CN108190873B - Equipment and method for preparing graphene and graphene prepared by equipment and method - Google Patents
Equipment and method for preparing graphene and graphene prepared by equipment and method Download PDFInfo
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- CN108190873B CN108190873B CN201711181994.1A CN201711181994A CN108190873B CN 108190873 B CN108190873 B CN 108190873B CN 201711181994 A CN201711181994 A CN 201711181994A CN 108190873 B CN108190873 B CN 108190873B
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Abstract
The equipment of preparation graphite alkene, including jar body and the support of fixed connection in jar body bottom, the bottom of jar body is equipped with the through-hole, still includes working electrode base, glass pipe, the glass pipe with be equipped with porous separator between the contact surface of working electrode board, graphite is arranged in the bottom of glass pipe and with porous separator and the contact of working electrode base, the top of graphite is equipped with glass fiber filtration membrane, glass fiber filtration membrane's upper surface is equipped with and stretches into through the through-hole the inside gravity squeezer of glass pipe, equipment still includes reference electrode and counter electrode. The method for preparing the graphene by using the equipment comprises the steps of placing graphite particles, extruding the graphite particles and connecting constant-voltage current, and the graphene is prepared by the method. The invention improves the production safety, and has environmental protection and popularization.
Description
Technical Field
The invention relates to the technical field of graphene preparation, in particular to equipment for preparing graphene, a method for preparing graphene by using the equipment and the graphene prepared by the method.
Background
Graphene, as a novel two-dimensional nanomaterial, is the lightest, thinnest and hardest nanomaterial discovered to date, and its excellent electrical properties determine its potential applications. The application fields of the electrode comprise a transparent electrode, a lithium battery, a sewage treatment film and the like. As the world's demand for emerging nanomaterials continues to increase, the yield and production capacity of graphene also increases year by year. However, the synthesis conditions adopted by the current main Top-down synthesis method inevitably use strong acid, high temperature, high pressure and other reaction conditions, for example, the traditional large-scale production method of graphene all comprises the use of explosive substances of potassium permanganate and strong acid, the substances and the severe reaction conditions not only have high potential safety hazard in large-scale production reaction, but also provide a very high problem for the treatment of the solution after the reaction under the large background of increasingly high requirements on environmental protection in the current Chinese society, and have serious environmental pollution problems.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, provides equipment for preparing graphene by adopting a constant-pressure electrochemical method to help graphite to be tightly stacked and effectively contacted in a reaction, uses a small amount of strong acid in a production process, and eliminates the use of explosive potassium permanganate, and also provides a method for preparing graphene by adopting the equipment, which is environment-friendly and popularized.
In order to solve the technical problems, the invention solves the problems by the following technical scheme:
the equipment of preparation graphite alkene, including jar body and the support of fixed connection in jar body bottom, the bottom of jar body is equipped with the through-hole, still including the working electrode basement of locating the support bottom, pass through-hole and the glass pipe of vertical fixation setting on the working electrode basement, the glass pipe with be equipped with porous separator between the contact surface of working electrode board, graphite is arranged in the bottom of glass pipe and with porous separator and the contact of working electrode basement, the top of graphite is equipped with glass fiber filtration membrane, glass fiber filtration membrane's upper surface is equipped with and stretches into through the through-hole the inside gravity squeezer of glass pipe, equipment still includes reference electrode and counter electrode, the reference electrode inserts to the bottom through gravity squeezer top, the counter electrode with the gravity squeezer is connected.
Specifically, a sealing film is further arranged between the glass tube and the working electrode substrate, an opening used for the porous separator to contact with the working electrode substrate is formed in the sealing film, and a cavity is formed in the surface, contacting with the glass fiber filter, below the gravity squeezer.
Specifically, the gravity squeezer includes the pipe that stretches into the glass pipe, sets up the stripper plate in the pipe bottom and sets up the backup pad at the pipe top, be equipped with the weight that is used for fixed reference electrode's through-hole and is used for exerting pressure in the backup pad.
Specifically, the working electrode substrate is made of a titanium material.
Specifically, the tank body is made of polyimide material, and the glass tube is made of epoxy resin material.
Based on the same concept, the invention also provides a method for preparing graphene by adopting the equipment for preparing graphene, which comprises the following steps:
s1: placing graphite particles at the bottom of a glass tube above the working electrode substrate and below a gravity press;
s2: pressing the graphite particles proximate to the working electrode substrate by applying gravity to a support plate on a gravity press;
s3: adding a water-soluble acid electrolyte into the empty pipe to immerse the graphite particles;
s4: gravity compression of the graphite material during the application of a constant current to the working electrode substrate and counter electrode and maintenance of the reaction.
Specifically, the aqueous acidic electrolyte mainly comprises perchloric acid, sulfuric acid, nitric acid, phosphoric acid and other inorganic acids.
Specifically, the density of the constant current is 7.5-30mA/cm2。
Specifically, the step S1 is preceded by a step of cleaning the working electrode substrate, in which the working electrode substrate is subjected to ultrasonic treatment in acetone for 10 minutes to wash off surface grease, then immersed in ethanol for two minutes, and finally rinsed with ultrapure water for several times.
Based on the same conception, the invention also provides graphene prepared by the equipment and the method, the surface resistance value of the graphene is 1000 omega/cm, and organic functional groups are arranged among the graphene.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the invention provides equipment for preparing graphene and a method for preparing graphene by the equipment, which get rid of the limitation and obstacle in the traditional chemical method graphene synthesis process, complete the stripping of graphite materials by an electrochemical mechanism and produce high-quality graphene. The method ensures the control of the reaction constant-pressure oxidation process by controlling the state research in the reaction of the graphite filter cake film, so that the reaction is fully performed, the electrolyte after the reaction is recycled and reused, the generation of reaction waste liquid is further reduced, the influence of a solvent used in the reaction on the environment is reduced to the minimum, the equipment and the method have high production possibility of enlarging the scale, the requirement on the graphene material is expanded at present, and the graphene material has the effect of great weight and the influence of profound significance to the modern society with enhanced environmental protection consciousness, and the prepared graphene has low resistance and high bonding performance with organic materials.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
Fig. 1 is a schematic cross-sectional structure diagram of an apparatus for preparing graphene according to the present invention.
Fig. 2 is a linear voltammetry scan graph in the graphene preparation method of the present invention.
Fig. 3 is a schematic structural view of the graphene film manufactured by the present invention under an electron microscope.
Fig. 4 is a XRD characteristic spectrum diagram of the graphene film product manufactured under different voltage intensity conditions according to the present invention.
FIG. 5 is a FTIR characteristic spectrum diagram of graphene film products manufactured under different voltage intensity conditions according to the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
As shown in fig. 1 to 5, an apparatus for preparing graphene according to the present invention is printed by a 3D printer, and is made of a semitransparent 1.75mm ABS plastic, the tank 1 is made of a polyimide material, the tank 1 is first disposed on a working electrode substrate 3 through a bracket 2, a glass tube 4 is inserted into a through hole and fixed on the working electrode substrate 3 by using a clamp, a sealing film (not marked in the figures) is used to seal the space between the glass tube 4 and the working electrode substrate 3, and an opening is cut in the sealing film, the porous separator 5 is first placed at the bottom of the glass tube 4, and when graphite particles are poured into the glass tube 4 and uniformly distributed in an area at the lower part of the glass tube 4, the graphite particles are fully contacted with the working electrode substrate 3 through the porous separator 5 because the bottom of the glass tube 4 is provided with an opening.
The glass fiber filtering membrane 6 is made into the shape of the glass tube 4 and is placed on the top of graphite particles, the gravity squeezer 7 extends into the glass tube 4 through the through hole 101, the bottom of the gravity squeezer is in contact with the glass fiber filtering membrane 6, a weight 8 for applying pressure is arranged on the top of the gravity squeezer, the graphite particles on the bottom of the glass tube 4 are pressurized, and gas inside the glass tube 4 and contact among the graphite particles can be effectively removed.
The surface of the lower part of the gravity squeezer 7, which is in contact with the glass fiber filter 6, is provided with a cavity which can promote the free movement of electrolyte and generated gas.
The reference electrode 9 is inserted into the bottom through the top of the gravity squeezer 9 for electrolysis, the counter electrode 10 is connected with the gravity squeezer 7, the counter electrode 10 is connected to a constant voltmeter, and the voltage in work is always kept stable.
The specific implementation process of the invention is as follows: firstly, before reaction, the working electrode substrate 1 is subjected to ultrasonic treatment in acetone for ten minutes, surface grease is washed off, then the substrate is immersed in ethanol for two minutes, finally the substrate is washed with ultrapure water for several times, the working electrode, the counter electrode 10 and the reference electrode 9 are connected to a constant voltage power supply, then an ammonium sulfate and sulfuric acid solution electrolyte is poured into the glass tube 4, and pressure is applied through a gravity squeezer 7 to enable graphite particles to be separated from a graphite bed, so that graphene is prepared.
The switch of the constant voltage power supply is turned on, three different current intensities are tested, and the three currents are distinguished according to the intensities and respectively: high-intensity current (21.55mA, the current density can be converted into 30mA/cm2 according to the bed area of graphite), medium-intensity current (10.77mA, the current density can be converted into 15mA/cm2 according to the bed area of graphite), low-intensity current (5.39mA, the current density can be converted into 7.5mA/cm2 according to the bed area of graphite), experimental time in the test is 80000 seconds (if no special description exists), 145100 (extension time), and corresponding linear voltammetry scanning curves are obtained as shown in FIG. 2.
Experiments show that graphene with less oxidizability can be generated under high-intensity current, and graphene can be more effectively oxidized under low-intensity current. Therefore, the electrochemical stripping method can effectively adjust the oxidation degree of the graphene.
After the reaction is finished, the instrument link lines are disconnected in sequence, the weights are taken down, and the electrolyte is poured out. Taking off the graphite product in the glass tube for analysis, firstly purifying the graphite product, including filtering the graphite product by using a vacuum filtration method. The filtration membrane used was a PVDF semipermeable membrane having a pore size of 0.1. mu.m. Before filtration, the semipermeable membrane needs to be carefully soaked with ethanol. The filter material was carefully and repeatedly washed with ultrapure water in a vacuum filter cup. The graphite filter cake was then transferred to a conical funnel and washed several times with ethanol. The wash solution was sonicated in 1L cold water for 4 minutes.
The solution was centrifuged at 4400rpm for 60 minutes in a 50ml centrifuge tube. After the solution was centrifuged, it was repeatedly washed with ethanol and ultrapure water. The centrifuge tube is also repeatedly sonicated to remove unwanted particles. This step serves to dissolve and dilute the various salts and acids remaining in the reaction. Repeating the steps until the washing is clean.
The graphite after sufficient washing was redispersed in an aqueous solution, the pH of the solution was checked and confirmed to be as neutral as that of ultrapure water, the solution in the centrifuge tube was vigorously shaken and left to settle for 30 seconds in order to remove larger and heavier non-dispersible particles, and the precipitated material was filtered with ultrapure water and through a MCE vacuum filter orifice of 0.1 μm pore size.
To be able to obtain accurate concentration data of the product solution, 4.8ml of the product solution was filtered using a 0.1 μm MCE semipermeable membrane and the filter cake was dried and the membrane mass was weighed. To characterize the fully dried product, thicker vacuum filtration membranes were used and the product was filtered through a custom made filtration apparatus, the diameter of the filter being 25 mm. 10-15ml of the product solution (ca. 3.5mg) was used for filtration for 2-3 hours, followed by drying the graphene oxide film overnight at ambient temperature and normal pressure.
The average resistance of the surface of a film with the thickness of 25mm measured by a system in which needles are linearly arranged by a Jandel four-point probe is 1000 omega/cm, the resistance measurement positions are all positioned at the center of the filter membrane in the experiment, and the average value is obtained by repeatedly measuring for more than four times.
Such low resistance graphene would have three major advantages: (1) the graphene can be used in conductive paste to prepare high-conductivity low-cost conductive ink; (2) the low resistance means high electrical conductivity, and the high electrical conductivity means higher thermal conductivity, so the graphene thin film can be used for manufacturing a graphene electric heating plate; (3) the graphene has flexibility, and after the graphene is combined with other flexible base materials such as silicon rubber, the obtained product can ensure that the graphene has conductivity similar to that of metal under the stretching condition, and the product has wide application prospects such as strain sensors, robot skin and the like.
In order to prepare an XRD sample, a round piece with the diameter of 7.5mm at the central position of the graphene oxide filtering membrane is cut at a fixed point by a perforating machine, and viscous liquid obtained by centrifuging at the rotation speed of 10000rpm of a centrifugal machine for 90 minutes is used for attaching the cut slice to an amorphous silicon-based XRD sample table. The XRD test used an X-ray diffractometer model a Bruker D8 advanced diffractometer and fitted with a graphite monochromator. All samples were tested under the same experimental conditions (temperature and humidity) using a radiation length of 1mm, the relative humidity in the experiment being 41% and the temperature 23.5 ℃.
The graphene material prepared under strong current has obvious characteristic peaks at 10.5 degrees, 24 degrees and 27.5 degrees respectively; the graphene material prepared under the medium current condition has a characteristic sharp peak at 10.5 degrees and has an unsharpened characteristic peak near 25 degrees; the graphene material prepared under low current has obvious characteristic peak positions at 10.5 degrees and 28 degrees; the graphene samples prepared by prolonged time at low current had characteristic XRD peak signals similar to those of the medium intensity current graphene samples.
The XRD peak signals show that the graphite particles are detached from the graphite bed, and at the peaks of 10.5 ° and 28 °, a part of graphene (10.5 °) is exfoliated from graphite and oxidized at low current, but a part of graphite (28 °) is still present, and at the peaks of 10.5 ° and 25 °, almost all graphene is expanded by ions at medium current, the peak position is shifted from 28 ° to 25 ° of graphite, and a sharp peak of 10.5 ° indicates that most graphene is exfoliated from graphite bed and oxidized. Graphene materials prepared under a high current not only effectively exfoliate graphene, but also partially oxidize to generate different organic functional groups, which increase the spacing of graphene, thereby causing characteristic peaks (24 ° and 27.5 °) at different positions.
The graphene material made by different currents is characterized by Fourier change infrared total reflection attenuation spectrum, and spectrum information is obtained. In preparing infrared spectra samples, vacuum filtered films were extruded onto diamond and spectra were obtained as 24 accumulations of the spectra measured in the experiment. The spectral baselines were smoothed by bruker opus7.2 software and all spectra were measured under the same conditions.
The signal of the infrared spectrum peak shows that the graphene product has a certain number of organic functional groups. They include epoxy (1000-. These organic functional groups can be used not only to facilitate the suspension of graphene in a solvent, but also to further combine with organic materials to produce organic composite materials.
Therefore, the method can fully oxidize the graphite particles and fully strip the graphene from the graphite bed, so that the graphene with low resistance is prepared, and the graphene has a certain number of functional groups, so that the graphene can be effectively combined with an organic material to obtain the organic composite material.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. The equipment for preparing graphene comprises a tank body and a support fixedly connected to the bottom of the tank body, wherein a through hole is formed in the bottom of the tank body, and the equipment is characterized in that: still including the working electrode base of locating the support bottom, pass through-hole and the glass pipe of vertical fixation setting on the working electrode base, the glass pipe with be equipped with porous separator between the contact surface of working electrode board, graphite is arranged in the bottom of glass pipe and with porous separator and the contact of working electrode base, the top of graphite are equipped with glass fiber filtration membrane, glass fiber filtration membrane's upper surface is equipped with and stretches into through the through-hole the inside gravity squeezer of glass pipe, equipment still includes reference electrode and counter electrode, the reference electrode inserts to the bottom through gravity squeezer top, the counter electrode with the gravity squeezer is connected, the gravity squeezer is including stretching into the pipe of glass pipe, setting up the stripper plate in the pipe bottom and setting up the backup pad at the pipe top.
2. The apparatus for preparing graphene according to claim 1, wherein: a sealing film is further arranged between the glass tube and the working electrode substrate, an opening used for the porous separator to contact with the working electrode substrate is formed in the sealing film, and a cavity is formed in the surface, contacting with the glass fiber filter, below the gravity squeezer.
3. The apparatus for preparing graphene according to claim 1, wherein: the supporting plate is provided with a through hole for fixing the reference electrode and a weight for applying pressure.
4. The apparatus for preparing graphene according to claim 1, wherein: the working electrode substrate is made of titanium material.
5. The apparatus for preparing graphene according to claim 1, wherein: the tank body is made of polyimide materials, and the glass tube is made of epoxy resin materials.
6. The preparation method of the graphene is characterized by comprising the following steps: a method for preparing graphene using the apparatus for preparing graphene according to any one of claims 1 to 5, comprising the steps of:
s1: placing graphite particles at the bottom of a glass tube above the working electrode substrate and below a gravity press;
s2: pressing the graphite particles proximate to the working electrode substrate by applying gravity to a support plate on a gravity press;
s3: adding a water-soluble acid electrolyte into the empty pipe to immerse the graphite particles;
s4: gravity compression of the graphite material during the application of a constant current to the working electrode substrate and counter electrode and maintenance of the reaction.
7. The method for producing graphene according to claim 6, wherein: the water-soluble acidic electrolyte mainly comprises perchloric acid, sulfuric acid, nitric acid and phosphoric acid.
8. The method for producing graphene according to claim 6, wherein: the density of the constant current is 7.5-30mA/cm2。
9. The method for producing graphene according to claim 6, wherein: the step of S1 is preceded by a step of cleaning the working electrode substrate, which comprises the steps of carrying out ultrasonic treatment on the working electrode substrate in acetone for 10 minutes, washing away surface grease, then immersing in ethanol for two minutes, and finally washing with ultrapure water for several times.
10. A graphene characterized by: the graphene prepared by the preparation method according to any one of claims 6 to 9, which has a surface resistance value of 1000 Ω/cm, and has organic functional groups between the graphene.
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| CN109504093A (en) * | 2018-11-19 | 2019-03-22 | 珠海市扬程玻璃制品有限公司 | A kind of preparation method of conductive pressure sensitive nanometer silicon rubber |
| CN115448302B (en) * | 2022-09-29 | 2023-07-21 | 深圳烯材科技有限公司 | Method for preparing graphene oxide based on pressure regulation and continuous electrolysis |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103080004A (en) * | 2010-08-11 | 2013-05-01 | 三星泰科威株式会社 | Method of post treating graphene and method of manufacturing graphene using the same |
| CN103991862A (en) * | 2013-12-27 | 2014-08-20 | 杭州金马能源科技有限公司 | Method for preparing high-quality graphene through electrochemical high-efficiency exfoliation |
| WO2016046529A1 (en) * | 2014-09-22 | 2016-03-31 | Bae Systems Plc | Graphene manufacture |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103080004A (en) * | 2010-08-11 | 2013-05-01 | 三星泰科威株式会社 | Method of post treating graphene and method of manufacturing graphene using the same |
| CN103991862A (en) * | 2013-12-27 | 2014-08-20 | 杭州金马能源科技有限公司 | Method for preparing high-quality graphene through electrochemical high-efficiency exfoliation |
| WO2016046529A1 (en) * | 2014-09-22 | 2016-03-31 | Bae Systems Plc | Graphene manufacture |
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Effective date of registration: 20221128 Address after: No. 9, Ecological Industrial Park, Rongxin Road, Rongjiawan Town, Yueyang County, Yueyang City, Hunan Province, 414000 Patentee after: HUNAN HENGYI MATERIAL TECHNOLOGY CO.,LTD. Address before: No.2 Longshan Avenue, Longshan Industrial Zone, Doumen Town, Doumen District, Zhuhai, Guangdong 519110 (workshop a) Patentee before: ZHUHAI YANGCHENG GLASS PRODUCTS CO.,LTD. |