CN112250062A - Reduced graphene oxide and preparation method thereof - Google Patents
Reduced graphene oxide and preparation method thereof Download PDFInfo
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- CN112250062A CN112250062A CN202011111021.2A CN202011111021A CN112250062A CN 112250062 A CN112250062 A CN 112250062A CN 202011111021 A CN202011111021 A CN 202011111021A CN 112250062 A CN112250062 A CN 112250062A
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Abstract
The invention discloses reduced graphene oxide and a preparation method thereof; the preparation method comprises the steps of cleaning, drying, grinding and sieving carbon rods in the waste zinc-manganese batteries to obtain carbon rod powder; mixing carbon rod powder and sodium hydroxide, and then melting and cooling to obtain a cooled alkali melt sample; mixing the cooled alkali molten sample with water, filtering to obtain filter residue, and finally reacting the filter residue with hydrochloric acid to obtain purified graphite powder; washing, drying, grinding and sieving solid manganese oxide in the waste zinc-manganese battery to obtain manganese oxide powder; stripping a zinc skin shell of the waste zinc-manganese battery, and then washing and cutting to obtain a zinc sheet; purifying graphite powder, manganese oxide powder and K 2 S 2 O 8 And reacting with sulfuric acid, then adding water and a zinc sheet, and continuing to react to obtain the reduced graphene oxide. The invention prepares the reduced graphene oxide by using the materials in the waste zinc-manganese battery for the first time, not only solves the problem of treatment of the waste battery, but also provides a new method for preparing the reduced graphene oxide.
Description
Technical Field
The invention belongs to the technical field of reduced graphene oxide, and particularly relates to reduced graphene oxide and a preparation method thereof.
Background
The environmental problems caused by the waste batteries are increasingly serious, particularly zinc-manganese batteries are taken as main batteries, and the batteries contain substances such as metal zinc, metal iron, graphite, manganese salt, zinc salt, ammonium salt and the like, so that the ecological environment is easily damaged. Therefore, if the components can be effectively recycled, waste materials are changed into valuable materials, the environmental pollution can be reduced, and economic benefits can be brought, wherein the recycling of the carbon rods is particularly important.
Graphene is a novel material and is widely used in the fields of electronics industry, biomedicine, energy industry, chemistry and chemical industry and the like. The reduced graphene oxide is expected to be used for preparing materials such as novel sensors, solar cells, semiconductor films, hydrogen storage materials, surfactants, catalyst carriers and the like. Generally, the reduced graphene oxide is prepared by oxidizing graphite with strong acid to obtain graphite oxide, stripping the graphite oxide into a monolayer molecular layer by using a physical or chemical method, and finally preparing the reduced graphene oxide by using a chemical reduction method, an electrochemical reduction method, a microwave stripping method or a combined multi-step reduction method, wherein the chemical reduction method mainly comprises the following steps of: sodium borohydride, vitamin C, hydrazine and derivatives, HI reduction, etc. However, the preparation of reduced graphene oxide from materials in waste zinc-manganese batteries has been reported.
Disclosure of Invention
The invention aims to provide a method for preparing reduced graphene oxide by using materials in waste zinc-manganese batteries. The method solves the problem of treatment of waste batteries and provides a new method for preparing reduced graphene oxide.
In order to achieve the above object, an aspect of the present invention provides a method for preparing reduced graphene oxide, the method comprising:
(1) Cleaning, drying, grinding and sieving carbon rods in the waste zinc-manganese batteries to obtain carbon rod powder;
(2) Mixing the carbon rod powder and sodium hydroxide, and then melting and cooling to obtain a cooled alkali melt sample; mixing the cooled alkali molten sample with water, filtering to obtain filter residue, and finally carrying out contact reaction on the filter residue and hydrochloric acid to obtain purified graphite powder;
(3) Washing, drying, grinding and sieving solid manganese oxide in the waste zinc-manganese battery to obtain manganese oxide powder;
(4) Stripping a zinc skin shell of the waste zinc-manganese battery, and then washing and cutting to obtain zinc sheets;
(5) Mixing the purified graphite powder, manganese oxide powder and K 2 S 2 O 8 And carrying out contact reaction with sulfuric acid, then adding water and zinc sheets, and continuing to carry out contact reaction to obtain the reduced graphene oxide.
According to the present invention, preferably, in the step (1), the sieving is performed by using an 80-120 mesh sieve.
According to the invention, in step (2), the melting temperature is 400-500 ℃ and the time is 8-10min;
the water is water with the temperature of 30-50 ℃;
and the contact reaction time of the filter residue and hydrochloric acid is 30-60min.
According to the invention, in the step (2), the mass ratio of the carbon rod powder to the sodium hydroxide is 1.8-2.2;
the feed-liquid ratio of the carbon rod powder to water is 1;
the feed-liquid ratio of the carbon rod powder to the hydrochloric acid is 1; the concentration of the hydrochloric acid is 2-3mol/L.
According to the present invention, preferably, in the step (3), washing with water; sieving with 40-60 mesh sieve.
According to the present invention, preferably, in the step (4), washing with water; the cutting is to cut into zinc sheets smaller than 2 x 2 cm.
In the present invention, in the step (3) and the step (4), washing with water is preferably carried out with hot water at 50 to 70 ℃.
According to the present invention, preferably, in the step (5), the purified graphite powder, manganese oxide powder and K 2 S 2 O 8 The mass ratio of (1);
the feed-liquid ratio of the purified graphite powder to the sulfuric acid is 1; the mass concentration of the sulfuric acid is 95-98%;
the mass ratio of the purified graphite powder to the zinc sheets is 1.
According to the invention, preferably, in the step (5), the purified graphite powder, the manganese oxide powder and the K are 2 S 2 O 8 Carrying out contact reaction with sulfuric acid for 8-10h;
the time for continuing the contact reaction is 2-3h.
According to the invention, preferably, in the step (5), the reaction material after the continuous contact reaction is finished is kept still to obtain a suspension; carrying out centrifugal separation on the suspension to obtain a precipitate; and drying the precipitate to obtain the reduced graphene oxide.
In the invention, the standing time is preferably 30-40min; the centrifugal speed of the centrifugal separation is preferably 8000-10000r/min, and the centrifugal time is preferably 10-12min.
Another aspect of the present invention provides reduced graphene oxide prepared by the above preparation method.
The technical scheme of the invention has the following beneficial effects:
(1) The invention prepares the reduced graphene oxide by using the materials in the waste zinc-manganese battery for the first time, solves the problem of treatment of the waste battery, and provides a new method for preparing the reduced graphene oxide.
(2) The result of XRD determination of the reduced graphene oxide of the invention shows that the reduced graphene oxide is pure reduced graphene oxide; 23.05 at 2 theta ° A broad peak exists, the intensity and the position of the peak are matched with the values of the literature, and no impurity peak is found, which indicates that the purity of the product is higher.
(3) Through SEM pictures, the reduced graphene oxide provided by the invention is observed to be of a wrinkled surface structure.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The above and other objects, features and advantages of the present invention will become more apparent by describing in more detail exemplary embodiments thereof with reference to the attached drawings, in which like reference numerals generally represent like parts throughout.
Fig. 1 shows a process scheme of a reduced graphene oxide preparation method according to one embodiment of the present invention.
Figure 2 shows an XRD pattern of reduced graphene oxide according to one embodiment of the present invention. Wherein the vertical axis CPS in the figure is the diffraction intensity.
Fig. 3 shows an SEM photo pattern of reduced graphene oxide according to one embodiment of the present invention.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
A process scheme of the preparation method of reduced graphene oxide according to the following embodiments is shown in fig. 1.
Example 1:
a preparation method of reduced graphene oxide comprises the following steps: (a) preparing carbon rod powder: taking out the carbon rods in the waste zinc-manganese batteries, cleaning, drying, ball-milling, and sieving by using a 80-mesh sample sieve. (b) purifying graphite: uniformly mixing a certain amount of carbon rod powder and sodium hydroxide, putting the mixture into a nickel crucible, putting the nickel crucible into a high-temperature furnace for melting for 8min, taking out the nickel crucible for cooling, dissolving the cooled alkali melt sample with a certain volume of warm water at 40 ℃, filtering, adding a certain volume of 2.0mol/L hydrochloric acid into filter residues, stirring for 30min, carrying out suction filtration, and washing with distilled water to obtain purified graphite powder; (c) preparing manganese oxide powder: taking out solid manganese oxide in the waste zinc-manganese battery, washing with hot water at 60 ℃, drying, grinding by a ball mill, and sieving by a 40-mesh sample sieve; (d) preparing zinc sheets: stripping a zinc skin shell of the waste zinc-manganese battery, washing with hot water at 60 ℃, and cutting into zinc sheets smaller than 2 x 2 cm; (e) reaction: will measure a certain amountPurified graphite powder, manganese oxide powder and K of 2 S 2 O 8 Adding to a volume of H 2 SO 4 Performing ultrasonic treatment on the solution for 8h to turn the solution into black brown, adding distilled water with the same volume as sulfuric acid and zinc sheets with certain mass, stirring and reacting at room temperature of 25 ℃ for 2h, standing for 30min, and collecting suspension; (f) separation: centrifuging to separate out precipitate in the suspension, wherein the centrifugal speed is 8000r/min, and the centrifugal time is 10min; (g) drying: and (3) drying the obtained precipitate in a vacuum drying oven at room temperature of 25 ℃ to obtain black brown powder, namely the reduced graphene oxide. Wherein the mass ratio of the carbon rod powder to the sodium hydroxide is 1.8, and the temperature of the high-temperature furnace is 400 ℃; the feed liquid ratio of the carbon rod powder to the dissolved alkali melt sample warm water is 1; the feed-liquid ratio of the carbon rod powder to the hydrochloric acid is 1; the purified graphite powder, manganese oxide powder and K 2 S 2 O 8 The mass ratio of (1); the feed liquid ratio of the purified graphite powder to the sulfuric acid is 1; the mass ratio of the purified graphite powder to the zinc sheets is 1; h 2 SO 4 The mass concentration of the solution was 98%.
Example 2
A preparation method of reduced graphene oxide comprises the following steps: (a) preparing carbon rod powder: taking out the carbon rods in the waste zinc-manganese batteries, cleaning, drying, ball-milling, and sieving by using a 100-mesh sample sieve. (b) purifying graphite: uniformly mixing a certain amount of carbon rod powder and sodium hydroxide, putting the mixture into a nickel crucible, putting the nickel crucible into a high-temperature furnace for melting for 9min, taking out the nickel crucible for cooling, dissolving the cooled alkali melt sample with a certain volume of warm water at 40 ℃, filtering, adding a certain volume of 2.5mol/L hydrochloric acid into filter residue, stirring for 40min, performing suction filtration, and washing with distilled water to obtain purified graphite powder; (c) preparing manganese oxide powder: taking out solid manganese oxide in the waste zinc-manganese battery, washing with hot water at 60 ℃, drying, grinding by a ball mill, and sieving by a 60-mesh sample sieve; (d) preparing zinc sheets: stripping a zinc skin shell of the waste zinc-manganese battery, washing with hot water at 60 ℃, and cutting into zinc sheets smaller than 2 x 2 cm; (e) reaction: mixing certain amounts of purified graphite powder, manganese oxide powder and K 2 S 2 O 8 Adding to a volume of H 2 SO 4 Performing ultrasonic treatment for 10h to turn the solution into black brown, adding distilled water with the same volume as sulfuric acid and zinc sheets with certain mass, stirring at room temperature of 25 ℃ for reaction for 3h, standing for 40min, and collecting suspension; (f) separation: centrifuging to separate out precipitate in the suspension, wherein the centrifugal rotation speed is 10000r/min, and the centrifugal time is 12min; (g) drying: and (3) drying the obtained precipitate in a vacuum drying oven at room temperature of 25 ℃ to obtain black brown powder, namely the reduced graphene oxide of the invention. Wherein the mass ratio of the carbon rod powder to the sodium hydroxide is 1; the material-liquid ratio of the carbon rod powder to the dissolved alkali melt sample warm water is 1; the feed-liquid ratio of the carbon rod powder to the hydrochloric acid is 1; the purified graphite powder, manganese oxide powder and K 2 S 2 O 8 The mass ratio of (1); the feed-liquid ratio of the purified graphite powder to the sulfuric acid is 1; the mass ratio of the purified graphite powder to the zinc sheets is 1; h 2 SO 4 The mass concentration of the solution was 96%.
Example 3
A preparation method of reduced graphene oxide comprises the following steps: (a) preparing carbon rod powder: taking out the carbon rods in the waste zinc-manganese batteries, cleaning, drying, ball-milling, and sieving by using a 120-mesh sample sieve. (b) purifying graphite: uniformly mixing a certain amount of carbon rod powder and sodium hydroxide, putting the mixture into a nickel crucible, putting the nickel crucible into a high-temperature furnace for melting for 10min, taking out the nickel crucible for cooling, dissolving the cooled alkali melt sample with a certain volume of warm water at 40 ℃, filtering, adding a certain volume of 3.0mol/L hydrochloric acid into filter residue, stirring for 35min, performing suction filtration, and washing with distilled water to obtain purified graphite powder; (c) preparing manganese oxide powder: taking out solid manganese oxide in the waste zinc-manganese battery, washing with hot water at 60 ℃, drying, grinding by a ball mill, and sieving by a 40-mesh sample sieve; (d) preparing zinc sheets: stripping a zinc skin shell of the waste zinc-manganese battery, washing with hot water at 60 ℃, and cutting into zinc sheets smaller than 2 x 2 cm; (e) reaction: mixing certain amounts of purified graphite powder, manganese oxide powder and K 2 S 2 O 8 Adding to a volume of H 2 SO 4 Ultrasonic treating for 9 hr to turn the solution into black brown, adding distilled water and certain amount of sulfuric acidStirring the zinc sheet at room temperature of 25 ℃ for reaction for 2.5h, standing for 35min, and collecting suspension; (f) separation: centrifuging to separate out precipitate in the suspension, wherein the centrifugal speed is 9000r/min, and the centrifugal time is 11min; (g) drying: and (3) drying the obtained precipitate in a vacuum drying oven at room temperature of 25 ℃ to obtain black brown powder, namely the reduced graphene oxide. Wherein the mass ratio of the carbon rod powder to the sodium hydroxide is 1; the material-liquid ratio of the carbon rod powder to the dissolved alkali melt sample warm water is 1; the feed-liquid ratio of the carbon rod powder to the hydrochloric acid is 1; the purified graphite powder, manganese oxide powder and K 2 S 2 O 8 The mass ratio of (1); the feed liquid ratio of the purified graphite powder to the sulfuric acid is 1; the mass ratio of the purified graphite powder to the zinc sheets is 1; h 2 SO 4 The mass concentration of the solution was 95%.
Example 4
A preparation method of reduced graphene oxide comprises the following steps: (a) preparing carbon rod powder: taking out the carbon rods in the waste zinc-manganese batteries, cleaning, drying, ball-milling, and sieving by using a 80-mesh sample sieve. (b) purifying graphite: uniformly mixing a certain amount of carbon rod powder and sodium hydroxide, putting the mixture into a nickel crucible, and melting the mixture in a high-temperature furnace for 10min, wherein the mass ratio of the carbon rod powder to the sodium hydroxide is 1. Taking out and cooling, dissolving the cooled alkali melt sample with a certain volume of warm water at 40 ℃, filtering, adding a certain volume of 3.0mol/L hydrochloric acid into filter residue, stirring for 50min, performing suction filtration, and washing with distilled water to obtain purified graphite powder; wherein the feed-liquid ratio of the carbon rod powder to the dissolved alkali melt warm water is 1; the feed-liquid ratio of the carbon rod powder to the hydrochloric acid is 1; (c) preparing manganese oxide powder: taking out solid manganese oxide in the waste zinc-manganese battery, washing with hot water at 60 ℃, drying, grinding by a ball mill, and sieving by a 40-mesh sample sieve; (d) preparing zinc sheets: stripping a zinc skin shell of the waste zinc-manganese battery, washing with hot water at 60 ℃, and cutting into zinc sheets smaller than 2 x 2 cm; (e) reaction: mixing a certain amount of purified graphite powder, manganese oxide and K 2 S 2 O 8 Adding to a volume of H 2 SO 4 In the solution, ultrasonic treatment is carried out for 10 hours, and the solution is dissolvedChanging the liquid into black brown, adding distilled water with the same volume as sulfuric acid and a certain mass of zinc sheets (the mass ratio of the purified graphite powder to the zinc sheets is 1; wherein the purified graphite powder, manganese oxide powder and K 2 S 2 O 8 The mass ratio of (1); the feed-liquid ratio of the purified graphite powder to the sulfuric acid is 1; (f) separation: centrifuging to separate out precipitate in the suspension, wherein the centrifugal rotation speed is 8000r/min, and the centrifugal time is 10min; (g) drying: and (3) drying the obtained precipitate in a vacuum drying oven at room temperature of 25 ℃ to obtain black brown powder, namely the reduced graphene oxide of the invention. The reduced graphene oxide of the present example was measured by XRD (as shown in fig. 2), and the result shows that it is pure reduced graphene oxide; the peak positions 2. Theta. Were 23.05 each ° The intensity and position of the peak are matched with the literature value, no impurity peak is found, and the purity of the product is higher. Through the SEM photograph (as shown in fig. 3), the morphology of the reduced graphene oxide of the present embodiment is observed to be a wrinkled surface structure.
Example 5
A preparation method of reduced graphene oxide comprises the following steps: (a) preparing carbon rod powder: and taking out the carbon rods in the waste zinc-manganese batteries, cleaning, drying, grinding by using a ball mill, and sieving by using a 100-mesh sample sieve. (b) purifying graphite: uniformly mixing 5.0g of carbon rod powder and 10g of sodium hydroxide, putting the mixture into a nickel crucible, putting the nickel crucible into a high-temperature furnace with the furnace temperature of 480 ℃ for melting for 9min, taking out the nickel crucible for cooling, dissolving the cooled alkali melt sample by 120mL of warm water at 40 ℃, filtering, adding 25mL of 2.0mol/L hydrochloric acid into filter residue, stirring for 40min, carrying out suction filtration, and washing by using distilled water to obtain purified graphite powder; (c) preparing manganese oxide powder: taking out solid manganese oxide in the waste zinc-manganese battery, washing with hot water at 60 ℃, drying, grinding by a ball mill, and sieving by a 60-mesh sample sieve; (d) preparing zinc sheets: stripping a zinc skin shell of the waste zinc-manganese battery, washing at 60 ℃, and cutting into zinc sheets smaller than 2 x 2 cm; (e) reaction: 4g of purified graphite powder, 2.0g of manganese oxide powder and 0.8g of K 2 S 2 O 8 And 200mL of 98% by mass 2 SO 4 Add to a 500mL conePerforming ultrasonic treatment for 9h in a bottle-shaped bottle, changing the solution into black brown, adding 200mL of distilled water and 10g of zinc sheets, stirring at room temperature of 25 ℃ for reaction for 3h, standing for 35min, and collecting the suspension; (f) separation: centrifuging to separate out the precipitate in the suspension, wherein the centrifugal speed is 10000r/min, and the centrifugal time is 12min; (g) drying: and (3) drying the obtained precipitate in a vacuum drying oven at room temperature of 25 ℃ to obtain black brown powder, namely the reduced graphene oxide of the invention.
Example 6
A preparation method of reduced graphene oxide comprises the following steps: (a) preparing carbon rod powder: and taking out the carbon rods in the waste zinc-manganese batteries, cleaning, drying, grinding by using a ball mill, and sieving by using a 120-mesh sample sieve. (b) purifying graphite: uniformly mixing 3.0g of carbon rod powder and 6.3g of sodium hydroxide, putting the mixture into a nickel crucible, putting the nickel crucible into a high-temperature furnace with the furnace temperature of 420 ℃ for melting for 8min, taking out the mixture for cooling, dissolving the cooled alkali melt sample with 75mL of warm water at 40 ℃, filtering, adding 15mL of 2.5mol/L hydrochloric acid into filter residue, stirring for 55min, carrying out suction filtration, and washing with distilled water to obtain purified graphite powder; (c) preparing manganese oxide powder: taking out solid manganese oxide in the waste zinc-manganese battery, washing with hot water at 60 ℃, drying, grinding by a ball mill, and sieving by a 60-mesh sample sieve; (d) preparing zinc sheets: stripping a zinc skin shell of the waste zinc-manganese battery, washing with hot water at 60 ℃, and cutting into zinc sheets smaller than 2 x 2 cm; (e) reaction: 2.4g of purified graphite powder, 1.0g of manganese oxide powder and 0.70g of K 2 S 2 O 8 And 120mL of 98% by mass 2 SO 4 Adding into a 500mL conical flask, performing ultrasonic treatment for 8h to turn the solution into black brown, adding 120mL distilled water and 6g zinc sheet, stirring at room temperature of 25 ℃ for reaction for 2h, standing for 30min, and collecting the suspension; (f) separation: centrifuging to separate out precipitate in the suspension, wherein the centrifugal speed is 8000r/min, and the centrifugal time is 11min; (g) drying: and (3) drying the obtained precipitate in a vacuum drying oven at room temperature of 25 ℃ to obtain black brown powder, namely the reduced graphene oxide of the invention.
Example 7
A preparation method of reduced graphene oxide comprises the following steps: (a) preparing carbon rod powder: will wasteAnd taking out the carbon rod in the old zinc-manganese battery, cleaning, drying, grinding by using a ball mill, and sieving by using a 100-mesh sample sieve. (b) purifying graphite: uniformly mixing 8.0g of carbon rod powder and 15g of sodium hydroxide, putting the mixture into a nickel crucible, putting the nickel crucible into a high-temperature furnace with the furnace temperature of 430 ℃ for melting for 9min, taking out the nickel crucible for cooling, dissolving the cooled alkali melt sample with 180mL of warm water at 40 ℃, filtering, adding 48mL of 2.0mol/L hydrochloric acid into filter residue, stirring for 60min, carrying out suction filtration, and washing with distilled water to obtain purified graphite powder; (c) preparing manganese oxide powder: taking out solid manganese oxide in the waste zinc-manganese battery, washing with hot water at 60 ℃, drying, grinding by a ball mill, and sieving by a 40-mesh sample sieve; (d) preparing zinc sheets: peeling the zinc skin shell of the waste zinc-manganese dioxide battery, washing with hot water at 60 ℃, and cutting into zinc sheets smaller than 2 x 2 cm; (e) reaction: 6g of purified graphite powder, 2.4g of manganese oxide powder and 1.8g of K 2 S 2 O 8 And 300mL of 95% by mass 2 SO 4 Adding into a 1000mL conical flask, performing ultrasonic treatment for 10h to turn the solution into black brown, adding 300mL distilled water and 12g zinc sheet, stirring at room temperature of 25 ℃ for reaction for 3h, standing for 40min, and collecting the suspension; (f) separation: centrifuging to separate out the precipitate in the suspension, wherein the centrifugal speed is 9000r/min, and the centrifugal time is 10min; (g) drying: and (3) drying the obtained precipitate in a vacuum drying oven at room temperature of 25 ℃ to obtain black brown powder, namely the reduced graphene oxide of the invention.
Example 8
A preparation method of reduced graphene oxide comprises the following steps: (a) preparing carbon rod powder: taking out the carbon rods in the waste zinc-manganese batteries, cleaning, drying, grinding by using a ball mill, and sieving by using a 80-mesh sample sieve. (b) purifying graphite: uniformly mixing 6.0g of carbon rod powder and 12g of sodium hydroxide, putting the mixture into a nickel crucible, putting the nickel crucible into a high-temperature furnace with the furnace temperature of 480 ℃ for melting for 10min, taking out the nickel crucible for cooling, dissolving the cooled alkali melt sample by using 150mL of warm water with the temperature of 40 ℃, filtering, adding 32mL of 3.0mol/L hydrochloric acid into filter residue, stirring for 40min, carrying out suction filtration, and washing by using distilled water to obtain purified graphite powder; (c) preparing manganese oxide powder: taking out solid manganese oxide from waste zinc-manganese battery, washing with 60 deg.C hot water, drying, grinding with ball mill, and sampling with 60 meshSieving; (d) preparing zinc sheets: stripping a zinc skin shell of the waste zinc-manganese battery, washing with hot water at 60 ℃, and cutting into zinc sheets smaller than 2 x 2 cm; (e) reaction: 4.8g of purified graphite powder, 2.0g of manganese oxide powder and 1.2g of K 2 S 2 O 8 And 240mL of 98% by mass 2 SO 4 Adding into a 1000mL conical flask, performing ultrasonic treatment for 9h to turn the solution into black brown, adding 240mL of distilled water and 10g of zinc sheet, stirring at room temperature of 25 ℃ for reaction for 2.5h, standing for 35min, and collecting the suspension; (f) separation: centrifuging to separate out precipitate in the suspension, wherein the centrifugal rotation speed is 10000r/min, and the centrifugal time is 12min; (g) drying: and (3) drying the obtained precipitate in a vacuum drying oven at room temperature of 25 ℃ to obtain black brown powder, namely the reduced graphene oxide of the invention.
While embodiments of the present invention have been described above, the above description is illustrative, not exhaustive, and not limited to the disclosed embodiments. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (10)
1. A preparation method of reduced graphene oxide is characterized by comprising the following steps:
(1) Cleaning, drying, grinding and sieving carbon rods in the waste zinc-manganese batteries to obtain carbon rod powder;
(2) Mixing the carbon rod powder and sodium hydroxide, and then melting and cooling to obtain a cooled alkali melt sample; mixing the cooled alkali molten sample with water, filtering to obtain filter residue, and finally carrying out contact reaction on the filter residue and hydrochloric acid to obtain purified graphite powder;
(3) Washing, drying, grinding and sieving solid manganese oxide in the waste zinc-manganese battery to obtain manganese oxide powder;
(4) Stripping a zinc skin shell of the waste zinc-manganese battery, and then washing and cutting to obtain zinc sheets;
(5) The purified graphite powder, manganese oxide powder and K are mixed 2 S 2 O 8 And carrying out contact reaction with sulfuric acid, then adding water and zinc sheets, and continuing to carry out contact reaction to obtain the reduced graphene oxide.
2. The method according to claim 1, wherein the step (1) is carried out by sieving with a 80-120 mesh sieve.
3. The preparation method according to claim 1, wherein in the step (2), the melting temperature is 400-500 ℃ and the time is 8-10min;
the water is water with the temperature of 30-50 ℃;
and the contact reaction time of the filter residue and hydrochloric acid is 30-60min.
4. The production method according to claim 1, wherein in the step (2), the mass ratio of the carbon rod powder to the sodium hydroxide is 1.8-2.2;
the feed-liquid ratio of the carbon rod powder to water is 1;
the material-liquid ratio of the carbon rod powder to the hydrochloric acid is 1-6 g/ml; the concentration of the hydrochloric acid is 2-3mol/L.
5. The production method according to claim 1, wherein, in the step (3), washing with water; sieving with 40-60 mesh sieve.
6. The production method according to claim 1, wherein, in the step (4), washing with water; the cutting is to cut into zinc sheets smaller than 2 multiplied by 2 cm.
7. The production method according to claim 1, wherein in the step (5), the purified graphite powder, manganese oxide powder and K are mixed 2 S 2 O 8 The mass ratio of (1);
the feed liquid ratio of the purified graphite powder to the sulfuric acid is 1; the mass concentration of the sulfuric acid is 95-98%;
the mass ratio of the purified graphite powder to the zinc sheets is 1.
8. The production method according to claim 1, wherein in the step (5), the purified graphite powder, manganese oxide powder, K are used 2 S 2 O 8 Carrying out contact reaction with sulfuric acid for 8-10h;
the time for continuing the contact reaction is 2-3h.
9. The preparation method according to claim 1, wherein in the step (5), the reaction material after the continuous contact reaction is finished is allowed to stand to obtain a suspension; carrying out centrifugal separation on the suspension to obtain a precipitate; and drying the precipitate to obtain the reduced graphene oxide.
10. Reduced graphene oxide prepared by the preparation method according to any one of claims 1 to 9.
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| CN109825708A (en) * | 2019-01-25 | 2019-05-31 | 中南大学 | Method for recovering positive and negative electrode substances in waste alkaline zinc-manganese dioxide battery |
| CN110054178A (en) * | 2019-05-13 | 2019-07-26 | 华南理工大学 | A kind of method of the quick redox graphene of room temperature |
| CN111710882A (en) * | 2020-06-28 | 2020-09-25 | 金汤杰 | Process for preparing lithium battery negative electrode material by using waste zinc-manganese battery |
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