CN110759341B - Method for recycling graphite material based on aluminum-graphite double-ion battery - Google Patents
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Abstract
The invention discloses a method for recycling a graphite material based on an aluminum-graphite double-ion battery, and relates to the technical field of battery recycling. The method comprises the following steps: s1, recycling the waste aluminum-graphite double-ion battery to obtain graphite powder; s2, mixing the graphite powder and a coating material, uniformly mixing, and performing coating granulation to obtain graphite particles; s3, carbonizing the graphite particles to obtain a recycled graphite material; in step S2, the coating material accounts for 1-15% of the total mass of the powder and the coating material mixture; the coating material is at least one of petroleum asphalt, coal asphalt, phenolic resin, sucrose, glucose, sodium carboxymethylcellulose, polyvinyl alcohol, polyallyl alcohol, polyacrylic acid and polyvinylpyrrolidone. According to the scheme, the recovered graphite powder is subjected to deep processing treatment, so that the grade of the graphite powder is improved, and the application field of the graphite powder is increased; the whole treatment process is energy-saving, environment-friendly, efficient and high in material utilization rate.
Description
Technical Field
The invention relates to the technical field of battery recycling, in particular to a method for recycling a graphite material based on an aluminum-graphite double-ion battery.
Background
In 2016, Tang Yong Arigh researchers and teams thereof, Shenzhen Advanced technology research institute of Chinese academy of sciences, made a breakthrough in the development research of novel efficient batteries, and the research results released a brand-new aluminum-graphite double-ion battery technology on Advanced Energy Materials (DOI: 10.1002/aenm.201502588) in the top-level journal of Energy Materials.
The aluminum-graphite double-ion battery comprises the following structural components: 1) the graphite which is cheap, easy to obtain and environment-friendly is used for replacing the traditional heavy metal transition oxide or lithium iron phosphate as a positive electrode material, and the aluminum foil is used as a positive electrode current collector; 2) aluminum foil is adopted as a negative electrode material and a negative electrode current collector at the same time; 3) preparing the obtained electrolyte by using conventional lithium salt and carbonate solvent according to a certain proportion; 4) separating the anode material and the cathode material by a diaphragm; the battery thus prepared is referred to as an aluminum-graphite bi-ion battery.
Therefore, the aluminum-graphite double-ion battery has high graphite material content, and the graphite obtained by the traditional battery recovery method has low purity, poor rate capability and low economic value.
Disclosure of Invention
The invention aims to solve the technical problem of how to recover the graphite anode material from the waste aluminum-graphite double-ion battery, improve the economic value of the recovered graphite material and improve the grade of the graphite material.
In order to solve the above problems, the present invention proposes the following technical solutions:
a method for recycling graphite materials based on an aluminum-graphite double-ion battery comprises the following steps:
s1, recycling the waste aluminum-graphite double-ion battery to obtain graphite powder;
s2, mixing the graphite powder and a coating material, uniformly mixing, and performing coating granulation to obtain graphite particles;
s3, carbonizing the graphite particles to obtain a recycled graphite material;
in step S2, the coating material accounts for 1-15% of the total mass of the powder and the coating material mixture;
the coating material is at least one of petroleum asphalt, coal asphalt, phenolic resin, sucrose, glucose, sodium carboxymethylcellulose, polyvinyl alcohol, polyallyl alcohol, polyacrylic acid and polyvinylpyrrolidone.
In the step S1, the particle size of the graphite powder is D10, D50, or D90.
The further technical scheme is that in the step S3, the carbonization treatment is specifically performed by roasting the graphite particles at the temperature of 500-1000 ℃ for 10-20h under the protection of inert gas.
The further technical scheme is that the graphite material obtained in the step S3 can be applied to a conventional lithium battery as a negative electrode material, or applied to an aluminum-graphite double-ion battery as a graphite positive electrode material.
The further technical scheme is that the specific operation of the step S1 is as follows:
s101, performing discharge treatment on the waste aluminum-graphite double-ion battery, and mechanically disassembling the discharged waste aluminum-graphite double-ion battery to obtain a mixture of a steel shell, a sleeve, a gasket, gummed paper, a diaphragm, graphite powder and aluminum foil with the particle size of 2-100 mm;
s102, screening by using a fan to obtain a heavy mixture comprising a steel shell, graphite powder and aluminum foil and a light mixture comprising a sleeve, a gasket, adhesive paper and a diaphragm;
s103, baking the heavy mixture at the temperature of 200-300 ℃ for 8-12 h;
and S104, stripping powder from the product obtained in the step S103, and sieving to remove a steel shell and aluminum foil to obtain the graphite powder.
The method further adopts the technical scheme that in the step S101, the waste aluminum-graphite double-ion battery is subjected to discharge treatment, specifically, the waste aluminum-graphite double-ion battery is placed in a detection cabinet with an energy recovery function, a discharge process step is set, the discharge multiplying power is 0.1-0.5C, the discharge lower limit voltage is 0-2.0V, and the discharged waste aluminum-graphite double-ion battery is obtained after the discharge process step is completed.
The further technical solution is that, the specific operation of the step S104 is,
kneading the baked heavy mixture for 3-5h to fully separate graphite powder on the aluminum foil, and screening out the steel shell and the aluminum foil;
and crushing the screened graphite powder by using an airflow crusher to obtain the graphite powder.
Compared with the prior art, the invention can achieve the following technical effects: the method provided by the invention has the advantages that the graphite in the waste aluminum-graphite double-ion battery is recycled, the recycled graphite powder is further deeply processed, the grade of the graphite powder is improved, and the application field of the graphite powder is increased; the whole treatment process is energy-saving, environment-friendly, efficient and high in material utilization rate.
During the use of the aluminum-graphite double-ion battery, hexafluorophosphate ions can be continuously inserted into and removed from the graphite anode material, and the radius of the hexafluorophosphate ions is larger than that of lithium ions, so that after the hexafluorophosphate ions are inserted into and removed from the graphite anode material, the interlayer spacing of the graphite material is large, and partial graphite sheets are stripped to fail. Therefore, the scheme recycles and reprocesses the waste aluminum-graphite battery graphite material, combines the method of coating and pelleting, enables the failed graphite material to have activity again, and finally processes the material into the graphite material with secondary particles with small particle size and large interlayer spacing. The material can realize the rapid ion embedding and releasing, thereby having the rapid charging characteristic and being applied to battery products in the fields of high multiplying power and low temperature. In addition, inorganic lithium-containing compounds cannot be generated on the surface when the hexafluorophosphate ions are embedded into the graphite, so that inorganic compound impurities which are difficult to remove do not exist on the surface of the graphite material, the difficulty in recycling the graphite material of the aluminum-graphite battery is reduced, and the recycled graphite material of the aluminum-graphite battery has economic value and social benefit.
Detailed Description
The technical solutions in the examples will be clearly and completely described below. It is apparent that the embodiments to be described below are only a part of the embodiments of the present invention, and not all of them. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiment of the invention provides a method for recycling a graphite material based on an aluminum-graphite double-ion battery, which comprises the following steps:
s1, recycling the waste aluminum-graphite double-ion battery, removing aluminum foil, steel shell and other substances in the battery, and recycling graphite electrode materials to obtain graphite powder;
s2, mixing the graphite powder and a coating material, uniformly mixing, and performing coating granulation to obtain graphite particles;
s3, carbonizing the graphite particles to obtain a recycled graphite material;
in step S2, the coating material accounts for 1-15% of the total mass of the powder and the coating material mixture;
the coating material is at least one of petroleum asphalt, coal asphalt, phenolic resin, sucrose, glucose, sodium carboxymethylcellulose, polyvinyl alcohol, polyallyl alcohol, polyacrylic acid and polyvinylpyrrolidone.
In other embodiments, in the step S1, the graphite powder has a particle size of D10, D50, or D90. The obtained graphite electrode material may be pulverized by pulverization.
In other embodiments, in the step S3, the carbonization treatment is performed by calcining the graphite particles at 500 ℃ 1000 ℃ for 10-20h under the protection of inert gas.
For example, in one embodiment, the carbonization step S3 is performed by calcining the graphite particles at 500 ℃ for 20h under protection of inert gas.
In one embodiment, the carbonization step S3 is specifically performed by calcining the graphite particles at 800 ℃ for 15h under the protection of inert gas.
In one embodiment, the carbonization step S3 is specifically performed by calcining the graphite particles at 1000 ℃ for 10 hours under the protection of inert gas.
The graphite material obtained in step S3 can be applied to a conventional lithium battery as a negative electrode material, or applied to an aluminum-graphite bi-ion battery as a graphite positive electrode material.
In the use process of the aluminum-graphite double-ion battery, hexafluorophosphate ions can be continuously inserted into and removed from the graphite anode material, and the radius of the hexafluorophosphate ions is larger than that of lithium ions, so that the hexafluorophosphate ions can be conveniently inserted into and removed from the graphite anode material, therefore, the interlayer spacing of the graphite material is large, and the graphite purity of the graphite anode material in the battery is high. Therefore, the scheme recycles and reprocesses the waste aluminum-graphite battery graphite material into the graphite material with large spacing, and obtains the graphite material with small particle size and large interlamellar spacing secondary particles by using a coating and re-granulating method. The material can realize the rapid ion embedding and releasing, thereby having the rapid charging characteristic and being applied to battery products in the fields of high multiplying power and low temperature. In addition, inorganic lithium-containing compounds cannot be generated on the surface when the hexafluorophosphate ions are embedded into the graphite, so that inorganic compound impurities which are difficult to remove do not exist on the surface of the graphite material, the difficulty in recycling the graphite material of the aluminum-graphite battery is reduced, and the recycled graphite material of the aluminum-graphite battery has economic value and social benefit.
In a specific implementation, the specific operation of step S1 is as follows:
s101, performing discharge treatment on the waste aluminum-graphite double-ion battery, and mechanically disassembling the discharged waste aluminum-graphite double-ion battery to obtain a mixture of a steel shell, a sleeve, a gasket, gummed paper, a diaphragm, graphite powder and aluminum foil with the particle size of 2-100 mm;
s102, screening by using a fan to obtain a heavy mixture comprising a steel shell, graphite powder and aluminum foil and a light mixture comprising a sleeve, a gasket, adhesive paper and a diaphragm;
s103, baking the heavy mixture at the temperature of 200-300 ℃ for 8-12 h;
and S104, stripping powder from the product obtained in the step S103, and sieving to remove a steel shell and aluminum foil to obtain the graphite powder.
The method for recovering the graphite electrode material from the battery in step S1 can be obtained by the conventional method or the method provided in the present example.
In specific implementation, the discharging treatment of the waste aluminum-graphite double-ion battery in the step S101 is specifically performed by placing the waste aluminum-graphite double-ion battery in a detection cabinet with an energy recovery function, setting a discharging step with a discharging rate of 0.1C-0.5C and a discharging lower limit voltage of 0V-2.0V, and completing the discharging step to obtain the discharged waste aluminum-graphite double-ion battery.
In a specific implementation, the specific operation of step S104 is,
kneading the baked heavy mixture for 3-5h to fully separate graphite powder on the aluminum foil, and screening out the steel shell and the aluminum foil;
and crushing the screened graphite powder by using an airflow crusher to obtain the graphite powder.
Another embodiment of the present invention provides a method for recycling a graphite material based on an aluminum-graphite bi-ion battery, comprising the steps of:
1) removing residual electric quantity: placing the battery in a detection cabinet with an energy recovery function, and setting a discharge process step, wherein the discharge multiplying power is 0.1-0.5C, and the discharge lower limit voltage is 0-2.0V;
the energy is recycled in the step, the energy can be used for power utilization of equipment in subsequent processes, and after the discharging step is completed, the battery core can be recycled into the box for the next process, so that the effects of recycling residual electric quantity in the waste battery and fully utilizing the guaranteed energy are achieved.
2) Battery crushing: mechanically disassembling and crushing the discharged battery; obtaining a mixture of substances such as a steel shell, a diaphragm, graphite powder, aluminum foil and the like with the particle size of 2-100 mm;
the step adopts a mechanical method, ensures the sufficient separation of materials such as powder, fluid and the like, and is convenient for subsequent screening.
3) Separating and centralizing lighter substances such as plastic diaphragms, sleeves, gaskets, gummed paper and the like in the disassembled and crushed mixture by adopting a comprehensive winnowing machine; collecting heavy mixtures such as graphite powder, aluminum foil, steel shell and the like;
through separating sleeve pipe, gasket, adhesive tape, when preventing follow-up high temperature treatment that carries on, this type of material softens the adhesion in graphite powder, aluminium foil, steel casing surface, hinders follow-up sorting.
4) Baking: placing the heavy mixture obtained by the first sorting in an oven at 200-300 ℃ for baking for 10 h;
through the heating and baking treatment at a lower temperature, the binding agents in the graphite powder and between the graphite powder and the aluminum foil at the stage lose efficacy, the separation at the subsequent stage is facilitated, and the energy consumption is low; meanwhile, electrolyte remained in the battery under the high-temperature environment can be further volatilized, and the part of volatilized electrolyte can be collected and then is subjected to centralized treatment;
5) stripping powder: kneading the baked heavy mixture for 3-5h to fully separate graphite powder on the aluminum foil, wherein the powder separation rate can reach 90-99% in the stage due to baking;
6) screening: screening the separated materials, wherein the final oversize products are a steel shell and an aluminum foil; the undersize is a graphite powder material with fine particles;
7) crushing graphite: treating the screened graphite powder material by using an airflow crusher to obtain a powder material with the particle size D10 of 0.5-3 um, D50 of 3-7 um and D90 of 7-15 um;
8) and (3) graphite granulation: mixing the crushed graphite powder and a coating material according to a certain proportion, and performing coating granulation in a granulator to obtain graphite particles; wherein the coating material is one or a mixture of two or more of petroleum asphalt, coal asphalt, phenolic resin, sucrose, glucose, sodium carboxymethylcellulose, polyvinyl alcohol, polyallyl alcohol, polyacrylic acid and polyvinylpyrrolidone; the content of the coating material is 1% -15%;
9) high-temperature carbonization treatment: under the protection of inert gas, the graphite particles are roasted for 10-20h and carbonized at the temperature of 500-1000 ℃. The graphite material with the quick charging performance can be obtained by screening the graphite after the carbonization treatment, and can be applied to a traditional lithium battery as a negative electrode material and can also be applied to an aluminum-graphite double-ion battery as a graphite positive electrode material.
The recovery work of the aluminum-graphite double-ion battery is completed through the steps. The whole work does not involve any additional chemical reagent, does not produce sewage, does not cause secondary pollution, and the recycled materials retain the original characteristics to the maximum extent, and have higher recycling rate;
the equipment and materials related by the invention can be normally purchased in the market.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
According to the method for recycling the graphite material based on the aluminum-graphite double-ion battery provided by the embodiment of the invention, the obtained graphite material is applied to a traditional lithium battery as a negative electrode material, wherein the method for preparing the conventional lithium ion battery comprises the following steps:
the capacity of the battery cell is designed to be 1000mAh, and different anode materials, PVDF and conductive carbon black are coated on an aluminum foil according to a ratio of 95:3:2 to be used as an anode plate. According to the ratio of the negative electrode capacity to the positive electrode capacity of 1.15, a graphite material with the specific capacity of 320mAh/g, CMC, SBR and conductive carbon black are coated on a copper foil according to the ratio of 95:1.5:2.5:1 to be used as a negative electrode sheet. The processing technology and the process control of the positive and negative pole pieces adopt the current industrialized technology, and finally, the processed positive and negative pole pieces are assembled into a full cell by using a cellgard 2400 polypropylene porous membrane in a glove box filled with argon gas, wherein the electrolyte is a mixed solution (the volume ratio is = 1: 1) of Ethylene Carbonate (EC) and dimethyl carbonate (DMC) of 1mol/L LiPF6, and the diaphragm is a diaphragm, so that a cell sample is obtained. According to the method, the graphite materials of the negative electrodes in the embodiments 1 to 38 and the comparative example 1 are prepared, and the graphite materials of the negative electrodes in the embodiments 1 to 38 are all the graphite materials prepared by the recovery and reprocessing method provided by the embodiment of the invention; comparative example 1 was prepared using the same graphite material as used for the recycled aluminum-graphite bi-ion battery. Table 1 is a table of parameters for making graphite materials of examples and comparative examples; table 2 shows the comparison of the properties of the examples and the comparative examples.
TABLE 1 Table of parameters for making graphite materials of examples and comparative examples
| Numbering | Positive electrode material | Graphite powder particle size D50(um) | Cladding material | Carbonization temperature (. degree.C.) | Carbonization time (h) |
| Example 1 | Lithium iron phosphate | 7 | 5% petroleum asphalt | 500 | 20 |
| Example 2 | Lithium iron phosphate | 8 | 3% petroleum asphalt | 800 | 15 |
| Example 3 | Lithium cobaltate | 9 | 7% petroleum asphalt | 1000 | 10 |
| Example 4 | Lithium iron phosphate | 10 | 6% petroleum asphalt | 700 | 18 |
| Example 5 | Lithium iron phosphate | 11 | 4% petroleum asphalt | 900 | 12 |
| Example 6 | Lithium iron phosphate | 6 | 8% petroleum asphalt | 600 | 14 |
| Example 7 | Lithium cobaltate | 5 | 15% petroleum asphalt | 550 | 9 |
| Example 8 | Lithium cobaltate | 7 | 16% petroleum asphalt | 650 | 12 |
| Example 9 | Ternary nickel cobalt manganese | 8 | 20% petroleum asphalt | 750 | 18 |
| Example 10 | Ternary nickel cobalt manganese | 9 | 1% petroleum asphalt | 950 | 11 |
| Example 11 | Lithium cobaltate | 10 | 0.5% petroleum asphalt | 1000 | 15 |
| Example 12 | Lithium iron phosphate | 11 | 8% coal tar pitch | 1000 | 10 |
| Example 13 | Lithium iron phosphate | 12 | 8% phenolic resin | 1000 | 12 |
| Example 14 | Lithium iron phosphate | 20 | 8% sucrose | 850 | 15 |
| Example 15 | Lithium iron phosphate | 16 | 8% glucose | 850 | 10 |
| Example 16 | Lithium iron phosphate | 12 | 8% sodium carboxymethylcellulose | 850 | 20 |
| Example 17 | Lithium iron phosphate | 12 | 8% polyvinyl alcohol | 850 | 12 |
| Example 18 | Lithium iron phosphate | 16 | 8% of polyallyl alcohol | 850 | 13 |
| Example 19 | Lithium cobaltate | 10 | 8% polyacrylic acid | 850 | 14 |
| Example 20 | Lithium cobaltate | 20 | 8% of polyvinylpyrrolidone | 800 | 10 |
| Example 21 | Lithium cobaltate | 4 | 4% of petroleum asphalt and 5% of phenolic resin | 750 | 10 |
| Example 22 | Lithium cobaltate | 15 | 4% coal tar pitch and 6% polypropylene glycol | 700 | 10 |
| Example 23 | Lithium cobaltate | 14 | 4% sucrose +3% polyacrylic acid | 650 | 20 |
| Example 24 | Lithium cobaltate | 13 | 4% glucose +2% sodium carboxymethylcellulose | 600 | 20 |
| Example 25 | Lithium cobaltate | 12 | 10% polyvinylpyrrolidone +2% sodium carboxymethylcellulose | 550 | 20 |
| Example 26 | Lithium cobaltate | 11 | 2% polyvinylpyrrolidone +2% carboxylSodium methyl cellulose +2% coal tar pitch | 500 | 20 |
| Example 27 | Lithium cobaltate | 10 | 4% of polyvinylpyrrolidone, 1% of sodium carboxymethylcellulose, 4% of coal tar pitch and 3% of phenolic resin | 1000 | 15 |
| Example 28 | Ternary nickel cobalt manganese | 15 | 4% of petroleum asphalt, 1% of cane sugar, 4% of coal tar and 3% of phenolic resin | 1000 | 12 |
| Example 29 | Ternary nickel cobalt manganese | 15 | 4% of petroleum asphalt, 1% of sucrose, 4% of polyvinyl alcohol and 3% of phenolic resin | 1000 | 11 |
| Example 30 | Ternary nickel cobalt manganese | 10 | 4% of petroleum asphalt, 1% of sucrose, 4% of polyvinyl alcohol and 3% of phenolic resin | 1000 | 18 |
| Example 31 | Ternary nickel cobalt manganese | 12 | 10% coal tar pitch | 1000 | 19 |
| Example 32 | Ternary nickel cobalt manganese | 16 | 15% phenolic resin | 1000 | 20 |
| Example 33 | Ternary nickel cobalt manganese | 20 | 12% sucrose | 480 | 20 |
| Example 34 | Ternary nickel cobalt manganese | 10 | 5% glucose | 450 | 25 |
| Example 35 | Ternary nickel cobalt manganese | 12 | 6% sodium methyl cellulose | 1100 | 10 |
| Example 36 | Ternary nickel cobalt manganese | 16 | 3% polyvinyl alcohol | 1200 | 20 |
| Example 37 | Ternary nickel cobalt manganese | 20 | 4% of polyvinylpyrrolidone | 1000 | 18 |
| Example 38 | Ternary nickel cobalt manganese | 6 | 11% petroleum asphalt | 1000 | 15 |
| Comparative example 1 | Lithium iron phosphate | 8 |
TABLE 2 comparison of the properties of the examples and comparative examples
| Numbering | Positive electrode material | Battery 1C discharge Capacity (mAh) | Battery 20C (vs1C) discharge Capacity maintenance ratio (%) |
| Example 1 | Lithium iron phosphate | 2000 | 91 |
| Example 2 | Lithium iron phosphate | 2000 | 93 |
| Example 3 | Lithium cobaltate | 2000 | 93 |
| Example 4 | Lithium iron phosphate | 2000 | 93.5 |
| Example 5 | Lithium iron phosphate | 2000 | 92.5 |
| Example 6 | Lithium iron phosphate | 2000 | 92.5 |
| Example 7 | Lithium cobaltate | 2000 | 92 |
| Example 8 | Lithium cobaltate | 2000 | 94 |
| Example 9 | Ternary nickel cobalt manganese | 2000 | 94 |
| Example 10 | Ternary nickel cobalt manganese | 2000 | 93.5 |
| Example 11 | Lithium cobaltate | 2000 | 90 |
| Example 12 | Lithium iron phosphate | 2000 | 93.5 |
| Example 13 | Lithium iron phosphate | 2000 | 93 |
| Example 14 | Lithium iron phosphate | 1950 | 92.5 |
| Example 15 | Lithium iron phosphate | 1980 | 93 |
| Example 16 | Lithium iron phosphate | 2000 | 93.5 |
| Example 17 | Lithium iron phosphate | 2000 | 93 |
| Example 18 | Lithium iron phosphate | 1995 | 92.5 |
| Example 19 | Lithium cobaltate | 2000 | 93.5 |
| Example 20 | Lithium cobaltate | 1990 | 91 |
| Example 21 | Lithium cobaltate | 2000 | 95 |
| Example 22 | Lithium cobaltate | 2000 | 92 |
| Example 23 | Lithium cobaltate | 2000 | 92.5 |
| Example 24 | Lithium cobaltate | 2000 | 92.5 |
| Example 25 | Lithium cobaltate | 2000 | 92 |
| Example 26 | Lithium cobaltate | 2000 | 92 |
| Example 27 | Lithium cobaltate | 2000 | 93.5 |
| Example 28 | Ternary nickel cobalt manganese | 1960 | 93 |
| Example 29 | Ternary nickel cobalt manganese | 1965 | 93 |
| Example 30 | Ternary nickel cobalt manganese | 2000 | 93.5 |
| Example 31 | Ternary nickel cobalt manganese | 2000 | 93.5 |
| Example 32 | Ternary nickel cobalt manganese | 1995 | 92.5 |
| Example 33 | Ternary nickel cobalt manganese | 1850 | 89 |
| Example 34 | Ternary nickel cobalt manganese | 1700 | 88 |
| Example 35 | Ternary nickel cobalt manganese | 1980 | 92 |
| Example 36 | Ternary nickel cobalt manganese | 1965 | 91.5 |
| Example 37 | Ternary nickel cobalt manganese | 1990 | 91.5 |
| Example 38 | Ternary nickel cobalt manganese | 2000 | 94 |
| Comparative example 1 | Lithium iron phosphate | 1990 | 83 |
From the table 2, when the particle size D50 of the reprocessed graphite negative electrode material is 5-20 um, the carbonization processing temperature is 500-1000 ℃, and the processing time is 10-20 hours, the rate capability of the material is superior to that of the originally used graphite material.
The embodiment of the invention provides a method for recycling a graphite material based on an aluminum-graphite double-ion battery, which fully utilizes the residual electric quantity of a waste battery to recycle the waste battery, thereby increasing the utilization value of the waste battery; meanwhile, the adhesion force of the graphite powder and the aluminum foil is reduced by adopting a low-temperature baking mode, the difficulty of subsequent kneading separation is reduced, and secondary pollution caused by a solvent soaking separation method is avoided; finally, the invention also carries out advanced treatment on the recovered graphite powder, improves the grade of graphite and widens the application field of the graphite powder.
In addition, no waste water, waste gas, waste acid, waste alkali and other wastes harmful to the environment are generated in the whole battery recycling process. Wherein the recycled graphite material can be applied to the field of lithium ion batteries or aluminum-graphite double-ion batteries again; after being recovered, the current collector aluminum foil can be further smelted by an aluminum processing manufacturer and then applied to the field of various aluminum products; the battery shell and the diaphragm can be crushed to form material resources which are directly recycled; meanwhile, the technical means also recycles the residual electric quantity in the battery, so that the resources can be fully utilized; the whole technical scheme has novel recovery technology, so that the recovery is pollution-free and the recovery benefit is great.
In the above embodiments, the descriptions of the respective embodiments have respective emphasis, and for parts that are not described in detail in a certain embodiment, reference may be made to related descriptions of other embodiments.
While the invention has been described with reference to specific embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (4)
1. A method for recycling graphite materials based on an aluminum-graphite double-ion battery is characterized by comprising the following steps:
s1, recycling the waste aluminum-graphite double-ion battery to obtain graphite powder;
s2, mixing the graphite powder and a coating material, uniformly mixing, and performing coating granulation to obtain graphite particles;
s3, carbonizing the graphite particles to obtain a recycled graphite material;
in step S2, the coating material accounts for 1-15% of the total mass of the powder and the coating material mixture;
the coating material is at least one of petroleum asphalt, coal asphalt, phenolic resin, sucrose, glucose, sodium carboxymethylcellulose, polyvinyl alcohol, polyallyl alcohol, polyacrylic acid and polyvinylpyrrolidone;
in the step S3, the carbonization treatment is specifically performed by roasting the graphite particles at a temperature of 500-1000 ℃ for 10-20h under the protection of an inert gas;
the specific operation of step S1 is as follows:
s101, performing discharge treatment on the waste aluminum-graphite double-ion battery, and mechanically disassembling the discharged waste aluminum-graphite double-ion battery to obtain a mixture of a steel shell, a sleeve, a gasket, gummed paper, a diaphragm, graphite powder and aluminum foil with the particle size of 2-100 mm;
s102, screening by using a fan to obtain a heavy mixture comprising a steel shell, graphite powder and aluminum foil and a light mixture comprising a sleeve, a gasket, adhesive paper and a diaphragm;
s103, baking the heavy mixture at the temperature of 200-300 ℃ for 8-12 h;
s104, stripping powder from the product obtained in the step S103, and sieving to remove a steel shell and aluminum foil to obtain the graphite powder;
the specific operation of the step S104 is that,
kneading the baked heavy mixture for 3-5h to fully separate graphite powder on the aluminum foil, and screening out the steel shell and the aluminum foil;
and crushing the screened graphite powder by using an airflow crusher to obtain the graphite powder.
2. The method for recycling graphite material based on aluminum-graphite bi-ion battery of claim 1, wherein in the step S1, the particle size of the graphite powder is D10, D50 or D90.
3. The method for recycling graphite material based on aluminum-graphite bi-ion battery as claimed in claim 1, wherein the graphite material obtained in step S3 can be applied to conventional lithium battery as negative electrode material or aluminum-graphite bi-ion battery as positive electrode material.
4. The method for recycling graphite materials based on aluminum-graphite bi-ion batteries according to claim 1, wherein the waste aluminum-graphite bi-ion batteries are subjected to discharge treatment in step S101, and the method is specifically operated in such a way that the waste aluminum-graphite bi-ion batteries are placed in a detection cabinet with an energy recovery function, a discharge process step is set, the discharge rate is 0.1C-0.5C, the lower limit voltage of discharge is 0V-2.0V, and the discharged waste aluminum-graphite bi-ion batteries are obtained after the discharge process step is completed.
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| CN112397801A (en) * | 2020-10-30 | 2021-02-23 | 北京佰利格瑞资源科技有限公司 | Lithium battery material recycling method |
| CN112436205B (en) * | 2020-11-19 | 2021-11-19 | 内蒙古杉杉科技有限公司 | Method for recycling negative pole piece waste of lithium ion battery |
| CN115558306B (en) * | 2021-07-02 | 2023-10-17 | 湖南中科星城石墨有限公司 | Isotropic asphalt material and preparation method and application thereof |
| CN114975868A (en) * | 2022-06-06 | 2022-08-30 | 同济大学 | Dual-ion battery positive electrode, preparation method and dual-ion battery comprising same |
| CN115275416B (en) * | 2022-08-08 | 2024-06-25 | 江苏正力新能电池技术有限公司 | Recovery method of graphite in waste lithium ion battery and high-capacity fast-charging anode material |
| CN115646981B (en) * | 2022-12-22 | 2023-03-10 | 湖南金阳烯碳新材料股份有限公司 | Method for lossless recovery of graphite negative plate of waste lithium ion battery |
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