CN113651320A - Method for preparing nitrogen-doped porous reduced graphene oxide by recycling waste lithium ion battery negative electrode graphite material - Google Patents
Method for preparing nitrogen-doped porous reduced graphene oxide by recycling waste lithium ion battery negative electrode graphite material Download PDFInfo
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Abstract
The application discloses a method for preparing nitrogen-doped porous reduced graphene oxide by recycling waste lithium ion battery negative electrode graphite materials, which comprises the following steps: preparing graphene oxide by using a graphite material of a negative electrode of a waste lithium ion battery; graphene oxide, a nitrogen source, an activating agent and water are used as raw materials, and a graphene macroscopic body is prepared through constant-temperature reaction, hydrothermal reaction and freeze-drying; and calcining, acid washing, water washing and drying the graphene macroscopic body to obtain the nitrogen-doped porous reduced graphene oxide. According to the method, the advantage that the waste lithium ion battery cathode graphite material has expanded interlamellar spacing can be fully utilized, and the loose porous, large interlamellar spacing and nitrogen-doped reduced graphene oxide can be obtained through the chemical change of graphite-graphene oxide-graphene macroscopic body-nitrogen-doped porous reduced graphene oxide, and the method has a long-range ordered structure, is favorable for keeping stable structure in the ion intercalation process, and improves the electrochemical performance of the material prepared from the recovered graphite.
Description
Technical Field
The invention relates to the technical field of recycling of waste lithium ion batteries, in particular to a method for preparing nitrogen-doped porous reduced graphene oxide by recycling a graphite material of a negative electrode of a waste lithium ion battery.
Background
The lithium ion battery has the advantages of high energy density, no memory effect, good cycle performance, low self-discharge rate and the like. After the lithium ion battery is industrialized, the lead-acid battery, the nickel-metal hydride battery and the like are rapidly defeated, and the lithium ion battery is widely applied to electronic digital equipment, electric automobiles and other equipment. With the annual increase of the sales volume of electric automobiles, the demand of power batteries is continuously increasing. According to statistics, the decommissioning scale of the power lithium battery in 2025 years in China reaches 73 ten thousand tons, so that the problem of urgent need to be solved in the face of recovery treatment after decommissioning of a large number of power batteries is solved. The effective recovery and reuse of the waste lithium ion battery can extract valuable materials, reduce the energy consumption of natural resource development and reduce the environmental pollution.
In the waste lithium ion batteries, ternary positive electrode materials such as nickel-cobalt-manganese and lithium cobaltate have higher values, so the current recovery technology of the lithium ion batteries focuses on the positive electrode materials, and related researches on the recovery and resource utilization of graphite negative electrode materials are still not much. The recycled graphite cathode material has the beneficial effects of enlarged interlayer spacing and contribution to realizing high-power energy. At present, the recovery and impurity removal of graphite cathodes are mainly carried out in a high-temperature calcination mode, most of binders and thickening agents can be effectively removed, but metal impurities remained in graphite are difficult to remove, so that the electrochemical performance of the recovered graphite is poor, and a high-energy-consumption method is not green and environment-friendly.
Disclosure of Invention
The application aims to provide a method for preparing nitrogen-doped porous reduced graphene oxide by recycling waste lithium ion battery negative graphite materials.
In order to achieve the purpose, the following technical scheme is adopted in the application:
the first aspect of the application discloses a method for preparing nitrogen-doped porous reduced graphene oxide by recycling waste lithium ion battery negative electrode graphite materials, which comprises the following steps:
preparing graphene oxide by using a graphite material of a negative electrode of a waste lithium ion battery;
graphene oxide, a nitrogen source, an activating agent and water are used as raw materials, and a graphene macroscopic body is prepared through constant-temperature reaction, hydrothermal reaction and freeze-drying;
and calcining, acid washing, water washing and drying the graphene macroscopic body to obtain the nitrogen-doped porous reduced graphene oxide.
It should be noted that, by recycling the graphite material of the negative electrode of the waste lithium ion battery, the method can fully utilize the advantage of the enlarged interlayer spacing of the graphite material of the negative electrode of the waste lithium ion battery, and obtain the loose, porous, large-interlayer spacing and nitrogen-doped reduced graphene oxide through the chemical change of graphite-graphene oxide-graphene macroscopic body-nitrogen-doped porous reduced graphene oxide.
Specifically, N can be introduced into graphene oxide through a constant temperature reaction, nitrogen atom doping can provide more active sites, and the carbon layer spacing is enlarged; the hydrothermal reaction can decompose carboxyl and hydroxyl on graphene oxide at high temperature and high pressure so as to reduce the graphene oxide, and the graphene macroscopic body obtained by freeze-drying has the characteristics of looseness, porosity, large specific surface area, three-dimensional sponge shape, low density, ultralight weight and stable structure; the method comprises the steps of calcining to remove oxygen-containing functional groups of a graphene macroscopic body to form a large number of defect structures and active sites, pickling to remove residual nitrate radicals, manganese ions and other impurities of the graphene macroscopic body, and washing with water to remove manganese sulfate, residual acid radical ions and metal ions in the graphene macroscopic body, so that the nitrogen-doped porous reduced graphene oxide prepared from the waste lithium ion battery cathode graphite material is obtained, and the electrochemical performance of the material prepared from recovered graphite is improved.
In an implementation manner of the present application, graphene oxide, a nitrogen source, an activator and water are used as raw materials, and the graphene macroscopic body prepared by constant temperature reaction, hydrothermal reaction and freeze-drying specifically includes:
mixing graphene oxide, a nitrogen source, an activating agent and water, reacting at a constant temperature, drying, and dissolving in water to obtain a graphene oxide aqueous solution;
and carrying out hydrothermal reaction and freeze-drying on the graphene oxide aqueous solution to obtain the graphene macroscopic body.
In an implementation manner of the present application, the mass ratio of the graphene oxide, the nitrogen source, and the activating agent is 1: (1-3): (1-3);
the nitrogen source is at least one of melamine, thiourea, polyaniline, ammonium chloride, urea, o-phenanthroline, biuret, ammonium nitrate and dicyandiamide;
the activating agent is at least one of potassium hydroxide, sodium hydroxide, potassium bicarbonate, phosphoric acid, zinc chloride, potassium acetate and potassium oxalate.
In one implementation mode of the method, the reaction temperature of the constant-temperature reaction is 70-90 ℃, and the hydrothermal time is 2-4 h;
the reaction temperature of the hydrothermal reaction is 100-180 ℃, and the reaction time is 10-24 h;
the calcining temperature is 700-900 ℃, and the calcining time is 1-3 h;
the acid adopted for acid washing is as follows: at least one of acetic acid, nitric acid, carbonic acid and phosphoric acid.
In an implementation manner of the present application, the method further includes, before preparing graphene oxide from a graphite material of a negative electrode of a waste lithium ion battery:
disassembling the waste lithium ion battery to obtain a graphite cathode;
soaking the graphite cathode in ethanol for ultrasonic treatment to peel and separate graphite on the cathode sheet from the copper foil so as to obtain mixed liquid containing graphite;
taking out the copper foil in the mixed liquid containing the graphite, carrying out suction filtration on the mixed liquid containing the graphite, and placing filter residues in an oven for drying to obtain a graphite body;
and (3) carrying out acid washing and water washing on the graphite body to be neutral and drying to obtain the graphite material of the waste lithium ion battery cathode.
In an implementation manner of the present application, the preparation of graphene oxide from graphite materials of the negative electrode of the waste lithium ion battery specifically includes:
the graphene oxide is prepared by utilizing a graphite material of a negative electrode of a waste lithium ion battery and adopting an improved Hummers method.
The second aspect of the application discloses nitrogen-doped porous reduced graphene oxide prepared by the preparation method.
The third aspect of the application discloses an application of the nitrogen-doped porous reduced graphene oxide in a potassium ion battery.
A fourth aspect of the present application discloses a negative electrode using the above nitrogen-doped porous reduced graphene oxide.
A fifth aspect of the present application discloses a potassium ion battery employing the above negative electrode.
The method has the advantages that compared with the common graphite material, the nitrogen-doped porous reduced graphene oxide prepared by recycling the waste lithium ion battery cathode graphite material has larger interlayer spacing due to overlong circulation, nitrogen atom doping can provide more active sites, the battery capacity is effectively improved, and the carbon layer spacing can be enlarged by nitrogen doping, so that the method is beneficial to keeping stable structure in the charging and discharging process and is convenient for the embedding and the removing of potassium ions; the porous structure shortens the ion diffusion distance and improves the multiplying power performance of the battery; the defect area of the in-plane porous graphene is increased, so that the pi-pi interaction between graphene sheet layers is weakened, the stacking problem of the graphene sheet layers is relieved, the in-plane porous graphene sheet layers can have more active surfaces, the edges of the in-plane porous graphene sheet layers have abundant chemical active sites, the in-plane porous graphene sheet layers have high catalytic activity, the in-plane porous graphene sheet layers have more active sites and larger effective surface area of electrochemical reaction, and the energy density of the battery is improved.
In one implementation manner of the present application, the electrolyte of the potassium ion battery is an ester electrolyte;
preferably, the solvent of the ester electrolyte includes one or more of Ethylene Carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC) and Ethyl Methyl Carbonate (EMC).
Preferably, the solute of the ester electrolyte is KPF6KFSI, KTFSI and KCF3SO3One or more of (a).
Due to the adoption of the technical scheme, the beneficial effects of the application are as follows:
according to the method, the graphite material of the negative electrode of the waste lithium ion battery is recovered, the advantage that the graphite material of the negative electrode of the waste lithium ion battery has expanded interlayer spacing can be fully utilized, and the loose, porous, large-interlayer spacing and nitrogen-doped reduced graphene oxide is obtained through the chemical change of graphite-graphene oxide-graphene macroscopic body-nitrogen-doped porous reduced graphene oxide, has a long-range ordered structure, is beneficial to keeping stable structure in the ion intercalation process, and improves the electrochemical performance of the material prepared from the recovered graphite.
Drawings
Fig. 1 is a scanning electron microscope image of nitrogen-doped porous reduced graphene oxide provided in example 1;
fig. 2 is a scanning electron microscope image of a specific element in a micro region of nitrogen-doped porous reduced graphene oxide provided in example 1.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments. In the following description, numerous details are set forth in order to provide a better understanding of the present application. However, those skilled in the art will readily recognize that some of the features may be omitted or replaced with other elements, materials, methods in different instances. In some instances, certain operations related to the present application have not been shown or described in detail in order to avoid obscuring the core of the present application from excessive description, and it is not necessary for those skilled in the art to describe these operations in detail, so that they may be fully understood from the description in the specification and the general knowledge in the art.
Furthermore, the features, operations, or characteristics described in the specification may be combined in any suitable manner to form various embodiments. Also, the various steps or actions in the method descriptions may be transposed or transposed in order, as will be apparent to one of ordinary skill in the art. Thus, the various sequences in the specification are for the purpose of clearly describing one embodiment only and are not meant to be necessarily order unless otherwise indicated where a certain order must be followed.
All starting materials for this application, without particular limitation as to their source, are either commercially available or prepared according to conventional methods well known to those skilled in the art.
All the raw materials in the present application are not particularly limited in purity, and the present invention preferably employs purity which is conventional in the field of analytical purification or air battery materials.
Example 1
A method for preparing nitrogen-doped porous reduced graphene oxide by recycling waste lithium ion battery graphite negative electrodes specifically comprises the following steps:
fully discharging the waste lithium ion battery, disassembling the shell, and stripping the battery cell to obtain a graphite cathode; soaking a graphite cathode in ethanol, wherein the mass ratio of the graphite cathode to the ethanol is 1:30, then carrying out ultrasonic treatment to peel and separate graphite from a copper foil, wherein the ultrasonic time is 1h and the ultrasonic frequency is 30KHz, taking out the copper foil, carrying out suction filtration on a mixed solution containing the graphite, and drying filter residues in an oven at 80 ℃ for 12 h. And soaking the dried graphite body into a 2:1 acetic acid solution, stirring for 1h, taking the precipitate, washing the precipitate to be neutral, and drying in a drying oven at 100 ℃ to obtain the negative electrode graphite material.
The graphene oxide is prepared by taking a graphite cathode as a raw material and adopting an improved Hummers method. The preparation method comprises the following steps: the cryostat was kept below-5 ℃, 8g of crystalline flake graphite and 4g of sodium nitrate were added to a glass beaker, and the glass beaker was placed in the cryostat and the powder was stirred for 10 min. After stirring uniformly, 190mL of concentrated sulfuric acid is added, and stirring is kept while adding sulfuric acid. After 20min, potassium permanganate is added, 32g of potassium permanganate is slowly added, a small amount of potassium permanganate is added for many times, and the temperature of reactants is controlled to be not higher than 15 ℃. After the potassium permanganate is added, the reactants are kept to continue to react for 2 hours under the low-temperature condition, and then the medium-temperature reaction stage is carried out. The reaction was warmed to 35 ℃ and incubated for 30min, after which 380mL of deionized water was added slowly dropwise. Then a high-temperature reaction stage is carried out, the temperature of the system is increased to be more than 95 ℃, and the temperature is kept for 1 h. The reaction product was diluted with 300mL of deionized water and 45mL of 30% aqueous hydrogen peroxide was added. Finally, a separation and washing step, in which the above reaction solution is filtered with filter paper, and the filter cake is washed with 5% dilute hydrochloric acid. Preparing the filter cake after the hydrochloric acid cleaning into an aqueous solution again, further adopting centrifugal washing, wherein the centrifugal rotating speed is 6000 r/min, each centrifugal time is 12 min until the supernatant is weakly acidic, drying the centrifuged precipitate to obtain graphite oxide, and stripping the graphite oxide into graphene oxide by utilizing ultrasonic, wherein the ultrasonic time is 1h, and the ultrasonic frequency is 40 KHz.
Mixing the ground graphene oxide, melamine and potassium oxalate in 80mL of deionized water according to the mass ratio of 1:1:1, controlling the heating temperature at 80 ℃, keeping the heating temperature for 2 hours, and drying in a drying oven at 80 ℃ for 24 hours. Mixing and ultrasonically treating the dried sample and deionized water to prepare a solution with the concentration of 2mgmL-1The aqueous solution of graphene oxide of (1). 80mL of the solution with the concentration of 2mgmL is taken-1Placing the graphene oxide aqueous solution in a hydrothermal kettle, placing the hydrothermal kettle in an explosion-proof oven at 180 ℃ for hydrothermal for 12 hours, and obtaining the hydrogel after the hydrothermal reaction is finished. And (3) freeze-drying the hydrogel to obtain a graphene oxide macroscopic body, and mashing the graphene oxide macroscopic body into powder.
Placing the graphene oxide macroscopic body in a tube furnace, and carrying out heat treatment at 800 ℃ for 2h at the heating rate of 5 ℃ for min-1Argon is taken as protective atmosphere. And soaking the heat-treated sample in a 3M hydrochloric acid solution, washing with deionized water and alcohol for three times respectively, and drying the material by using a forced air oven to obtain the nitrogen-doped porous reduced graphene oxide material serving as the negative electrode material of the potassium ion battery. Nitrogen-doped porous reduced graphene oxide prepared by the embodimentThe scanning electron microscope image of (a) is shown in fig. 1, and a scanning electron microscope image of fig. 2 is obtained by scanning a specific element on a microscopic region of the nitrogen-doped porous reduced graphene oxide prepared in this example.
Example 2
A method for preparing nitrogen-doped porous reduced graphene oxide by recycling waste lithium ion battery graphite negative electrodes specifically comprises the following steps:
fully discharging the waste lithium ion battery, disassembling the shell, and stripping the battery cell to obtain a graphite cathode; soaking a graphite cathode in ethanol, wherein the mass ratio of the graphite cathode to the ethanol is 1:30, then carrying out ultrasonic treatment to peel and separate graphite from a copper foil, wherein the ultrasonic time is 1h and the ultrasonic frequency is 30KHz, taking out the copper foil, carrying out suction filtration on a mixed solution containing the graphite, and drying filter residues in an oven at 80 ℃ for 12 h. And soaking the dried graphite body into a 2:1 acetic acid solution, stirring for 1h, taking the precipitate, washing the precipitate to be neutral, and drying in a drying oven at 100 ℃ to obtain the negative electrode graphite material.
The graphene oxide is prepared by taking a graphite cathode as a raw material and adopting an improved Hummers method. The specific preparation process is referred to example 1.
Mixing the ground graphene oxide, melamine and potassium oxalate in 80mL of deionized water according to the mass ratio of 1:1:2, controlling the heating temperature at 80 ℃, keeping the heating temperature for 2 hours, and drying in a drying oven at 80 ℃ for 24 hours. Mixing and ultrasonically treating the dried sample and deionized water to prepare a solution with the concentration of 2mgmL-1The aqueous solution of graphene oxide of (1). 80mL of the solution with the concentration of 2mgmL is taken-1Placing the graphene oxide aqueous solution in a hydrothermal kettle, placing the hydrothermal kettle in an explosion-proof oven at 180 ℃ for hydrothermal for 12 hours, and obtaining the hydrogel after the hydrothermal reaction is finished. And (3) freeze-drying the hydrogel to obtain a graphene oxide macroscopic body, and mashing the graphene oxide macroscopic body into powder.
Placing the graphene oxide macroscopic body in a tube furnace, and carrying out heat treatment at 800 ℃ for 2h at the heating rate of 5 ℃ for min-1Argon is taken as protective atmosphere. Soaking the heat-treated sample in 3M hydrochloric acid solution, and respectively washing with deionized water and alcoholAnd drying the material by using a blast oven, and finally obtaining the nitrogen-doped porous reduced graphene oxide material which is used as the negative electrode material of the potassium ion battery.
Example 3
A method for preparing nitrogen-doped porous reduced graphene oxide by recycling waste lithium ion battery graphite negative electrodes specifically comprises the following steps:
fully discharging the waste lithium ion battery, disassembling the shell, and stripping the battery cell to obtain a graphite cathode; soaking a graphite cathode in ethanol, wherein the mass ratio of the graphite cathode to the ethanol is 1:30, then carrying out ultrasonic treatment to peel and separate graphite from a copper foil, wherein the ultrasonic time is 1h and the ultrasonic frequency is 30KHz, taking out the copper foil, carrying out suction filtration on a mixed solution containing the graphite, and drying filter residues in an oven at 80 ℃ for 12 h. And soaking the dried graphite body into a 2:1 acetic acid solution, stirring for 1h, taking the precipitate, washing the precipitate to be neutral, and drying in a drying oven at 100 ℃ to obtain the negative electrode graphite material.
The graphene oxide is prepared by taking a graphite cathode as a raw material and adopting an improved Hummers method. The specific preparation process is referred to example 1.
Mixing the ground graphene oxide, melamine and potassium oxalate in 80mL of deionized water according to the mass ratio of 1:2:1, controlling the heating temperature at 80 ℃, keeping the heating temperature for 2 hours, and drying in a drying oven at 80 ℃ for 24 hours. Mixing and ultrasonically treating the dried sample and deionized water to prepare a solution with the concentration of 2mgmL-1The aqueous solution of graphene oxide of (1). 80mL of the solution with the concentration of 2mgmL is taken-1Placing the graphene oxide aqueous solution in a hydrothermal kettle, placing the hydrothermal kettle in an explosion-proof oven at 180 ℃ for hydrothermal for 12 hours, and obtaining the hydrogel after the hydrothermal reaction is finished. And (3) freeze-drying the hydrogel to obtain a graphene oxide macroscopic body, and mashing the graphene oxide macroscopic body into powder.
Placing the graphene oxide macroscopic body in a tube furnace, and carrying out heat treatment at 800 ℃ for 2h at the heating rate of 5 ℃ for min-1Argon is taken as protective atmosphere. Soaking the heat-treated sample in 3M hydrochloric acid solution, washing with deionized water and alcohol for three times, and drying the material in a forced air ovenAnd then obtaining the nitrogen-doped porous reduced graphene oxide material which is used as a negative electrode material of the potassium ion battery.
Example 4
A method for preparing nitrogen-doped porous reduced graphene oxide by recycling waste lithium ion battery graphite negative electrodes specifically comprises the following steps:
fully discharging the waste lithium ion battery, disassembling the shell, and stripping the battery cell to obtain a graphite cathode; soaking a graphite cathode in ethanol, wherein the mass ratio of the graphite cathode to the ethanol is 1:30, then carrying out ultrasonic treatment to peel and separate graphite from a copper foil, wherein the ultrasonic time is 1h and the ultrasonic frequency is 30KHz, taking out the copper foil, carrying out suction filtration on a mixed solution containing the graphite, and drying filter residues in an oven at 80 ℃ for 12 h. And soaking the dried graphite body into a 2:1 acetic acid solution, stirring for 1h, taking the precipitate, washing the precipitate to be neutral, and drying in a drying oven at 100 ℃ to obtain the negative electrode graphite material.
The graphene oxide is prepared by taking a graphite cathode as a raw material and adopting an improved Hummers method. The specific preparation process is referred to example 1.
Mixing the ground graphene oxide, melamine and potassium oxalate in 80mL of deionized water according to the mass ratio of 1:2:2, controlling the heating temperature at 80 ℃, keeping for 2 hours, and drying in a drying oven at 80 ℃ for 24 hours. Mixing and ultrasonically treating the dried sample and deionized water to prepare a solution with the concentration of 2mgmL-1The aqueous solution of graphene oxide of (1). 80mL of the solution with the concentration of 2mgmL is taken-1Placing the graphene oxide aqueous solution in a hydrothermal kettle, placing the hydrothermal kettle in an explosion-proof oven at 180 ℃ for hydrothermal for 12 hours, and obtaining the hydrogel after the hydrothermal reaction is finished. And (3) freeze-drying the hydrogel to obtain a graphene oxide macroscopic body, and mashing the graphene oxide macroscopic body into powder.
Placing the graphene oxide macroscopic body in a tube furnace, and carrying out heat treatment at 800 ℃ for 2h at the heating rate of 5 ℃ for min-1Argon is taken as protective atmosphere. Soaking the heat-treated sample in 3M hydrochloric acid solution, washing with deionized water and alcohol for three times, and drying the material with a blast oven to obtain the nitrogen-doped porous reduced graphite oxideThe alkene material is used as a negative electrode material of the potassium ion battery.
Example 5
A method for preparing nitrogen-doped porous reduced graphene oxide by recycling waste lithium ion battery graphite negative electrodes specifically comprises the following steps:
fully discharging the waste lithium ion battery, disassembling the shell, and stripping the battery cell to obtain a graphite cathode; soaking a graphite cathode in ethanol, wherein the mass ratio of the graphite cathode to the ethanol is 1:30, then carrying out ultrasonic treatment to peel and separate graphite from a copper foil, wherein the ultrasonic time is 1h and the ultrasonic frequency is 30KHz, taking out the copper foil, carrying out suction filtration on a mixed solution containing the graphite, and drying filter residues in an oven at 80 ℃ for 12 h. And soaking the dried graphite body into a 2:1 acetic acid solution, stirring for 1h, taking the precipitate, washing the precipitate to be neutral, and drying in a drying oven at 100 ℃ to obtain the negative electrode graphite material.
The graphene oxide is prepared by taking a graphite cathode as a raw material and adopting an improved Hummers method. The specific preparation process is referred to example 1.
Mixing the ground graphene oxide, melamine and potassium oxalate in 80mL of deionized water according to the mass ratio of 1:3:2, controlling the heating temperature at 80 ℃, keeping the heating temperature for 2 hours, and drying in a drying oven at 80 ℃ for 24 hours. Mixing and ultrasonically treating the dried sample and deionized water to prepare a solution with the concentration of 2mgmL-1The aqueous solution of graphene oxide of (1). 80mL of the solution with the concentration of 2mgmL is taken-1Placing the graphene oxide aqueous solution in a hydrothermal kettle, placing the hydrothermal kettle in an explosion-proof oven at 180 ℃ for hydrothermal for 12 hours, and obtaining the hydrogel after the hydrothermal reaction is finished. And (3) freeze-drying the hydrogel to obtain a graphene oxide macroscopic body, and mashing the graphene oxide macroscopic body into powder.
Placing the graphene oxide macroscopic body in a tube furnace, and carrying out heat treatment at 800 ℃ for 2h at the heating rate of 5 ℃ for min-1Argon is taken as protective atmosphere. Soaking the heat-treated sample in a 3M hydrochloric acid solution, respectively washing with deionized water and alcohol for three times, and drying the material with a forced air oven to obtain a nitrogen-doped porous reduced graphene oxide material which is used as a potassium ion battery negative electrodeA pole material.
The present application has been described with reference to specific examples, which are provided only to aid understanding of the present invention and are not intended to limit the present invention. For a person skilled in the art to which the invention pertains, several simple deductions, modifications or substitutions may be made according to the idea of the invention.
Claims (10)
1. A preparation method for preparing nitrogen-doped porous reduced graphene oxide by recycling waste lithium ion battery negative electrode graphite materials is characterized by comprising the following steps:
preparing graphene oxide by using a graphite material of a negative electrode of a waste lithium ion battery;
graphene oxide, a nitrogen source, an activating agent and water are used as raw materials, and a graphene macroscopic body is prepared through constant-temperature reaction, hydrothermal reaction and freeze-drying;
and calcining, acid washing, water washing and drying the graphene macroscopic body to obtain the nitrogen-doped porous reduced graphene oxide.
2. The preparation method according to claim 1, wherein graphene oxide, a nitrogen source, an activator and water are used as raw materials, and the preparation of the graphene macroscopic body through constant-temperature reaction, hydrothermal reaction and freeze-drying specifically comprises the following steps:
mixing graphene oxide, a nitrogen source, an activating agent and water, reacting at a constant temperature, drying, and dissolving in water to obtain a graphene oxide aqueous solution;
carrying out hydrothermal reaction and freeze-drying on a graphene oxide aqueous solution to obtain a graphene macroscopic body;
the mass ratio of the graphene oxide to the nitrogen source to the activating agent is 1: (1-3): (1-3);
the nitrogen source is at least one of melamine, thiourea, polyaniline, ammonium chloride, urea, o-phenanthroline, biuret, ammonium nitrate and dicyandiamide;
the activating agent is at least one of potassium hydroxide, sodium hydroxide, potassium bicarbonate, phosphoric acid, zinc chloride, potassium acetate and potassium oxalate.
3. The preparation method according to claim 1 or 2, wherein the reaction temperature of the isothermal reaction is 70-90 ℃, and the hydrothermal time is 2-4 h;
the reaction temperature of the hydrothermal reaction is 100-180 ℃, and the reaction time is 10-24 h;
the calcining temperature is 700-900 ℃, and the calcining time is 1-3 h;
the acid adopted by the acid washing is as follows: at least one of acetic acid, nitric acid, carbonic acid and phosphoric acid.
4. The preparation method according to claim 1, wherein before the step of preparing the graphene oxide by using the graphite material of the cathode of the waste lithium ion battery, the preparation method further comprises:
disassembling the waste lithium ion battery to obtain a graphite cathode;
soaking the graphite cathode in ethanol for ultrasonic treatment to peel and separate graphite on the cathode sheet from the copper foil so as to obtain mixed liquid containing graphite;
taking out the copper foil in the mixed liquid containing the graphite, carrying out suction filtration on the mixed liquid containing the graphite, and placing filter residues in an oven for drying to obtain a graphite body;
and (3) carrying out acid washing and water washing on the graphite body to be neutral and drying to obtain the graphite material of the waste lithium ion battery cathode.
5. The preparation method according to claim 1, wherein the graphene oxide prepared by using the graphite material of the negative electrode of the waste lithium ion battery is specifically:
the graphene oxide is prepared by utilizing a graphite material of a negative electrode of a waste lithium ion battery and adopting an improved Hummers method.
6. A nitrogen-doped porous reduced graphene oxide prepared by the preparation method of any one of claims 1 to 5.
7. Use of the nitrogen-doped porous reduced graphene oxide according to claim 6 in a potassium ion battery.
8. A negative electrode using the nitrogen-doped porous reduced graphene oxide of claim 6.
9. A potassium ion battery using the anode according to claim 8.
10. The potassium ion battery of claim 9, wherein the electrolyte of the potassium ion battery is an ester electrolyte;
the solvent of the ester electrolyte comprises one or more of Ethylene Carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC) and Ethyl Methyl Carbonate (EMC);
the solute of the ester electrolyte is KPF6KFSI, KTFSI and KCF3SO3One or more of (a).
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