CN113942999A - A method for recycling graphite from negative electrode carbon powder of lithium battery and preparation method of graphene oxide - Google Patents
A method for recycling graphite from negative electrode carbon powder of lithium battery and preparation method of graphene oxide Download PDFInfo
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Abstract
本发明公开了一种锂电池负极碳粉回收石墨的方法及氧化石墨烯的制备方法，涉及电池回收领域，包括：将碳粉加入球磨机中；将球磨后的碳粉与氯化铵研磨；将混合物在氩气下焙烧；将碳粉放入容器中，控制温度40～70℃，插入超声震振动棒，超声处理；抽滤，得到石墨；将石墨与浓H2SO4混合，滴加KMnO4；加去离子水稀释，加入双氧水，过滤和洗涤，干燥，得氧化石墨，将氧化石墨分散在氢氧化钠溶液中，超声分离，离心，过滤，洗涤，干燥。本发明的有益效果是球磨处理碳粉，用低温氯化焙烧的方法处理负极材料，水浸并施加超声场，将负极碳粉中的锂、钴、镍、锰、铜等金属浸出，经沉淀及分离提纯，获得再生石墨后氧化处理得氧化石墨烯。The invention discloses a method for recovering graphite from a negative electrode carbon powder of a lithium battery and a method for preparing graphene oxide, and relates to the field of battery recycling, comprising: adding carbon powder to a ball mill; grinding the ball-milled carbon powder with ammonium chloride; The mixture is roasted under argon; the carbon powder is put into a container, the temperature is controlled at 40-70 ° C, an ultrasonic vibration rod is inserted, and ultrasonic treatment is performed; suction filtration is performed to obtain graphite ; 4 ; dilute with deionized water, add hydrogen peroxide, filter and wash, dry to obtain graphite oxide, disperse the graphite oxide in sodium hydroxide solution, ultrasonically separate, centrifuge, filter, wash, and dry. The beneficial effects of the present invention are that the carbon powder is processed by ball milling, the negative electrode material is treated by a low-temperature chlorination roasting method, water immersed and an ultrasonic field is applied, and metals such as lithium, cobalt, nickel, manganese, and copper in the negative electrode carbon powder are leached out, and then precipitated. and separation and purification to obtain regenerated graphite and then oxidized to obtain graphene oxide.
Description
Technical Field
The invention relates to the technical field of battery recovery, in particular to a method for recovering graphite from lithium battery cathode carbon powder and a preparation method of graphene oxide.
Background
Lithium ion batteries are almost related to various aspects of human life due to their high energy density and efficiency, as well as long cycle life and environmental friendliness. Since these batteries can be used for portable devices, notebook computers, personal computers, and cellular phones, and can constitute a high-power source for electric vehicles. The potential application significance is great. However, the service life of the lithium battery is usually two to three years, so the number of the waste lithium batteries is greatly increased, and the environment is seriously polluted.
How to solve the problem of environmental pollution caused by lithium batteries also becomes a research hotspot of global scientists. The waste lithium ion battery contains chemical substances such as lithium hexafluorophosphate, polyvinylidene fluoride and the like, and toxic metals such as cobalt, copper, nickel, manganese, aluminum and the like. Cobalt and lithium in these metals are more valuable than their families. This means that the economic benefit that the spent lithium ion battery can produce if it can be effectively recycled is predictable. If not properly handled, leaching of toxic metals and release of electrolytes, the disposal of lithium batteries can threaten ecosystem and human health.
The current separation process for treating waste lithium ion batteries goes through three steps: (1) discharging the waste battery, peeling the shell, and screening to obtain the electrode material. (2) The electrode material is dissolved and leached, so that various metals are leached into the solution. (3) And (4) separating and recovering the metal in the dissolved solution or directly synthesizing an electrode material. The upgrading cycle of the negative electrode material is less concerned, and the negative electrode material accounts for 12-21% of the total mass of the waste lithium ion battery. However, the number of discarded lithium batteries in China is huge, and if the negative electrode materials of the lithium batteries cannot be effectively recycled, the negative electrode materials cause great harm to the environments such as water, soil and the like. The structure and oxidation of negative electrode graphite after failure can vary due to the operating voltage of lithium ion batteries and the wide variation of electrolytes, binders, and conductive agents. More importantly, the type, generation and removal mechanisms of organic and inorganic contaminants on the graphite electrodes of spent lithium ion batteries will become more complex. Therefore, based on the complex pollutants adsorbed by the graphite electrode of the multi-source waste lithium ion battery, the waste graphite is urgently required to be prepared into regenerated graphite or graphene, and the development of high-value utilization of the waste graphite is greatly promoted.
Disclosure of Invention
The invention aims to at least solve one of the technical problems in the prior art and provides a method for recovering graphite from lithium battery negative carbon powder and a preparation method of graphene oxide. And then carrying out oxidation, ultrasonic treatment and the like on the recovered graphite to obtain the graphene oxide.
The technical solution of the invention is as follows:
a method for recycling graphite from lithium battery cathode carbon powder is characterized by comprising the following steps:
(1) adding negative electrode material carbon powder into a ball mill, and grinding into fine particles;
(2) mixing the negative electrode material carbon powder subjected to ball milling in the step (1) with ammonium chloride, and fully grinding to obtain a mixture;
(3) placing the ground mixture obtained in the step (2) in a container, and roasting for 15-60 min under the argon atmosphere and at the temperature of 280-500 ℃;
(4) putting the roasted negative electrode material carbon powder in the step (3) into a container, adding deionized water, controlling the temperature of the solution to be 40-70 ℃, inserting an ultrasonic vibration rod into the solution, opening the ultrasonic vibration rod, and carrying out ultrasonic treatment for 1-3 hours;
(5) and (4) after the reaction in the step (4) is finished, carrying out suction filtration on the reaction liquid to obtain graphite.
Preferably, in the step (1), negative electrode material carbon powder is added into the ball mill, the rotating speed of the ball mill is controlled to be 300-500 r/min, and the ball milling time is controlled to be 30-90 min.
Preferably, in the step (2), the negative electrode material carbon powder subjected to ball milling in the step (1) is mixed with ammonium chloride according to a mass ratio of 1-4: 1.
Preferably, in the step (3), the temperature rise rate is 2-10 ℃/min.
Preferably, in the step (4), the power of the ultrasonic vibration vibrator is controlled to be 100-300W.
Preferably, the solid obtained after suction filtration is washed with deionized water for 2-3 times, and then dried for 20-28 hours to obtain graphite.
The invention also provides a preparation method of graphene oxide, which is used for preparing the graphene oxide by taking the recovered graphite as a raw material, and the specific preparation method comprises the following steps:
s1, drying the recovered graphite, and then mixing the graphite with concentrated H2SO4Mixing in a beaker, and fixing the beaker in a low-temperature reactor;
s2, mixing KMnO4Slowly adding the mixture into a beaker in batches at a constant speed, keeping the temperature of a reaction system at 1-5 ℃, reacting for 10-40 min, and then raising the temperature to 25-50 ℃;
s3, adding ionized water into the beaker to 100mL, and then adding hydrogen peroxide into the suspension to terminate gas generation;
s4, filtering and washing the mixture obtained in the step S3 with hydrochloric acid and deionized water, and then drying the solid-phase product at 40-80 ℃ to obtain graphite oxide;
s5, dispersing the graphite oxide obtained in the step S4 in 50mL of sodium hydroxide solution, and carrying out ultrasonic reaction for 2 hours at the temperature of 40-50 ℃ under the condition of 150-300W;
s6, centrifuging the solution obtained in the step S5, and removing impurities to obtain a stable graphene oxide suspension;
s7, vacuum-filtering and collecting the suspension liquid obtained in the step S6 through a microfiltration membrane, washing the graphene product with deionized water for several times, and then drying to obtain graphene oxide.
Preferably, in the step S1, every 1g of graphite is mixed with 10-30 mL of concentrated H2SO4Mixing;
preferably, in the step S2, KMnO4The addition amount of (A) is 1-3.5 times of the mass of the graphite.
Preferably, in the step S3, the hydrogen peroxide is added until bubbles no longer appear in the solution, and then the addition is stopped;
preferably, in step S5, the graphite oxide is dispersed in 50mL of a sodium hydroxide solution per 0.1 to 0.3g of the graphite oxide, and the pH of the sodium hydroxide solution is 9 to 11.
Preferably, in the step S6, the solution of the step S5 is centrifuged at 10000rpm for 3min to remove impurities;
preferably, in the step S7, the suspension obtained in the step S6 is vacuum-filtered and collected through a 0.22 μm microfiltration membrane, and the graphene product is washed with deionized water for several times and then dried at 40-80 ℃ for 24 hours to obtain graphene oxide.
According to the invention, the carbon powder is treated by ball milling, the particle size of the carbon powder is reduced after ball milling, the specific surface area of the carbon powder is increased, the carbon powder can be fully contacted with ammonium chloride, and the chlorination conversion efficiency is effectively improved; and then treating the waste lithium ion battery cathode material by using a low-temperature chlorination roasting method, then soaking in water and applying an ultrasonic field, leaching valuable metals such as lithium, cobalt, nickel, manganese, copper and the like in the lithium battery cathode carbon powder into the leachate, and performing reprecipitation, separation and purification to obtain a recyclable graphite material. Then the invention takes the recovered high-purity graphite as raw material and adds concentrated H2SO4Treating graphite powder, and then adding KMnO4Oxidizing graphite to obtain high-concentration H2SO4And KMnO4 oxidationThen, oxygen-containing groups are inserted between the graphite oxide layers. The oxidation reaction between graphite layers causes some oxygen-containing groups to appear, thereby improving the water solubility and the dispersibility of the graphite oxide. By controlling the electrostatic repulsion between layers under different pH values, stable graphite oxide suspension can be obtained. The oxidation treatment of the process can oxidize graphite into graphite oxide, so that graphene oxide can be obtained under the mechanical stress of an ultrasonic field, the obtained graphene oxide has few surface holes, and a dispersion layer in an organic solvent is not easy to curl. The method and the process are applied to the lithium ion battery cathode material with larger waste amount, and the carbon powder is purified, recovered and reused, thereby generating larger economic value. The method can organically combine the chlorination roasting of the lithium battery and the resource recovery, thereby realizing the effective purification and resource utilization of the carbon powder of the cathode material of the waste lithium ion battery.
The invention has at least one of the following beneficial effects:
1. after the lithium battery cathode material carbon powder is subjected to ball milling, the particle size is reduced, the specific surface area of the carbon powder is increased, the carbon powder is fully contacted with ammonium chloride, and the chlorination conversion efficiency is effectively improved. Different from the common wet method, the ammonium chloride used in the invention has low toxicity, low cost, capability of evaporation and recovery and environmental protection.
2. The method disperses the agglomerated carbon powder through the ultrasonic field, accelerates the speed of particles in the solution, makes the particle collision more violent, accelerates the dissolution of chloride, increases the leaching efficiency and also increases the formation of graphene oxide.
3. The invention has simple process, low energy consumption and low cost due to low-temperature roasting for front-end graphite purification.
4. The method provided by the invention is applied to the lithium ion battery cathode material with larger waste amount, has obvious effects of purifying, recycling and reusing carbon powder and recovering heavy metals, and generates larger economic value.
5. The invention takes graphite recovered from a negative electrode material as a raw material, and concentrated H is added2SO4Treating graphite, and adding KMnO4Oxidizing graphite into graphite oxide to obtain graphene oxide under the mechanical stress of an ultrasonic field, wherein the obtained graphene oxide has few surface holes and is organicThe dispersed layer in the solvent is not easy to curl, and the resistivity of the reduced graphene is high.
Detailed Description
The present invention will be described in further detail with reference to the following examples, but the present invention is not limited to the following examples.
Example 1
A method for recovering graphite from lithium battery cathode carbon powder and preparing graphene oxide by taking the recovered graphite as a raw material comprises the following specific steps:
(1) 3g of lithium battery negative electrode material carbon powder is added into the ball mill, the rotating speed is controlled to be 380r/min, and the ball milling is carried out for 60 min.
(2) 9g of ammonium chloride and 3g of negative electrode material carbon powder were sufficiently ground.
(3) And (3) placing the ground mixture into a tube furnace, heating to 300 ℃ at a heating rate of 5 ℃/min under an argon atmosphere, and then roasting for 30 min.
(4) And after the roasting is finished, taking out the carbon powder, putting the carbon powder into a 250mL beaker, adding 100mL deionized water, controlling the temperature to be 40 ℃, inserting an ultrasonic vibration vibrating rod into the solution, turning on the ultrasonic vibration vibrating rod, controlling the power to be 150W, and controlling the ultrasonic time to be 1 h.
(5) And after the reaction is finished, leaching the leaching solution and carbon powder, washing the carbon powder with deionized water for 3 times, and drying for 24 hours to obtain graphite.
(6) After the graphite obtained in the step (5) is dried, 1g of graphite and 30mL of concentrated H are added2SO4Mix in a beaker, fix the beaker in the low temperature reactor.
(7) 2.5g of KMnO4Slowly added in portions at a constant speed to the beaker of step (6). The temperature of the reaction system was maintained at 5 ℃ and the reaction was carried out for 30min, and then the temperature was raised to 35 ℃.
(8) And (4) adding ionic water into the beaker in the step (7) to 100mL, and then adding hydrogen peroxide into the suspension until no gas is generated.
(9) Filtering and washing the mixture obtained in the step (8) by using hydrochloric acid and deionized water. And finally, drying the solid-phase product at 60 ℃ to obtain the graphite oxide.
(10) 0.2g of graphite oxide obtained in step (9) was dispersed in 50mL of a sodium hydroxide solution (pH 11) and subjected to ultrasonic reaction at 40 ℃ for 2 hours under 150W.
(11) And (4) centrifuging the solution obtained in the step (10) at 10000rpm for 3min to remove impurities, so as to obtain the stable graphene oxide suspension.
(12) The suspension of step (11) was collected by vacuum filtration through a 0.22 μm microfiltration membrane. And finally, washing the graphene product with deionized water for several times, and drying at 60 ℃ for 24 hours to obtain the graphene oxide.
Example 2
A method for recovering graphite from lithium battery cathode carbon powder and a method for preparing graphene oxide by taking the recovered graphite as a raw material comprise the following specific steps:
(1) 3g of lithium battery negative electrode material carbon powder is added into the ball mill, the rotating speed is controlled to be 300r/min, and the ball milling is carried out for 90 min.
(2) 3g of ammonium chloride and 3g of negative electrode material carbon powder were sufficiently ground.
(3) And (3) placing the ground mixture into a tube furnace, heating to 380 ℃ at a heating rate of 2 ℃/min under an argon atmosphere, and then roasting for 30 min.
(4) And after the roasting is finished, taking out the carbon powder, putting the carbon powder into a 250mL beaker, adding 100mL deionized water, controlling the temperature to be 50 ℃, inserting an ultrasonic vibration vibrating rod into the solution, turning on the ultrasonic vibration vibrating rod, controlling the power to be 200W, and controlling the ultrasonic time to be 1.5 h.
(5) And after the reaction is finished, leaching the leaching solution and carbon powder, washing the carbon powder with deionized water for 3 times, and drying for 24 hours to obtain graphite.
(6) Drying the graphite obtained in the step (5), and mixing 1g of graphite with 10mL of concentrated H2SO4Mix in a beaker, fix the beaker in the low temperature reactor.
(7) 1gKMnO4Slowly added in portions at a constant speed to the beaker of step (6). The temperature of the reaction system was maintained at 4 ℃ and the reaction was carried out for 30min, and then the temperature was raised to 25 ℃.
(8) And (4) adding the ionic water into the beaker in the step (7) to 100mL, then adding hydrogen peroxide into the suspension until bubbles do not appear in the solution any more, and stopping adding the hydrogen peroxide to stop generating the gas.
(9) Filtering and washing the mixture obtained in the step (8) by using hydrochloric acid and deionized water. And finally, drying the solid-phase product at 50 ℃ to obtain the graphite oxide.
(10) 0.2g of graphite oxide obtained in step (9) was dispersed in 50mL of a sodium hydroxide solution (pH 10.5) and subjected to ultrasonic reaction at 45 ℃ for 2 hours under 200W.
(11) And (4) centrifuging the solution obtained in the step (10) at 10000rpm for 3min to remove impurities, so as to obtain the stable graphene oxide suspension.
(12) The suspension of step (11) was collected by vacuum filtration through a 0.22 μm microfiltration membrane. And finally, washing the graphene product with deionized water for several times, and drying at 40 ℃ for 24 hours to obtain the graphene oxide.
Example 3
A method for recovering graphite from lithium battery cathode carbon powder and a method for preparing graphene oxide by taking the recovered graphite as a raw material comprise the following specific steps:
(1) 3g of lithium battery negative electrode material carbon powder is added into the ball mill, the rotating speed is controlled to be 450r/min, and the ball milling is carried out for 45 min.
(2) 6g of ammonium chloride and 3g of negative electrode material carbon powder were sufficiently ground.
(3) And (3) placing the ground mixture into a tube furnace, heating to 450 ℃ at a heating rate of 8 ℃/min under an argon atmosphere, and then roasting for 30 min.
(4) And after the roasting is finished, taking out the carbon powder, putting the carbon powder into a 250mL beaker, adding 100mL deionized water, controlling the temperature to be 60 ℃, inserting an ultrasonic vibration vibrating rod into the solution, turning on the ultrasonic vibration vibrating rod, controlling the power to be 250W, and controlling the ultrasonic time to be 2 h.
(5) And after the reaction is finished, leaching the leaching solution and carbon powder, washing the carbon powder with deionized water for 3 times, and drying for 24 hours to obtain graphite.
(6) After the graphite obtained in the step (5) is dried, 1g of graphite and 20mL of concentrated H2SO4Mix in a beaker, fix the beaker in the low temperature reactor.
(7) 2gKMnO4Slowly added in portions at a constant speed to the beaker of step (6). The temperature of the reaction system was maintained at 3 ℃ and the reaction was carried out for 30min, and then the temperature was raised to 40 ℃.
(8) And (4) adding ionic water into the beaker in the step (7) to 100mL, and then adding hydrogen peroxide into the suspension until no gas is generated.
(9) Filtering and washing the mixture obtained in the step (8) by using hydrochloric acid and deionized water. And finally, drying the solid-phase product at 50 ℃ to obtain the graphite oxide.
(10) 0.2g of graphite oxide obtained in step (9) was dispersed in 50mL of a sodium hydroxide solution (pH 10) and subjected to ultrasonic reaction at 50 ℃ for 2 hours under 250W.
(11) And (4) centrifuging the solution obtained in the step (10) at 10000rpm for 3min to remove impurities, so as to obtain the stable graphene oxide suspension.
(12) The suspension of step (11) was collected by vacuum filtration through a 0.22 μm microfiltration membrane. And finally, washing the graphene product with deionized water for several times, and drying at 62 ℃ for 24 hours to obtain the graphene oxide.
Example 4
A method for recovering graphite from lithium battery cathode carbon powder and a method for preparing graphene oxide by taking the recovered graphite as a raw material comprise the following specific steps:
(1) 3g of lithium battery negative electrode material carbon powder is added into the ball mill, the rotating speed is controlled to be 500r/min, and the ball milling is carried out for 30 min.
(2) 12g of ammonium chloride and 3g of negative electrode material carbon powder were sufficiently ground.
(3) And (3) placing the ground mixture into a tube furnace, heating to 500 ℃ at a heating rate of 10 ℃/min under an argon atmosphere, and then roasting for 20 min.
(4) And after the roasting is finished, taking out the carbon powder, putting the carbon powder into a 250mL beaker, adding 100mL deionized water, controlling the temperature to be 70 ℃, inserting an ultrasonic vibration vibrating rod into the solution, turning on the ultrasonic vibration vibrating rod, controlling the power to be 300W, and controlling the ultrasonic time to be 2.5 h.
(5) And after the reaction is finished, leaching the leaching solution and carbon powder, washing the carbon powder with deionized water for 3 times, and drying for 24 hours to obtain graphite.
(6) After the graphite obtained in step (5) is dried, 1g of graphite is mixed with 25mL of concentrated H2SO4Mix in a beaker, fix the beaker in the low temperature reactor.
(7) 3.5g of KMnO4Slowly added in portions at a constant speed to the beaker of step (6). The temperature of the reaction system was maintained at 2 ℃ and the reaction was carried out for 30min, and then the temperature was raised to 50 ℃.
(8) And (4) adding ionic water into the beaker in the step (7) to 100mL, and then adding hydrogen peroxide into the suspension until no gas is generated.
(9) Filtering and washing the mixture obtained in the step (8) by using hydrochloric acid and deionized water. And finally, drying the solid-phase product at 70 ℃ to obtain the graphite oxide.
(10) 0.2g of graphite oxide obtained in step (9) was dispersed in 50mL of a sodium hydroxide solution (pH 9) and subjected to ultrasonic reaction at 42 ℃ for 2 hours under 300W.
(11) And (4) centrifuging the solution obtained in the step (10) at 10000rpm for 3min to remove impurities, so as to obtain the stable graphene oxide suspension.
(12) The suspension of step (11) was collected by vacuum filtration through a 0.22 μm microfiltration membrane. And finally, washing the graphene product with deionized water for several times, and drying at 60 ℃ for 24 hours to obtain the graphene oxide.
Comparative example 1
The difference from example 2 is that: in the step (1), the lithium battery negative electrode material carbon powder is not subjected to ball milling treatment.
Comparative example 2
The difference from example 2 is that: in the step (3), the mixture is heated to 800 ℃ at a heating rate of 20 ℃/min in an argon atmosphere and then is roasted for 30 min.
Comparative example 3
The difference from example 2 is that: in the step (4), the ultrasonic vibration vibrating rod is not inserted into the solution, namely, ultrasonic treatment is not carried out.
And (4) detecting a result:
the method comprises the following steps of (A) detecting the condition of each element in the recovered battery by adopting the methods in examples 1-4 and comparative examples 1-3, wherein the detection method comprises the following steps: 1g of waste lithium battery cathode carbon powder is digested by aqua regia, and the metal solubility in the digestion solution is detected by using ICP-MS (inductively coupled plasma mass spectrometer). And (4) detecting the metal solubility of the leaching solution in the step (5) by using an ICP-MS (inductively coupled plasma mass spectrometer), wherein the ratio of the metal solubility to the metal solubility is the leaching rate of the metal.
(II) reducing the graphene oxide prepared in the step (12) of the embodiments 1 to 4 and the comparative examples 1 to 3, wherein the reduction method comprises the following steps: will N2H4·H2And adding O into the graphene oxide suspension, and stirring at a constant speed for 12h at the temperature of 90 ℃ to obtain the graphene colloid suspension. The obtained graphene colloidal suspension was collected by vacuum filtration through a 0.22 μm microfiltration membrane. And finally, washing the graphene product with deionized water for several times, drying at 60 ℃ for 24 hours to obtain reduced graphene, and detecting the resistivity of the reduced graphene by using a resistivity tester.
The results are shown in table 1:
TABLE 1
As can be seen from table 1, in examples 1 to 4, the leaching rates of Li, Mn, Ni, Co, and Cu were all 81% or more, and the highest leaching rates of Li, Mn, Ni, Co, and Cu were 98%, 96%, 95%, 89%, and 87%, respectively. And the resistivity of the graphene prepared by using the graphite in the embodiments 1-4 as the raw material is more than 14210S/m.
Comparing examples 1-4 with comparative examples 1-3, it can be seen that the leaching rates of Li, Mn, Ni, Co and Cu in examples 1-4 are all significantly higher than those in comparative example 1 (step 1, ball milling treatment is not performed on carbon powder of a negative electrode material of a lithium battery), comparative example 2 (step 3, roasting temperature is different) and comparative example 3 (step 4, ultrasonic treatment is not performed), which indicates that whether ball milling treatment, roasting temperature, vibration treatment and the like are performed on carbon powder of the negative electrode material affects the leaching of metal elements in the negative electrode material, and thus affects the purity of recovered graphite. Meanwhile, the resistivity of the graphene prepared in examples 1 to 4 is obviously higher than that of comparative example 1 (in step 1, the lithium battery negative electrode material carbon powder is not subjected to ball milling treatment), comparative example 2 (in step 3, the roasting temperature is different) and comparative example 3 (in step 4, ultrasonic treatment is not performed), which indicates that whether the negative electrode material carbon powder is subjected to ball milling treatment, roasting temperature and vibration treatment also affects the resistivity of the graphene reduced by the recovered graphene oxide, and this may be because the above process affects the purity of the recovered graphite, thereby affecting the resistivity of the graphene.
The above are merely characteristic embodiments of the present invention, and do not limit the scope of the present invention in any way. All technical solutions formed by equivalent exchanges or equivalent substitutions fall within the protection scope of the present invention.
Claims (10)
1. A method for recycling graphite from lithium battery cathode carbon powder is characterized by comprising the following steps:
(1) adding negative electrode material carbon powder into a ball mill, and grinding into fine particles;
(2) mixing the negative electrode material carbon powder subjected to ball milling in the step (1) with ammonium chloride, and fully grinding to obtain a mixture;
(3) placing the ground mixture obtained in the step (2) in a container, and roasting for 15-60 min under the argon atmosphere and at the temperature of 280-500 ℃;
(4) putting the roasted negative electrode material carbon powder in the step (3) into a container, adding deionized water, controlling the temperature of the solution to be 40-70 ℃, inserting an ultrasonic vibration rod into the solution, opening the ultrasonic vibration rod, and carrying out ultrasonic treatment for 1-3 hours;
(5) and (4) after the reaction in the step (4) is finished, carrying out suction filtration on the reaction liquid to obtain graphite.
2. The method for recycling graphite from lithium battery negative electrode carbon powder according to claim 1, wherein in the step (1), negative electrode material carbon powder is added into a ball mill, the rotating speed of the ball mill is controlled to be 300-500 r/min, and the ball milling time is controlled to be 30-90 min.
3. The method for recycling graphite from lithium battery negative electrode carbon powder according to claim 1, wherein in the step (2), the negative electrode material carbon powder subjected to ball milling in the step (1) is mixed with ammonium chloride according to a mass ratio of 1-4: 1.
4. The method for recycling graphite from lithium battery negative electrode carbon powder according to claim 1, wherein in the step (3), the temperature rise rate is 2-10 ℃/min.
5. The method for recycling graphite from lithium battery negative electrode carbon powder as claimed in claim 1, wherein in the step (4), the power of the ultrasonic vibration rod is controlled to be 100-300W.
6. The method for recycling graphite from lithium battery negative electrode carbon powder according to claim 1, wherein the solid obtained after suction filtration is washed with deionized water for 2-3 times and then dried for 20-28 hours to obtain graphite.
7. A preparation method of graphene oxide is characterized in that the graphite of any one of claims 1 to 6 is used as a raw material, and the preparation method specifically comprises the following steps:
s1, drying the recovered graphite, and then mixing the graphite with concentrated H2SO4Mixing in a beaker, and fixing the beaker in a low-temperature reactor;
s2, mixing KMnO4Slowly adding the mixture into a beaker in batches at a constant speed, keeping the temperature of a reaction system at 1-5 ℃, reacting for 10-40 min, and then raising the temperature to 25-50 ℃;
s3, adding ionized water into the beaker to 100mL, and then adding hydrogen peroxide into the suspension to terminate gas generation;
s4, filtering and washing the mixture obtained in the step S3 with hydrochloric acid and deionized water, and then drying the solid-phase product at 40-80 ℃ to obtain graphite oxide;
s5, dispersing the graphite oxide obtained in the step S4 in a sodium hydroxide solution, and carrying out ultrasonic reaction for 2 hours at the temperature of 40-50 ℃ under the power of 150-300W;
s6, centrifuging the solution obtained in the step S5, and removing impurities to obtain a stable graphene oxide suspension;
s7, vacuum-filtering and collecting the suspension liquid obtained in the step S6 through a microfiltration membrane, washing the graphene product with deionized water for several times, and then drying to obtain graphene oxide.
8. The method for preparing graphene oxide according to claim 7,
in the step S1, 1g of graphite and 10-30 mL of concentrated H are mixed2SO4Mixing;
in step S2, KMnO4The addition amount of (A) is 1-3.5 times of the mass of the graphite.
9. The method for preparing graphene oxide according to claim 7,
in the step S3, adding hydrogen peroxide until bubbles no longer appear in the solution and then stopping adding;
in step S5, graphite oxide is dispersed in 50mL of a sodium hydroxide solution at a pH of 9 to 11 per 0.1 to 0.3g of graphite oxide.
10. The method for preparing graphene oxide according to claim 7,
in the step S6, centrifuging the solution in the step S5 at 10000rpm for 3min to remove impurities;
in the step S7, the suspension obtained in the step S6 is vacuum filtered and collected through a 0.22-micron microfiltration membrane, the graphene product is washed with deionized water for several times, and then the graphene product is dried for 24 hours at the temperature of 40-80 ℃ to obtain graphene oxide.
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