CN108892123B - Preparation method of porous graphene - Google Patents
Preparation method of porous graphene Download PDFInfo
- Publication number
- CN108892123B CN108892123B CN201810586526.0A CN201810586526A CN108892123B CN 108892123 B CN108892123 B CN 108892123B CN 201810586526 A CN201810586526 A CN 201810586526A CN 108892123 B CN108892123 B CN 108892123B
- Authority
- CN
- China
- Prior art keywords
- graphene
- oxidation
- porous graphene
- graphite
- reacting
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
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
- C01B32/184—Preparation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- C01B32/198—Graphene oxide
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of porous graphene, which comprises the following steps of firstly, carrying out oxidation treatment on a graphite raw material to obtain graphite oxide; secondly, oxidizing the graphite oxide for the second time by using potassium ferrate, wherein the generated oxygen can convert the graphite oxide into graphene oxide; then residual Fe in the solution after secondary oxidation is recycled2+Forming a Fenton reagent with hydrogen peroxide, and carrying out third oxidation on the oxidized graphene after the second oxidation so as to generate nano holes on the surface of the oxidized graphene sheet layer; and carrying out reduction reaction on the graphene oxide rich in the nano holes obtained after the third oxidation to obtain the porous graphene. The preparation method is simple in process, can quickly finish the preparation of the porous graphene, is easy to realize large-scale production, avoids adding more strong acid and strong base in the preparation process, saves the cost and reduces the pollution to the environment. The porous graphene prepared by the invention is used as a lithium ion battery cathode material, and shows excellent electrochemical performance in the aspects of energy density and charge-discharge rate.
Description
Technical Field
The invention relates to the technical field of graphene, in particular to a preparation method of porous graphene, and the porous graphene material is suitable for a negative electrode material of a lithium ion battery.
Background
Graphene is a new carbonaceous material with a two-dimensional planar structure formed by tightly stacking single-layer carbon atoms, and is a basic structural unit for constructing zero-dimensional fullerene, one-dimensional carbon nano-tubes and three-dimensional graphite. Graphene is not only the thinnest one of the known materials (the theoretical thickness is only 0.35nm), but also has very high strength (110GPa), and the theoretical specific surface area is 2630m2(ii) in terms of/g. The unique atomic structure of graphene endows the graphene with excellent performances in the aspects of electricity, thermal property, mechanics and the like, and has wide application prospects in various fields.
At present, a great number of reports are made on taking graphene as a negative electrode material of a lithium ion battery. The graphene is formed by closely arranging single-layer carbon atoms, lithium ions can be stored on two sides of a graphene sheet layer and also can be stored in the edge and holes of the graphene sheet layer, and the theoretical capacity of the graphene is 740-780 mA h/g, which is about 2 times of that of a traditional graphite cathode. The graphene is used as the lithium ion battery cathode material, so that the lithium storage capacity of the cathode material is greatly improved, and the energy density is further improved. In addition, when the graphene is used as the lithium ion battery cathode material, the diffusion path of lithium ions in the graphene material is short, the conductivity is high, and the rate capability of the lithium ion battery can be improved to a great extent. Therefore, the graphene has good application prospect as the lithium ion battery cathode material.
However, graphene negative electrode materials are expensive, lithium ions are difficult to transfer vertically, and diffusion of lithium ions in the negative electrode material is hindered particularly in high-rate charge and discharge. Therefore, researchers have focused on preparing porous graphene. Holes are formed in the graphene in various modes, and the blocking effect of the graphene on lithium ion diffusion is reduced to the minimum by adjusting the size and the number of the holes. NaOH, KOH, HNO3、KMnO4Concentrated H2SO4The equistrong acid and strong base reagent is widely applied to the graphene pore-forming technology. However, the use of these strong acid and strong base oxidizing agents and the increased subsequent work not only cause a large increase in the cost of graphene, but also form a large amount of wastewater that is difficult to treat, increasing environmental pollution and treatment cost.
Therefore, a preparation method of porous graphene, which has a simple preparation process and low cost and does not cause environmental pollution, is needed.
Disclosure of Invention
The invention aims to provide a preparation method of porous graphene, which is simple in preparation process, low in cost and free from aggravating environmental pollution.
In order to achieve the purpose, the technical scheme of the invention is as follows: a preparation method of porous graphene comprises the following steps:
1) carrying out oxidation treatment on a graphite raw material to obtain graphite oxide;
2) adding potassium ferrate into the graphite oxide, and carrying out secondary oxidation on the graphite oxide to obtain graphene oxide;
3) carrying out third oxidation on the oxidized graphene after the second oxidation by using a Fenton reagent so as to generate nano holes on the surface of the oxidized graphene sheet layer;
4) and carrying out reduction reaction on the graphene oxide rich in the nano holes obtained after the third oxidation to obtain the porous graphene.
Further, the step 1) of carrying out oxidation treatment on the graphite raw material is to carry out low-temperature oxidation on graphite by using a Hummers method; the graphite is natural crystalline flake graphite with the purity of more than or equal to 99.5 percent; the Hummers method comprises the following specific steps: adding the flake graphite raw material into a beaker filled with concentrated sulfuric acid at the temperature of below 1 ℃, stirring and reacting for 1-5h, then slowly adding potassium permanganate to react for 1-12h, wherein the adding amount of the potassium permanganate is 2-10 times of the mass of the graphite, and the system temperature is kept below 4 ℃, thus obtaining graphite oxide after reaction.
Further, performing secondary oxidation on the graphite oxide by using potassium ferrate in the step 2), and stripping the graphite oxide into graphene oxide by using a large amount of oxygen generated by the reaction of the potassium ferrate; wherein the purity of the potassium ferrate is more than 97 percent, the addition amount of the potassium ferrate is 0.1 to 8 times of the mass of the graphite, and the reaction time is 0.1 to 48 hours.
Further, after the step 3) of secondary oxidation, adding a proper amount of hydrogen peroxide into the graphene oxide solution, and mixing with Fe in the solution2+Reacting to form a Fenton reagent, and carrying out third oxidation on the graphite oxide subjected to secondary oxidation to generate nanopores on the surface of the graphite oxide sheet;
specifically, after the graphene oxide solution after secondary oxidation is subjected to oil bath at the constant temperature of 38 ℃ for 0.3-0.8 h, sufficient deionized water is slowly added, after reaction for 20-40 min, hydrogen peroxide is added, and Fe after reaction with potassium ferrate in the solution2+Reacting to generate a Fenton reagent, and carrying out third oxidation on the oxidized graphene after the second oxidation; the Feton reagent is prepared according to the following parameters: the concentration of hydrogen peroxide is 0.5-2 mmol/L, (H)2O2)：(Fe2+) The molar ratio is 1: 1-8, the pH value is 2-5, and the third timeThe reaction time of the oxidation is 10-120 min.
Further, in the step 4), the graphene oxide rich in the nano-pores obtained after the third oxidation is reduced by using a chemical reagent or high-temperature treatment, so as to obtain the porous graphene.
Wherein, the reducing chemical reagent comprises one of hydrazine hydrate, hydroiodic acid, sodium borohydride, vitamin C, alcohols and phenols or the mixture of 2 to 6 of the above in any proportion; the reaction time may be from 0.1 to 12 hours.
The high-temperature treatment is to place the graphene oxide powder rich in the nano-pores into an atmosphere furnace or a muffle furnace in a vacuum environment at 800 ℃ of 200-; the treatment time may be 0.1-5 h.
Compared with the prior art, the invention has the beneficial effects that:
the preparation method of the porous graphene has simple process, is easy to realize large-scale production, only adds one potassium ferrate with low price, changes the primary oxidation in the original Hummers method into tertiary oxidation, omits the intermediate medium-temperature reaction and the highest-temperature reaction, avoids adding more strong acid and strong base in the preparation process, saves the cost and reduces the pollution to the environment.
The porous graphene prepared by the method is directly used for a lithium battery cathode material, the specific capacity is up to 800mA h/g, the reversible specific capacity of 645mAh/g is still available under the current density of 3C (1C-372 mA h/g), and the porous graphene shows excellent electrochemical performance in the aspects of energy density and rate capability.
Drawings
Fig. 1 is a charge and discharge curve of the porous graphene prepared in example 1 (VS Li/Li + in ordinate represents the potential of the graphene negative electrode with respect to the metallic lithium negative electrode);
fig. 2 is a rate curve of porous graphene prepared in example 1;
fig. 3 is a comparison graph of the porous graphene/graphite composite material prepared in example 2 (mass ratio of porous graphene to graphite is 1: 7), and a charge-discharge curve of graphite (VS Li/Li + in ordinate represents potential of a graphene negative electrode with respect to a metallic lithium negative electrode);
wherein A1 and A2 are charge-discharge curves of graphite, and B1 and B2 are charge-discharge curves of the porous graphene/graphite composite material;
fig. 4 is a cycle curve of the porous graphene/graphite composite material prepared in example 2.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Other embodiments, which can be derived by those skilled in the art from the embodiments of the present invention without any creative effort, shall fall within the protection scope of the present invention.
In the step 1) of the invention, the mass concentration of the concentrated sulfuric acid is 80%, and the graphite powder is natural crystalline flake graphite with the purity of more than 99.5%.
In each example, step 2), the potassium ferrate was more than 97% pure.
Example 1
A preparation method of porous graphene comprises the following steps:
1) weighing 150mL of concentrated sulfuric acid, pouring the concentrated sulfuric acid into a 500mL beaker, putting the beaker into an ice bath, cooling to below 1 ℃, weighing 5g of graphite powder, putting the graphite powder into the beaker, stirring and reacting for 1h, slowly adding 10g of potassium permanganate, controlling the temperature to be not more than 4 ℃, and reacting for about 2 h;
2) then 0.5g of potassium ferrate is added, the reaction is continued for 2 hours, and the graphite oxide is oxidized for the second time, so that the surface of the graphite oxide is locally corroded.
3) Transferring the beaker to a constant-temperature oil bath kettle, controlling the temperature at 38 ℃, reacting for 0.5h, finally slowly adding 100mL of deionized water into the obtained mixed solution, reacting for 30min, adding 5mL (0.5mol/L) of hydrogen peroxide, and reacting with Fe in the solution after potassium ferrate reacts2+And (3) reacting to generate a Fenton reagent, controlling the pH value to be 2, and carrying out third oxidation on the obtained graphite oxide for 60min to form a plurality of nano holes.
4) And putting the prepared porous graphene oxide into a vacuum drying oven, vacuumizing to 0.1Mpa, and reacting for 1h at 200 ℃ to obtain the porous graphene.
Uniformly mixing the obtained porous graphene, a conductive agent Super-P and a binder LA132 according to a mass ratio of 8:1:1, grinding the mixture in a mortar to prepare a uniform paste, coating the paste on a bright copper foil with the thickness of 12 microns as a current collector, rolling an electrode plate by using a roller press after water is completely volatilized, punching the electrode plate into an electrode plate with a required diameter, drying the electrode plate for 12 hours at 105 ℃ in a vacuum oven, removing trace water contained in the electrode plate, and quickly transferring the electrode plate into a glove box. The metal lithium is used as a counter electrode, Celgard 2400 is used as a diaphragm, an electrolyte is 1mol/l LiPF6 containing 2% VC (vinylene carbonate), a solvent is EC/DMC/EMC (volume ratio is 1:1:1), and the CR2032 type button battery is assembled. The specific capacity and the rate capability of the electrode (the current density is 0.2C, 1C and 3C, wherein 1C is equal to 372mAh/g, and the test voltage range is 0.01-3.0V) are respectively tested, and the test results are shown in fig. 1 and fig. 2.
As shown in fig. 1, under a current density of 0.2C, the porous graphene as a negative electrode material of a lithium ion battery has a specific capacity of 800mAh/g, which is more than twice of that of a conventional graphite negative electrode material, and shows a significant advantage in energy density. In addition, the materials were subjected to 1C and 3C rate discharges, and their specific capacities reached 750mAh/g and 650mAh/g, respectively, showing excellent rate characteristics (as shown in FIG. 2).
Example 2
A preparation method of porous graphene comprises the following steps:
1) weighing 150mL of concentrated sulfuric acid, pouring the concentrated sulfuric acid into a 500mL beaker, putting the beaker into an ice bath, cooling to below 1 ℃, weighing 5g of graphite powder, putting the graphite powder into the beaker, slowly adding 15g of potassium permanganate after 5 hours, controlling the temperature to be not more than 4 ℃, and reacting for about 12 hours;
2) then 20g of potassium ferrate is added, the reaction is continued for 0.1h, and the graphite oxide is oxidized for the second time, so that the surface of the graphite oxide is locally corroded.
3) Transferring the beaker to a constant-temperature oil bath kettle, controlling the temperature at 38 ℃, reacting for 0.2h, and finally slowly adding 100mL of the mixed solutionReacting for 40min, adding 6.3mL (2mol/L) of hydrogen peroxide, and reacting with Fe in the solution after potassium ferrate reaction2+And (3) reacting to generate a Fenton reagent, controlling the pH of a reaction system to be 2-3, carrying out third oxidation on the obtained graphite oxide for 120min to form a plurality of nano holes, and controlling the reaction temperature to be higher than 95 ℃ at this stage.
4) And (3) placing the prepared porous graphene oxide into an 800 ℃ tube furnace filled with argon, and reacting for 5min to obtain the porous graphene.
Uniformly mixing the obtained porous graphene, a graphite negative electrode, a conductive agent Super-P and a binder LA132 according to a mass ratio of 1:7:1:1, grinding the mixture in a mortar to prepare a uniform paste, coating the paste on a bright copper foil which is 12 microns thick and is used as a current collector, rolling an electrode plate by using a roller press after water is completely volatilized, punching the electrode plate into an electrode plate with a required diameter, drying the electrode plate in a vacuum oven at 105 ℃ for 12 hours, removing trace water contained in the electrode plate, and quickly transferring the electrode plate into a glove box. The metal lithium is used as a counter electrode, Celgard 2400 is used as a diaphragm, an electrolyte is 1mol/l LiPF6 containing 2% VC (vinylene carbonate), a solvent is EC/DMC/EMC (volume ratio is 1:1:1), and the CR2032 type button battery is assembled. The specific capacity and the rate capability of the electrode (current density is 0.2C, 1C and 3C, wherein 1C is equal to 372mAh/g, and the test voltage range is 0.01-3.0V) are respectively tested, and the test results are shown in fig. 3 and fig. 4.
As shown in fig. 3, under a rate of 0.2, the porous graphene/graphite is used as a negative electrode material of a lithium ion battery, and the specific capacity of the porous graphene/graphite is up to 450mAh/g, which is 1.3 times of that of a conventional graphite negative electrode. In addition, under the magnification of 1C, the specific capacity of the porous graphene/graphite is up to 355mAh/g, 328mAh/g is still left after 600 times of circulation, and the capacity retention rate is up to 92% (as shown in FIG. 4).
Because the graphene used in the embodiment is less, the cost of the material is favorably controlled, and the graphene is expected to be a substitute of the traditional graphite cathode.
Example 3
A preparation method of porous graphene comprises the following steps:
1) weighing 150mL of concentrated sulfuric acid, pouring the concentrated sulfuric acid into a 500mL beaker, putting the beaker into an ice bath, cooling to below 1 ℃, weighing 5g of graphite powder, putting the graphite powder into the beaker, slowly adding 50g of potassium permanganate after 2 hours, controlling the temperature to be not more than 4 ℃, and reacting for about 3 hours;
2) then 30g of potassium ferrate is added, the reaction is continued for 48 hours, and the graphite oxide is oxidized for the second time, so that the surface of the graphite oxide is locally corroded.
3) Transferring the beaker to a constant-temperature oil bath kettle, controlling the temperature at 38 ℃, reacting for 0.8h, finally slowly adding 100mL of deionized water into the obtained mixed solution, reacting for 10min, adding 38mL (1mol/L) of hydrogen peroxide, and reacting with Fe in the solution after potassium ferrate reacts2+And (3) reacting to generate a Fenton reagent, controlling the pH value of a reaction system to be 2-3, carrying out third oxidation on the obtained graphite oxide for 10min to form a plurality of nano holes, and controlling the reaction temperature to be higher than 95 ℃ at this stage.
4) Dissolving the prepared porous graphene oxide in water, preparing 100ml of 1mg/ml porous graphene oxide solution, dropwise adding 0.1g hydrazine hydrate into the solution, reacting at 90 ℃ for 1h, filtering, and freeze-drying to obtain the porous graphene.
Uniformly mixing the obtained porous graphene, a graphite negative electrode, a conductive agent Super-P and a binder LA132 according to a mass ratio of 1:7:1:1, grinding the mixture in a mortar to prepare a uniform paste, coating the paste on a bright copper foil which is 12 microns thick and is used as a current collector, rolling an electrode plate by using a roller press after water is completely volatilized, punching the electrode plate into an electrode plate with a required diameter, drying the electrode plate in a vacuum oven at 105 ℃ for 12 hours, removing trace water contained in the electrode plate, and quickly transferring the electrode plate into a glove box. The metal lithium is used as a counter electrode, Celgard 2400 is used as a diaphragm, an electrolyte is 1mol/l LiPF6 containing 2% VC (vinylene carbonate), a solvent is EC/DMC/EMC (volume ratio is 1:1:1), and the CR2032 type button battery is assembled. And respectively testing the specific capacity and the rate capability of the electrode (the current density is 0.2C, 1C and 3C, wherein 1C is equal to 372mAh/g, and the test voltage range is 0.01-3.0V).
Under the multiplying power of 0.2, the porous graphene/graphite is used as a lithium ion battery cathode material, the specific capacity of the porous graphene/graphite is up to 510mAh/g, and is 1.4 times of that of the traditional graphite cathode. In addition, under the multiplying power of 1C, the specific capacity of the porous graphene/graphite is up to 395mAh/g, 358mAh/g still exists after 600 times of circulation, and the capacity retention rate is up to 90%.
Example 4
The present embodiment is different from embodiment 3 in that: in the step 4), 20ml of HI solution with the mass concentration of 55% is adopted, the reaction temperature is 100 ℃, the reaction time is 60s, and then the reacted solution is quickly washed by ethanol to remove excessive HI.
Uniformly mixing the obtained porous graphene, a graphite negative electrode, a conductive agent Super-P and a binder LA132 according to a mass ratio of 1:7:1:1, grinding the mixture in a mortar to prepare a uniform paste, coating the paste on a bright copper foil which is 12 microns thick and is used as a current collector, rolling an electrode plate by using a roller press after water is completely volatilized, punching the electrode plate into an electrode plate with a required diameter, drying the electrode plate in a vacuum oven at 105 ℃ for 12 hours, removing trace water contained in the electrode plate, and quickly transferring the electrode plate into a glove box. The metal lithium is used as a counter electrode, Celgard 2400 is used as a diaphragm, an electrolyte is 1mol/l LiPF6 containing 2% VC (vinylene carbonate), a solvent is EC/DMC/EMC (volume ratio is 1:1:1), and the CR2032 type button battery is assembled. And respectively testing the specific capacity and the rate capability of the electrode (the current density is 0.2C, 1C and 3C, wherein 1C is equal to 372mAh/g, and the test voltage range is 0.01-3.0V).
Under the multiplying power of 0.2, the porous graphene/graphite is used as a lithium ion battery cathode material, the specific capacity of the porous graphene/graphite is up to 490mAh/g, and is 1.36 times of that of the traditional graphite cathode. In addition, under the multiplying power of 1C, the specific capacity of the porous graphene/graphite is up to 375mAh/g, 343mAh/g still exists after 600 times of circulation, and the capacity retention rate is up to 91%.
Claims (5)
1. A preparation method of porous graphene is characterized by comprising the following steps: the method comprises the following steps:
1) adding a flake graphite raw material into a beaker filled with concentrated sulfuric acid at the temperature of below 1 ℃, stirring and reacting for 1-5h, then slowly adding potassium permanganate to react for 1-12h, wherein the adding amount of the potassium permanganate is 2-10 times of the mass of the flake graphite raw material, the system temperature is kept below 4 ℃, and graphite oxide is obtained after reaction;
2) adding potassium ferrate with the addition amount of 0.1-8 times of the mass of the flake graphite raw material into graphite oxide, reacting for 0.1-48h, and carrying out secondary oxidation on the mixture to obtain graphene oxide;
3) after the graphene oxide solution subjected to secondary oxidation is subjected to oil bath at the constant temperature of 38 ℃ for 0.3-0.8 h, slowly adding a proper amount of deionized water, reacting for 20-40 min, adding hydrogen peroxide, and reacting the hydrogen peroxide with Fe obtained after the potassium ferrate in the graphene oxide solution reacts2+Reacting to generate a Fenton reagent, and carrying out third oxidation on the oxidized graphene after the second oxidation so as to generate nano holes on the surface of the sheet layer of the oxidized graphene; wherein the Fenton reagent is prepared according to the following parameters: the concentration of the hydrogen peroxide is 0.5-2 mol/L, and the hydrogen peroxide and the Fe are2+The molar ratio of (1: 1) - (8), the pH value is 2-5, and the reaction time of the third oxidation is 10-120 min;
4) and carrying out reduction reaction on the graphene oxide rich in the nano holes obtained after the third oxidation to obtain the porous graphene.
2. The method for preparing porous graphene according to claim 1, wherein: the purity of the potassium ferrate in the step 2) is more than 97 percent.
3. The method for preparing porous graphene according to claim 1, wherein: and in the step 4), reducing the graphene oxide rich in the nano-pores obtained after the third oxidation by using a chemical reagent or high-temperature treatment to obtain the porous graphene.
4. The method for preparing porous graphene according to claim 3, wherein: the reducing chemical reagent comprises hydrazine hydrate, hydroiodic acid, sodium borohydride, vitamin C, alcohols and phenols, or the mixture of more than one of the hydrazine hydrate, the hydroiodic acid, the sodium borohydride, the vitamin C, the alcohols and the phenols in any proportion.
5. The method for preparing porous graphene according to claim 3, wherein: the high-temperature treatment is to put the graphene oxide powder rich in the nano-pores into a vacuum box at the temperature of 200-800 ℃ or hydrogen, nitrogen, argon or a mixture of the two in a volume ratio of 1:1 in a tubular furnace under a mixed hydrogen/argon atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810586526.0A CN108892123B (en) | 2018-06-08 | 2018-06-08 | Preparation method of porous graphene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810586526.0A CN108892123B (en) | 2018-06-08 | 2018-06-08 | Preparation method of porous graphene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108892123A CN108892123A (en) | 2018-11-27 |
| CN108892123B true CN108892123B (en) | 2021-10-15 |
Family
ID=64344243
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810586526.0A Active CN108892123B (en) | 2018-06-08 | 2018-06-08 | Preparation method of porous graphene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108892123B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112357909B (en) * | 2020-11-11 | 2022-02-15 | 四川恒瑞天成科技有限公司 | Preparation method and application of graphene porous membrane |
| CN114014306B (en) * | 2021-12-15 | 2022-08-09 | 陇东学院 | Preparation method and application of oxygen-enriched layered porous graphene |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103723705A (en) * | 2012-10-15 | 2014-04-16 | 海洋王照明科技股份有限公司 | Graphene/nano-aluminum compound and preparation method thereof |
| KR101532769B1 (en) * | 2013-03-19 | 2015-06-30 | 서울대학교산학협력단 | Scalable porous graphene for rechargeable batteries and method for preparing the same |
| CN105439128A (en) * | 2015-11-09 | 2016-03-30 | 国网智能电网研究院 | Preparation method for porous graphene lithium ion battery positive electrode material |
| CN106185880A (en) * | 2016-06-07 | 2016-12-07 | 黑龙江省宝泉岭农垦帝源矿业有限公司 | A kind of method that porous graphene directly prepared by graphene oxide slurry utilizing pre-purification |
| CN106430156A (en) * | 2016-08-30 | 2017-02-22 | 张华� | Preparation of porous graphene and porous graphene prepared accordingly and application of porous graphene |
| CN106430175A (en) * | 2016-11-07 | 2017-02-22 | 山东欧铂新材料有限公司 | Rapid preparation methods of graphene oxide and graphene |
| CN106744828A (en) * | 2016-11-23 | 2017-05-31 | 西安工业大学 | A kind of preparation method of Novel electro-Fenton cathode material and application |
-
2018
- 2018-06-08 CN CN201810586526.0A patent/CN108892123B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN108892123A (en) | 2018-11-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113410440B (en) | Cobalt diselenide @ porous nitrogen-doped carbon nanocomposite, potassium ion battery and preparation method of cobalt diselenide @ porous nitrogen-doped carbon nanocomposite | |
| CN102602978B (en) | Preparation method of CuO micro-/nano-array electrode for lithium ion battery | |
| CN105470481A (en) | Nitrogen-doped carbon-coated manganese monoxide composite material with one-dimensional porous core-shell structure and preparation method of nitrogen-doped carbon-coated manganese monoxide composite material | |
| CN112582615A (en) | One-dimensional porous silicon-carbon composite negative electrode material, preparation method and application thereof | |
| CN102299326A (en) | Graphene modified lithium iron phosphate/carbon composite material and its application | |
| CN109904408B (en) | MoS2Preparation method and application of composite material with nanosheet embedded in carbon substrate | |
| CN110739446B (en) | Silicon/carbon composite anode material and preparation method thereof | |
| CN104377346B (en) | Method for preparing modified graphite negative electrode material of sodium ion battery | |
| CN108892123B (en) | Preparation method of porous graphene | |
| CN112803018B (en) | Silicon-doped graphene composite material and preparation method and application thereof | |
| CN104638248A (en) | Method for preparing graphene/lead compound composite material | |
| CN105826552A (en) | Method for producing graphene-composited lithium cobalt oxide positive electrode material | |
| CN112349875A (en) | Lithium ion battery copper-copper oxide integrated cathode based on hollow tubular three-dimensional nano porous structure and preparation method | |
| CN114824202B (en) | FeS with multi-core shell structure 2 Preparation method and application of @ C nanocapsule material | |
| CN114843459B (en) | Antimony pentasulfide-based material and preparation method and application thereof | |
| CN109256547A (en) | A kind of preparation method of porous graphene-lithium iron phosphate positive material | |
| CN110589818B (en) | Preparation method and application of nitrogen-doped mesoporous carbon material | |
| CN110828819B (en) | Pyrrhotite type iron sulfide negative electrode material for potassium ion battery and preparation method thereof | |
| CN109301198B (en) | Nickel nanosheet array loaded zinc oxide composite electrode and preparation method thereof | |
| CN112374552A (en) | Composite modified graphite negative electrode material and preparation method thereof | |
| CN108807889B (en) | Preparation method and application of porous iron-doped vanadium oxide electrode material | |
| CN113241427A (en) | High-performance silicon-carbon negative electrode material and preparation method thereof | |
| CN112490432A (en) | Germanium-doped ferrous oxalate lithium ion battery composite negative electrode material and preparation method thereof | |
| CN111261857B (en) | FePS for sodium ion battery3/NC composite negative electrode material, preparation method thereof and sodium ion battery | |
| CN116169288B (en) | Metal quantum dot/hard carbon negative electrode material 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20211229 Address after: 2201, building 1, COFCO Chuangxin R & D center, 69 Xingdong community, Xin'an street, Bao'an District, Shenzhen City, Guangdong Province Patentee after: Chuangpus (Shenzhen) New Energy Technology Co.,Ltd. Address before: 1-3 / F, building F2, No. 1001, Zhongshan Park Road, Nanshan District, Shenzhen City, Guangdong Province Patentee before: SHENZHEN NEW HENGYE BATTERY TECHNOLOGY Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230419 Address after: 710075 No. 6, Yingzhou 1st Street, Gaozhuang Town, Jinghe new town, Xixian New District, Xi'an City, Shaanxi Province Patentee after: Shaanxi epno electric energy storage technology Co.,Ltd. Address before: 2201, building 1, COFCO Chuangxin R & D center, 69 Xingdong community, Xin'an street, Bao'an District, Shenzhen City, Guangdong Province Patentee before: Chuangpus (Shenzhen) New Energy Technology Co.,Ltd. |
|
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 710075 No. 6, Yingzhou 1st Street, Gaozhuang Town, Jinghe new town, Xixian New District, Xi'an City, Shaanxi Province Patentee after: Shaanxi Epuno New Energy Technology Co.,Ltd. Address before: 710075 No. 6, Yingzhou 1st Street, Gaozhuang Town, Jinghe new town, Xixian New District, Xi'an City, Shaanxi Province Patentee before: Shaanxi epno electric energy storage technology Co.,Ltd. |