 0.5h, is packed into
In the water heating kettle of 200ml, 16h is reacted under conditions of 180 DEG C, reaction end is eluted 3 times with pure water.(EDS indicates that C content is
75%)
Alkaline soak: the hydrogel of synthesis is dipped into the 200mlKOH aqueous solution of 3M, and it is extra that processing is removed for 24 hours
KOH aqueous solution is dried in vacuo for 24 hours at 120 DEG C.
The activation of carbon alkali mixture: the sample after drying is put into nickel pot, is sent into high-temperature process in tube furnace, N2Atmosphere
Under, 800 DEG C are risen to the rate of 10 DEG C/min, and reaction 1h is kept at 800 DEG C;Gained sample is washed, pickling: water
Ph7~8 are washed till, pickling stirs 2h in 5% HCl, and in filtering and washing to neutrality, 120 DEG C of vacuum drying obtain sample for 24 hours
Product.
BET detection is carried out to porous graphene prepared by the embodiment of the present invention 3, the results showed that, BET shows the ratio table of sample
Area is 1296.13m2/g。
Supercapacitor is prepared using porous graphene prepared by the embodiment of the present invention 3, briefly steps are as follows:
This active carbon is mixed into homogenate with CMC with binder SBR, is uniformly coated on aluminium foil, through drying, is rolled, punching
After be assembled into button capacitor (organic system, 2.7V).
The supercapacitor prepared to the embodiment of the present invention 3 detects, the results showed that, quality specific capacitance is 29.20F/
g。
Above to a kind of preparation method and super capacitor of the porous graphene for supercapacitor provided by the invention
Device is described in detail, and used herein a specific example illustrates the principle and implementation of the invention, with
The explanation of upper embodiment is merely used to help understand method and its core concept of the invention, including best mode, and also makes
The present invention, including any device or system of manufacture and use can be practiced by obtaining any person skilled in the art, and implement to appoint
The method what is combined.It should be pointed out that for those skilled in the art, before not departing from the principle of the invention
It puts, can be with several improvements and modifications are made to the present invention, these improvement and modification also fall into the guarantor of the claims in the present invention
It protects in range.The range of the invention patent protection is defined by the claims, and may include that those skilled in the art can think
The other embodiments arrived.If these other embodiments have the structural element for being not different from claim character express, or
If person they include equivalent structural elements with the character express of claim without essence difference, these other embodiments
It should also be included in the scope of the claims.
Claims (10)
1. a kind of preparation method of porous graphene, which comprises the following steps:
A after) mixing graphene oxide hydrogel and aqueous slkali, mixture is obtained;
B) under protective atmosphere, the mixture that above-mentioned steps are obtained obtains porous graphene after Overheating Treatment.
2. preparation method according to claim 1, which is characterized in that the alkali includes potassium hydroxide, sodium hydroxide, dense ammonia
One of water, urea, sodium carbonate and tetrapropylammonium hydroxide are a variety of;
The mass ratio of the graphene oxide hydrogel and the alkali is 1:(4~8).
3. preparation method according to claim 1, which is characterized in that the step A) specifically:
After graphene oxide absorbed aqueous slkali, mixture is obtained;
The concentration of the aqueous slkali is 1~4mol/L.
4. preparation method according to claim 1, which is characterized in that the graphene oxide hydrogel is by graphene oxide
Aqueous dispersion liquid forms 3D shape graphene oxide hydrogel after hydro-thermal reaction.
5. the preparation method according to claim 4, which is characterized in that the concentration of the graphene oxide aqueous dispersion liquid is
8 ‰~9 ‰;
The temperature of the hydro-thermal reaction is 120~180 DEG C;
The time of the hydro-thermal reaction is 12~16h;
It further include rinsing step after the hydro-thermal reaction.
6. preparation method according to claim 1, which is characterized in that further include vacuum drying step after the mixing;
The vacuum drying temperature is 80~120 DEG C.
7. preparation method according to claim 1, which is characterized in that the time of the heat treatment is 45~75min;
The temperature of the heat treatment is 800~900 DEG C;
The heating rate of the heat treatment is 5~15 DEG C/min.
8. preparation method according to claim 1, which is characterized in that further include washing and/or drying after the heat treatment
Step;
The mass concentration of the spent pickling acid is 1%~10%.
9. preparation method according to claim 1, which is characterized in that the specific surface area of the porous graphene be 1200~
1500m2/g;
The oxygen content of the porous graphene is less than or equal to 0.3%;
In the porous graphene, the ratio of the quantity of micropore and middle hole number is 1:(3~5);
The aperture of the micropore is less than or equal to 2nm;
The aperture of the mesoporous is 2~50nm.
10. a kind of supercapacitor, which is characterized in that comprising prepared by preparation method described in any one of claim 1 to 9
Porous graphene.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810273067.0A CN110316723A (en) | 2018-03-29 | 2018-03-29 | A kind of preparation method and supercapacitor of the porous graphene for supercapacitor |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810273067.0A CN110316723A (en) | 2018-03-29 | 2018-03-29 | A kind of preparation method and supercapacitor of the porous graphene for supercapacitor |
Publications (1)
Publication Number | Publication Date |
---|---|
CN110316723A true CN110316723A (en) | 2019-10-11 |
Family
ID=68110983
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810273067.0A Pending CN110316723A (en) | 2018-03-29 | 2018-03-29 | A kind of preparation method and supercapacitor of the porous graphene for supercapacitor |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN110316723A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112599366A (en) * | 2020-11-24 | 2021-04-02 | 张茜茜 | TiO22Nano flower loaded nitrogen-doped graphene supercapacitor material and preparation method thereof |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101941693A (en) * | 2010-08-25 | 2011-01-12 | 北京理工大学 | Graphene aerogel and preparation method thereof |
CN102730680A (en) * | 2012-07-23 | 2012-10-17 | 清华大学深圳研究生院 | High-density high-rigidity graphene porous carbon material as well as preparation method and applications thereof |
CN102887508A (en) * | 2012-09-28 | 2013-01-23 | 上海理工大学 | Method for preparing high-strength graphite oxide aerogel |
CN102923698A (en) * | 2012-11-19 | 2013-02-13 | 中南大学 | Preparation method for three-dimensional porous graphene for supercapacitor |
WO2016037565A1 (en) * | 2014-09-11 | 2016-03-17 | 中国科学院上海应用物理研究所 | Graphene hydrogel and graphene aerogel as well as preparation methods therefor and applications thereof |
CN105858648A (en) * | 2016-05-23 | 2016-08-17 | 北京光科博冶科技有限责任公司 | Preparation method of environment-friendly and energy-saving graphene and obtained product |
US20170309365A1 (en) * | 2014-10-22 | 2017-10-26 | Fuzhou University | Compressive graphene hydrogel and preparation method therefor |
-
2018
- 2018-03-29 CN CN201810273067.0A patent/CN110316723A/en active Pending
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101941693A (en) * | 2010-08-25 | 2011-01-12 | 北京理工大学 | Graphene aerogel and preparation method thereof |
CN102730680A (en) * | 2012-07-23 | 2012-10-17 | 清华大学深圳研究生院 | High-density high-rigidity graphene porous carbon material as well as preparation method and applications thereof |
CN102887508A (en) * | 2012-09-28 | 2013-01-23 | 上海理工大学 | Method for preparing high-strength graphite oxide aerogel |
CN102923698A (en) * | 2012-11-19 | 2013-02-13 | 中南大学 | Preparation method for three-dimensional porous graphene for supercapacitor |
WO2016037565A1 (en) * | 2014-09-11 | 2016-03-17 | 中国科学院上海应用物理研究所 | Graphene hydrogel and graphene aerogel as well as preparation methods therefor and applications thereof |
US20170309365A1 (en) * | 2014-10-22 | 2017-10-26 | Fuzhou University | Compressive graphene hydrogel and preparation method therefor |
CN105858648A (en) * | 2016-05-23 | 2016-08-17 | 北京光科博冶科技有限责任公司 | Preparation method of environment-friendly and energy-saving graphene and obtained product |
Non-Patent Citations (2)
Title |
---|
刘雷英等: "石墨烯三维多孔凝胶在超级电容器中的应用研究", 《陕西理工学院学报(自然科学版)》 * |
李萍等: "活性石墨烯的制备及其电化学电容特性的研究", 《沈阳理工大学学报》 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112599366A (en) * | 2020-11-24 | 2021-04-02 | 张茜茜 | TiO22Nano flower loaded nitrogen-doped graphene supercapacitor material and preparation method thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN106966386B (en) | A kind of preparation method and applications of graphene film vertical orientation thin-film material | |
CN105780364B (en) | A kind of method for preparing ultramicropore flexibility carbon cloth and products thereof and application | |
Zhu et al. | Recycling PM2. 5 carbon nanoparticles generated by diesel vehicles for supercapacitors and oxygen reduction reaction | |
CN106783197B (en) | A kind of ZIF-8 pyrolysis porous carbon-graphene composite material and its preparation method and application | |
Hu et al. | Nitrogen-doped mesoporous carbon thin film for binder-free supercapacitor | |
CN105883906B (en) | A kind of nano-stannic oxide and graphene composite material and preparation method and application | |
CN105148744A (en) | Adjustable and controllable ultrathin two-dimensional nano g-C3N4 film, and preparation method and application thereof | |
CN109360740B (en) | Two-dimensional nitrogen-doped porous carbon nanosheet and preparation method thereof | |
CN104045077A (en) | Graphene three-dimensional hierarchical porous carbon material and preparation method thereof | |
CN103833032A (en) | Graphene-based composite cathode material | |
CN106517133B (en) | Ultra-thin layer of charcoal of nitrating three-dimensional co-continuous porous structure and its preparation method and application | |
Qin et al. | Alginate-derived porous carbon obtained by nano-ZnO hard template-induced ZnCl2-activation method for enhanced electrochemical performance | |
CN107265443B (en) | One kind is with SiO2-NH2The method for preparing nitrogen-doped graphene aeroge as template and nitrogen dopant simultaneously | |
CN110416548A (en) | A kind of preparation method and applications of the two-dimensional structure of N doping porous carbon | |
Wei et al. | Electrosorption of toxic heavy metal ions by mono S-or N-doped and S, N-codoped 3D graphene aerogels | |
Al-Enizi et al. | Carbon quantum dots (CQDs)/Ce doped NiO nanocomposite for high performance supercapacitor | |
CN109860526A (en) | The preparation method of graphite type material doping metals oxalates lithium battery composite negative pole material | |
CN103762356B (en) | Ni nano wire, NiO/Ni self-supported membrane and its preparation method and application | |
Liu et al. | Enhanced supercapacitor performance of Bi2O3 by Mn doping | |
CN107954420A (en) | A kind of Anodic peels off the method that graphite prepares three-dimensional grapheme | |
Wei et al. | Transition metal oxide hierarchical nanotubes for energy applications | |
Shan et al. | Wood-based hierarchical porous nitrogen-doped carbon/manganese dioxide composite electrode materials for high-rate supercapacitor | |
CN105692585A (en) | Carbon nanomaterial containing graphene structure as well as preparation method and application of carbon nanomaterial | |
Kang et al. | Binder-free and flexible carbon-encapsulated oxygen-vacancy cerium dioxide electrode for high-performance supercapacitor | |
CN110316723A (en) | A kind of preparation method and supercapacitor of the porous graphene for supercapacitor |
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 | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20191011 |