CN109950651B - Comprehensive treatment method for recycling carbon from waste lithium iron phosphate batteries - Google Patents
Comprehensive treatment method for recycling carbon from waste lithium iron phosphate batteries Download PDFInfo
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Abstract
The invention discloses a comprehensive treatment method for recovered carbon of waste lithium iron phosphate batteries, which utilizes the characteristics of larger interlayer spacing, increased defects and impurity Fe of graphite components in the recovered carbon2O3、CuO、Al2O3The method has the characteristics that the graphite intercalation compound is prepared without adding an intercalation reagent, and graphite is stripped into graphene nanosheets through low-temperature calcination. The method can realize high value-added recovery of the graphite material in the recovered carbon of the waste lithium iron phosphate battery, and can also recover metal impurities in the carbon in the form of chloride, so that the method has a strong application prospect and feasibility. In addition, the technology can realize the cyclic utilization of hydrochloric acid and steam heat, and has the advantages of low energy consumption, low cost, environmental protection and the like.
Description
Technical Field
The invention belongs to the technical field of waste battery recovery, and particularly relates to a comprehensive treatment method for recovering carbon from waste lithium iron phosphate batteries.
Background
Lithium iron phosphate (LiFePO)4) The power battery has the advantages of low cost, high safety performance, good cycle performance and the like, and is widely applied to the fields of large-scale passenger vehicles, hybrid electric vehicles and the like. Due to the limited service life of the battery (3-5 years) and the rapid development of new energy industry, a large number of lithium iron phosphate batteries face the problem of scrapping treatment, and the batteries contain chemical substances such as lithium hexafluorophosphate, organic carbonate and polyolefin diaphragms, and will cause serious pollution to the atmosphere, water and soil if not subjected to recycling treatment.
The basic steps of the existing lithium iron phosphate battery recovery include two parts of pretreatment (disassembly, pyrolysis and the like) and element recovery (or material regeneration). The pretreatment is to separate positive and negative pole pieces after the battery is crushed, and separate positive and negative active substances from a current collector by adopting a pyrogenic process treatment mode. In the element recovery process, inorganic acid solution is usually adopted to leach out metal elements in the active substance, and then metal elements such as lithium, cobalt and the like are recovered by a wet metallurgy method.
Compared with typical commercial negative electrode graphite, the recycled carbon of the waste lithium iron phosphate battery has the following special physical and chemical properties: 1) the graphite component in the recovered carbon has the characteristics of increased graphite layer spacing and increased gaps. 2) In the treatment processes of disassembly, pyrogenic pretreatment and the like, Fe is easily introduced into recovered carbon by using waste lithium iron phosphate batteries2O3、CuO、Al2O3And the like. At present, the recovery of the negative electrode carbon material of the waste lithium ion battery is also reported, and patent CN101710632B discloses a recovery and repair method of the negative electrode graphite of the waste lithium ion battery, wherein after impurity removal, cellulose acetate is used as a surface modifier, and acetone is used as a solvent to perform surface modification on the graphite, so as to obtain a carbon material with high purity and the surface coated with amorphous carbon. Patent CN201610041766 discloses a method for recycling waste lithium ion battery graphite negative electrode, which is characterized in that excessive organic matters in the negative electrode are removed by adding ferrous salt or zinc salt, and surface modification is performed on graphite particles to obtain a regenerated graphite negative electrode material. The above patent recovers and recycles the waste lithium ion battery cathode carbon material by a modification mode, but the recovered product cannot be compared with the commercial carbonaceous material due to the structural defect of the recovered carbon material, and the competitive advantage is not obvious; meanwhile, valuable metal impurities (iron, copper, aluminum and the like) in the recovered carbon are removed by acid liquor and discharged as wastes, and the recovered carbon is not recycled, so that the waste of resources is caused.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a comprehensive treatment method for recovering carbon from waste lithium iron phosphate batteries, which realizes high value-added recovery of graphite materials and recovery of valuable metal elements in the recovered carbon, and simultaneously realizes cyclic utilization of hydrochloric acid and steam heat in the process, thereby reducing resource consumption and operation cost.
The recovered carbon in the invention refers to carbon obtained by disassembling and crushing the waste lithium iron phosphate power battery, separating the positive and negative electrode active substances from the current collector by high-temperature heat treatment, recovering valuable metal elements in the active substances from the solution by a hydrometallurgy method, and finally filtering and recovering the valuable metal elements from the solution.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
a comprehensive treatment method for recycling carbon from waste lithium iron phosphate batteries comprises the following steps:
(1) adding the recovered carbon into a mixed acid solution A of hydrochloric acid and other acidic substances according to a liquid-solid mass ratio of 5-10: 1, wherein the concentration of the hydrochloric acid in the mixed acid solution A is 3-10 mol/L, the total concentration of the other acidic substances is 0.5-1 mol/L, and stirring at the temperature of 30-60 ℃ for 6-12 hours to obtain a solution B;
(2) adding an oxidant into the solution B according to 10-30 wt% of the mass of the recovered carbon, carrying out ultrasonic treatment at 25-85 ℃, wherein the power is 400-800W, the frequency is 20-300 KHz, and the ultrasonic time is 1-3 h, and then adding a reducing agent to obtain a solution C;
(3) volatilizing and collecting hydrochloric acid in the solution C, filtering to obtain filter residue and filtrate respectively, heating the crystallization stock solution in the step (5) by using heat in hydrochloric acid steam, mixing the collected hydrochloric acid with the filtrate to obtain mixed acid solution D for later use, washing the filter residue until the pH of an eluate is 5-7, and drying to obtain a solid substance;
(4) in the mixed atmosphere of oxygen and protective gas, preserving the heat of the solid matter for 1-3 h at 400-500 ℃, wherein the heating rate is 5-10 ℃/min; or subjecting the solid substance to microwave treatment at 500-1200W for 0.5-2 min to obtain a solid mixture E;
(5) placing the solid mixture E in a mixed acid solution D, stirring for 6-12 h at 30-60 ℃, and filtering to obtain a carbon material containing graphene nanosheets and a crystallization stock solution;
firstly, keeping the temperature of the crystallization stock solution at 100-120 ℃ for 1-2 h to volatilize and collect hydrochloric acid in the crystallization stock solution, and adding AlCl with the mass of 5-8 wt% of the recovered carbon into the residual solution3Seeding with AlCl3Crystallizing, separating to obtain AlCl3Crystals and primary filtrate;
preserving the temperature of the primary filtrate at 80-100 ℃ for 1-2 h, and adding CuCl accounting for 5-8 wt% of the mass of the recovered carbon2Seeding with CuCl2Crystallizing, separating to obtain CuCl2Crystals and secondary filtrate;
preserving the heat of the secondary filtrate at 80-100 ℃ for 1-2 h, and adding FeCl accounting for 5-8 wt% of the mass of the recovered carbon3Seed crystal of FeCl3Crystallizing, separating to obtain FeCl3Crystals and tertiary filtrate;
and (3) heating the solution C in the step (3) by using the heat in the hydrochloric acid steam, mixing the collected hydrochloric acid with the third filtrate, and returning to the step (1) for recycling.
Preferably, in the step (1), the stirring manner is at least one selected from mechanical stirring, gas flow stirring and jet stirring.
Preferably, in step (1), the other acidic substance is selected from H2SO4、HNO3、H3PO4、HPO3、HClO3、HClO、H2FeO4HCOOH and CH3At least one of COOH.
Preferably, in step (2), the oxidant is selected from NaClO and NaClO3、NaClO4、KClO、KClO3、KClO4、NH4ClO3、NH4ClO4、Na2S2O8、K2S2O8、(NH4)2S2O8、K2FeO4And Na2FeO4At least one of (1).
Preferably, in step (2), the reducing agent is selected from H2O2、FeSO4Reduced iron powder and FeCl2、H2C2O4And Na2SO3At least one of reducing agent and oxidizing agentThe molar ratio of the agents is 0.8-2: 1.
Preferably, in the step (3), the temperature for volatilizing and collecting the hydrochloric acid is 80-120 ℃.
Preferably, in the step (4), the flow rate of the mixed atmosphere is 30-200 mL/min, wherein the volume ratio of oxygen is 21-40%, and the protective gas is at least one selected from nitrogen and argon.
Compared with the prior art, the invention has the following beneficial effects:
(1) the traditional method for recycling the lithium iron phosphate battery stacks the negative carbon material as waste residues, but the method provided by the invention utilizes the increase of interlamellar spacing and defect of the graphite component in the recycled carbon and the impurity Fe2O3、CuO、Al2O3The method has the characteristics that under the condition that no additional intercalation reagent is needed, a graphite intercalation compound is prepared by adopting a method of combining chemical oxidation intercalation-ultrasonic treatment, and then a carbon material containing graphene nanosheets is obtained by stripping, so that the additional value of the recovery of the lithium ion battery cathode carbon material is increased; and valuable metal components (iron, copper and aluminum) in the recovered carbon can be recovered in the form of metal chloride, so that resources are saved.
(2) Compared with the existing stripping method of Graphite Intercalation Compound (GIC), the method converts graphite into FeCl by a chemical oxidation intercalation method3-CuCl2-AlCl3-GIC interlayer compound, then subjecting the intercalation agent to a hydrolysis reaction to convert the interlayer compound to Fe (OH)3-Cu(OH)2-Al(OH)3GIC, and finally conversion of the interlaminar compound to Fe by dehydration of the metal hydroxide by heating at elevated temperature2O3-CuO-Al2O3And (4) GIC, stripping the graphite layer by utilizing the thrust generated by water vapor, and finally obtaining the graphene nanosheet-containing carbonaceous material. Heating temperature required in the stripping process and FeCl3/CuCl2/AlCl3Compared with the stripping mode of gas volatilization expansion, the stripping mode is lower, only 400-500 ℃, and the energy consumption and the cost are reduced.
(3) The hydrochloric acid used by the process can be recovered in an evaporation and condensation mode and used for other steps of the process, so that the cyclic utilization of the hydrochloric acid is realized, and the discharge amount of the acidic wastewater is greatly reduced. The heat required by the solution evaporation can be recycled through the mutual exchange of the heat between the vapor and the liquid, so that the energy consumption and the cost of the preparation process are reduced, and the environment is protected.
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FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The invention is explained in detail with the concrete operation example below; the scope of protection of the claims of the invention is not limited by the embodiments.
Example 1
(1) Adding the recovered carbon into HCl with the concentration of 10mol/L and H2SO4Mechanically stirring the mixed acid solution A with the concentration of 1mol/L for 12 hours at the temperature of 60 ℃ in a liquid-solid mass ratio of 10:1 to obtain a solution B;
(2) adding NaClO with the mass percent of the recovered carbon being 30% into the solution B, carrying out ultrasonic treatment at 85 ℃, wherein the ultrasonic power is 800W, the frequency is 300KHz, the ultrasonic time is 3H, and then adding H2O2To remove excess NaClO, added H2O2The molar ratio of the NaClO to the NaClO is 2:1, and a solution C is obtained;
(3) heating the solution C to 120 ℃ to volatilize hydrochloric acid in the solution C, filtering the residual solution, and then respectively collecting filter residue and filtrate, heating the crystallization stock solution in the step (5) by heat in hydrochloric acid steam in a heat convection mode, mixing hydrochloric acid obtained by steam condensation with the filtrate collected in the step to obtain mixed acid solution D for later use, and cleaning the surface of the filter residue by deionized water until the pH value of eluate is 7 to obtain a solid substance;
(4) placing the solid matter obtained in the step (3) in a heating furnace, keeping introducing gas with the oxygen volume fraction accounting for 40% and the rest gas components being nitrogen at the flow rate of 200mL/min, raising the temperature from room temperature to 500 ℃, heating at the speed of 10 ℃/min, and preserving the heat for 3h to obtain a solid mixture E;
(5) and (3) placing the solid mixture E in a mixed acid solution D, mechanically stirring for 12h at the temperature of 60 ℃, and filtering to obtain the graphene nanosheet-containing carbonaceous material and a crystallization stock solution. Heating the crystallization stock solution to 120 ℃ firstly and preserving the heat for 2hAdding AlCl with 8 percent of the mass of the recovered carbon3Seeding with AlCl3Crystallizing, filtering and recovering. Then the solution is kept at 100 ℃ for 2h, and CuCl with the mass of 8 percent of the recovered carbon is added2Seeding with CuCl2Crystallizing, filtering and recovering. Finally, the residual solution is kept at 100 ℃ for 2h, and FeCl with the mass of 8 percent of the recovered carbon is added3Seed crystal of FeCl3Crystallizing, filtering and recovering. Implementing FeCl3、CuCl2And AlCl3And classified recovery of the filtrate. And (3) heating the solution C in the step (3) by heat convection in the steam of the hydrochloric acid, and mixing the hydrochloric acid obtained by condensing the steam with the crystallization mother liquor to obtain the mixed acid liquid A in the step (1).
The carbonaceous material containing the graphene nanosheet with the number of the layers being 3 is prepared and recovered to obtain FeCl3、CuCl2And AlCl3The purities were 99.14%, 98.90%, and 99.28%, respectively.
Example 2
(1) Adding the recovered carbon into HCl with the concentration of 6mol/L and HNO3And (3) stirring the mixed acid solution A with the concentration of 0.8mol/L for 10 hours at the temperature of 45 ℃ by air flow in a liquid-solid mass ratio of 8:1 to obtain a solution B.
(2) Adding (NH) with 20 percent of the mass of the recovered carbon into the solution B4)2S2O8Ultrasonic treatment is carried out at 55 ℃, the ultrasonic power is 600W, the frequency is 150KHz, the ultrasonic time is 2h, and then FeCl is added2To remove excess (NH)4)2S2O8Added FeCl2And (NH)4)2S2O8At a molar ratio of 1.4:1, to obtain a solution C;
(3) heating the solution C to 100 ℃ to volatilize hydrochloric acid, filtering the residual solution, and collecting filter residue and filtrate respectively. And (3) heating the crystallization stock solution in the step (5) by heat in the hydrochloric acid steam in a heat convection mode, and mixing hydrochloric acid obtained by steam condensation with the filtrate collected in the step to obtain mixed acid solution D for later use. Washing the surface of the filter residue with deionized water until the pH of the eluate is 6 to obtain a solid substance;
(4) placing the solid matter obtained in the step (3) in a heating furnace, keeping introducing gas with the oxygen volume fraction accounting for 30% and the rest gas component being nitrogen at the flow rate of 120mL/min, heating the temperature from room temperature to 450 ℃, heating the temperature at the speed of 7 ℃/min, and keeping the temperature for 2h to obtain a solid mixture E;
(5) and (3) placing the solid mixture E in a mixed acid solution D, stirring for 10 hours at 45 ℃ by using air flow, and filtering to obtain the graphene nanosheet-containing carbonaceous material and a crystallization stock solution. Heating the crystallization stock solution to 110 ℃ firstly, preserving the heat for 1.5h, and adding AlCl with the mass of 7 percent of the recovered carbon3Seeding with AlCl3Crystallizing, filtering and recovering. Then the solution is kept warm for 1.5h at 90 ℃, CuCl with the mass percent of the recovered carbon being 7 percent is added2Seeding with CuCl2Crystallizing, filtering and recovering. Finally, the residual solution is kept at 90 ℃ for 2h, and FeCl with the mass of 7 percent of the recovered carbon is added3Seed crystal of FeCl3Crystallizing, filtering and recovering. Implementing FeCl3、CuCl2And AlCl3And classified recovery of the filtrate. Heating the solution C in the step (3) by heat convection in the steam of hydrochloric acid, and mixing hydrochloric acid obtained by steam condensation and crystallization mother liquor to obtain mixed acid liquid A in the step (1);
this example produced a carbonaceous material containing graphene nanoplatelets having 5 number of the sheet layers. Recovering to obtain FeCl3、CuCl2And AlCl3The purities were 98.79%, 98.60%, and 98.90%, respectively.
Example 3
(1) Adding the recovered carbon into HCl with the concentration of 3mol/L and H2SO4、H3PO4、CH3And (3) in the mixed acid solution A with the total concentration of 0.5mol/L of COOH, the liquid-solid mass ratio is 5:1, and the mixture is stirred for 6 hours by jetting at the temperature of 30 ℃ to obtain a solution B.
(2) Adding Na with the mass percent of 10 percent of the recovered carbon into the solution B2FeO4Ultrasonic treatment at 25 deg.C with ultrasonic power of 400W and frequency of 20KHz for 1h, and adding Na2SO3To remove excessive Na2FeO4Added Na2SO3With Na2FeO4At a molar ratio of 0.8:1, to obtain solution C.
(3) Heating the solution C to 80 ℃ to volatilize hydrochloric acid, and filtering to collect filter residue and filtrate respectively. And (3) heating the crystallization stock solution in the step (5) by heat in the hydrochloric acid steam in a heat convection mode, and mixing hydrochloric acid obtained by steam condensation with the filtrate collected in the step to obtain mixed acid solution D for later use. And washing the surface of the filter residue with deionized water until the pH of the eluate is 5 to obtain a solid substance.
(4) And (4) placing the solid substance obtained in the step (3) in a microwave device with 500W power for treating for 0.5min, and keeping introducing gas with the oxygen volume fraction of 21% and the rest gas components of nitrogen at the flow rate of 30mL/min to obtain a solid mixture E.
(5) And (3) placing the solid mixture E in a mixed acid solution D, carrying out jet stirring for 6h at the temperature of 30 ℃, and filtering to obtain the graphene nanosheet-containing carbonaceous material and a crystallization stock solution. Heating the crystallization stock solution to 100 ℃ firstly, preserving the heat for 1h, adding AlCl with the mass of 5 percent of the recovered carbon3Seeding with AlCl3Crystallizing, filtering and recovering. Then the solution is kept at 80 ℃ for 1h, and CuCl with the mass of 5 percent of the recovered carbon is added2Seeding with CuCl2Crystallizing, filtering and recovering. Finally, the residual solution is kept at 80 ℃ for 1h, and FeCl with the mass of 5 percent of the recovered carbon is added3Seed crystal of FeCl3Crystallizing, filtering and recovering. Implementing FeCl3、CuCl2And AlCl3And classified recovery of the filtrate. And (3) heating the solution in the step (3) in a thermal convection mode by using heat in the hydrochloric acid steam, and mixing hydrochloric acid obtained by steam condensation and the crystallization mother liquor to obtain the mixed acid liquid A in the step (1).
The carbonaceous material containing the graphene nanosheet with the number of the layers being 8 is prepared and recovered to obtain FeCl3、CuCl2And AlCl3The purities were 98.40%, 98.33%, and 97.96%, respectively.
Example 4
This example is substantially the same as example 3, except that step (4) the intercalated graphite obtained in step (3) was placed in a 1200W power microwave apparatus for treatment for 2 min. The carbonaceous material containing the graphene nanosheet with the number of the layers being 5 is prepared and recovered to obtain FeCl3、CuCl2And AlCl3The purities were 98.29%, 97.96%, and 98.34%, respectively.
Comparative example 1
This comparative example is substantially the same as example 1 except that the HCl concentration in step (1) is 1 mol/L. This comparative example produced a carbonaceous material containing a few layers of graphite flakes, and the number of graphite flake layers exceeded 15. Recovering to obtain FeCl3、CuCl2And AlCl3The purities were 95.29%, 94.96%, and 93.34%, respectively.
Comparative example 2
This comparative example is substantially the same as example 1 except that the amount of NaClO added in step (2) is 3% by mass of the recovered carbon. This comparative example produced a carbonaceous material containing a few layers of graphite flakes, and the number of graphite flake layers exceeded 15. Recovering to obtain FeCl3、CuCl2And AlCl3The purities were 98.64%, 97.46%, and 98.66%, respectively.
Comparative example 3
This comparative example is substantially the same as example 1 except that the power of the ultrasonic treatment in step (2) was 200W. This comparative example produced a carbonaceous material containing a few layers of graphite flakes, and the number of graphite flake layers exceeded 12. Recovering to obtain FeCl3、CuCl2And AlCl3The purities were 98.27%, 97.86%, and 98.24%, respectively.
Comparative example 4
This comparative example is substantially the same as example 1 except that the time for the ultrasonic treatment in step (2) was 0.5 hours. This comparative example produced a carbonaceous material containing a few layers of graphite flakes, and the number of graphite flake layers exceeded 20. Recovering to obtain FeCl3、CuCl2And AlCl3The purities were 98.21%, 97.86%, and 98.34%, respectively.
Comparative example 5
This comparative example is substantially the same as example 1 except that the ultrasonic treatment frequency in step (2) was 10 KHz. This comparative example produced a carbonaceous material containing a few layers of graphite flakes, and the number of graphite flake layers exceeded 18. Recovering to obtain FeCl3、CuCl2And AlCl3Each purity was 98.39％，97.85％，98.77％。
Comparative example 6
This comparative example is substantially the same as example 1 except that the heating holding time of the solid matter in step (4) was 0.5 hours. This comparative example produced a carbonaceous material containing a few layers of graphite flakes, and the number of graphite flake layers exceeded 15. Recovering to obtain FeCl3、CuCl2And AlCl3The purities were 98.49%, 97.66%, and 98.22%, respectively.
Comparative example 7
This comparative example is substantially the same as example 1 except that the heating temperature of the solid matter in step (4) was 200 ℃. This comparative example produced a carbonaceous material containing a few layers of graphite flakes, and the number of graphite flake layers exceeded 20. Recovering to obtain FeCl3、CuCl2And AlCl3The purities were 98.41%, 97.56%, and 98.32%, respectively.
Comparative example 8
This comparative example is substantially the same as example 3 except that the solid matter was treated in step (4) by placing it in a microwave apparatus of 200W power. This comparative example produced a carbonaceous material containing a few layers of graphite flakes, and the number of graphite flake layers exceeded 18. Recovering to obtain FeCl3、CuCl2And AlCl3The purities were 98.61%, 97.38%, and 98.63%, respectively.
Comparative example 9
This comparative example is substantially the same as example 3 except that the solid matter was left in the microwave apparatus for a treatment time of 10 seconds in step (4). This comparative example produced a carbonaceous material containing a few layers of graphite flakes, and the number of graphite flake layers exceeded 20. Recovering to obtain FeCl3、CuCl2And AlCl3The purities were 98.51%, 97.64% and 98.78%, respectively.
Comparative example 10
This comparative example is substantially the same as example 1 except that in step (5), FeCl was carried out while the acidic filtrate was always heated to 80 deg.C3、CuCl2And AlCl3The three are classified and recycled. This example is to prepareRecovering the carbonaceous material containing the graphene nanosheet with the number of the layers being 3 to obtain FeCl3、CuCl2And AlCl3The purities were 79.34%, 76.32%, and 80.96%, respectively.
Comparative example 11
This comparative example is substantially the same as example 1 except that AlCl was used in step (5)3Seed crystal, CuCl2Seed crystal and FeCl3The addition amount of the seed crystal was 2% by mass of the recovered carbon. The carbonaceous material containing the graphene nanosheet with the number of the layers being 3 is prepared and recovered to obtain FeCl3、CuCl2And AlCl3The purities were 75.36%, 71.38%, and 76.55%, respectively.
Comparative example 12
This comparative example is substantially the same as example 1 except that the stirring manner in step (1) is manual stirring. This comparative example produced a carbonaceous material containing a few layers of graphite flakes, and the number of graphite flake layers exceeded 18. Recovering to obtain FeCl3、CuCl2And AlCl3The purities were 97.51%, 97.48%, and 98.13%, respectively.
Claims (7)
1. A comprehensive treatment method for recycling carbon from waste lithium iron phosphate batteries is characterized by comprising the following steps:
(1) adding the recovered carbon into a mixed acid solution A of hydrochloric acid and other acidic substances according to a liquid-solid mass ratio of 5-10: 1, wherein the concentration of the hydrochloric acid in the mixed acid solution A is 3-10 mol/L, the total concentration of the other acidic substances is 0.5-1 mol/L, and stirring at the temperature of 30-60 ℃ for 6-12 hours to obtain a solution B;
(2) adding an oxidant into the solution B according to 10-30 wt% of the mass of the recovered carbon, carrying out ultrasonic treatment at 25-85 ℃, wherein the power is 400-800W, the frequency is 20-300 KHz, and the ultrasonic time is 1-3 h, and then adding a reducing agent to obtain a solution C;
(3) volatilizing and collecting hydrochloric acid in the solution C, filtering to obtain filter residue and filtrate respectively, heating the crystallization stock solution in the step (5) by using heat in hydrochloric acid steam, mixing the collected hydrochloric acid with the filtrate to obtain mixed acid solution D for later use, washing the filter residue until the pH of an eluate is 5-7, and drying to obtain a solid substance;
(4) in the mixed atmosphere of oxygen and protective gas, preserving the heat of the solid matter for 1-3 h at 400-500 ℃, wherein the heating rate is 5-10 ℃/min; or subjecting the solid substance to microwave treatment at 500-1200W for 0.5-2 min to obtain a solid mixture E;
(5) placing the solid mixture E in a mixed acid solution D, stirring for 6-12 h at 30-60 ℃, and filtering to obtain a carbon material containing graphene nanosheets and a crystallization stock solution;
firstly, keeping the temperature of the crystallization stock solution at 100-120 ℃ for 1-2 h to volatilize and collect hydrochloric acid in the crystallization stock solution, and adding AlCl with the mass of 5-8 wt% of the recovered carbon into the residual solution3Seeding with AlCl3Crystallizing, separating to obtain AlCl3Crystals and primary filtrate;
preserving the temperature of the primary filtrate at 80-100 ℃ for 1-2 h, and adding CuCl accounting for 5-8 wt% of the mass of the recovered carbon2Seeding with CuCl2Crystallizing, separating to obtain CuCl2Crystals and secondary filtrate;
preserving the heat of the secondary filtrate at 80-100 ℃ for 1-2 h, and adding FeCl accounting for 5-8 wt% of the mass of the recovered carbon3Seed crystal of FeCl3Crystallizing, separating to obtain FeCl3Crystals and tertiary filtrate;
the heat in the hydrochloric acid steam is used for heating the solution C in the step (3), and the collected hydrochloric acid is mixed with the third filtrate and then returns to the step (1) for recycling;
the recovered carbon is carbon obtained by disassembling and crushing the waste lithium iron phosphate power battery, separating the positive and negative active substances from the current collector by high-temperature heat treatment, recovering valuable metal elements in the active substances from the solution by adopting a hydrometallurgy method, and finally filtering and recovering the solution.
2. The comprehensive treatment method for recycling carbon from waste lithium iron phosphate batteries according to claim 1, characterized in that: in the step (1), the stirring manner is at least one selected from mechanical stirring, gas flow stirring and jet stirring.
3. The comprehensive treatment method for recycling carbon from waste lithium iron phosphate batteries according to claim 1, characterized in that: in step (1), the other acidic substance is selected from H2SO4、HNO3、H3PO4、HPO3、HClO3、HClO、H2FeO4HCOOH and CH3At least one of COOH.
4. The comprehensive treatment method for recycling carbon from waste lithium iron phosphate batteries according to claim 1, characterized in that: in the step (2), the oxidant is selected from NaClO and NaClO3、NaClO4、KClO、KClO3、KClO4、NH4ClO3、NH4ClO4、Na2S2O8、K2S2O8、(NH4)2S2O8、K2FeO4And Na2FeO4At least one of (1).
5. The comprehensive treatment method for recycling carbon from waste lithium iron phosphate batteries according to claim 1, characterized in that: in the step (2), the reducing agent is selected from H2O2、FeSO4Reduced iron powder and FeCl2、H2C2O4And Na2SO3At least one of the reducing agent and the oxidizing agent, wherein the molar ratio of the reducing agent to the oxidizing agent is 0.8-2: 1.
6. The comprehensive treatment method for recycling carbon from waste lithium iron phosphate batteries according to claim 1, characterized in that: in the step (3), the temperature for volatilizing and collecting the hydrochloric acid is 80-120 ℃.
7. The comprehensive treatment method for recycling carbon from waste lithium iron phosphate batteries according to claim 1, characterized in that: in the step (4), the flow rate of the mixed atmosphere is 30-200 mL/min, wherein the volume ratio of oxygen is 21-40%, and the protective gas is at least one of nitrogen and argon.
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| CN110581323B (en) * | 2019-09-25 | 2021-10-22 | 深圳清华大学研究院 | In-situ regeneration method of waste lithium iron phosphate battery positive electrode material |
| CN111009660B (en) * | 2019-11-26 | 2021-04-13 | 宁夏百川新材料有限公司 | Method for preparing lithium iron phosphate positive electrode material from waste lithium iron phosphate battery |
| CN113023703A (en) * | 2021-03-24 | 2021-06-25 | 郑州中科新兴产业技术研究院 | Method for recycling waste lithium iron phosphate powder |
| CN113108291B (en) * | 2021-04-22 | 2022-10-18 | 红河州现代德远环境保护有限公司 | Device for pretreating dichloroethane by pyrogenic process |
| CN113594420B (en) * | 2021-09-30 | 2022-02-01 | 中南大学 | Regeneration method of lithium ion battery graphite cathode and regenerated graphite cathode thereof |
| CN114497796B (en) * | 2022-02-15 | 2022-08-09 | 湖南工程学院 | Full-component resource recycling method for lithium iron phosphate-carbon waste |
| CN114853004A (en) * | 2022-04-25 | 2022-08-05 | 蜂巢能源科技股份有限公司 | Negative electrode material and preparation method and application thereof |
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