CN113937339A - Recovery method of waste lithium iron phosphate battery - Google Patents
Recovery method of waste lithium iron phosphate battery Download PDFInfo
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- CN113937339A CN113937339A CN202111325110.1A CN202111325110A CN113937339A CN 113937339 A CN113937339 A CN 113937339A CN 202111325110 A CN202111325110 A CN 202111325110A CN 113937339 A CN113937339 A CN 113937339A
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- lithium
- iron
- aluminum
- copper
- battery
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- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000002699 waste material Substances 0.000 title claims abstract description 18
- 238000011084 recovery Methods 0.000 title abstract description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229910052742 iron Inorganic materials 0.000 claims abstract description 32
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 26
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000010949 copper Substances 0.000 claims abstract description 26
- 229910052802 copper Inorganic materials 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 239000012535 impurity Substances 0.000 claims abstract description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 13
- 239000003792 electrolyte Substances 0.000 claims abstract description 12
- 238000002386 leaching Methods 0.000 claims abstract description 12
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 60
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 30
- 238000001914 filtration Methods 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 239000000843 powder Substances 0.000 claims description 26
- AWYIAKPIDHLQNQ-UHFFFAOYSA-N lithium iron(2+) trinitrate Chemical compound [N+](=O)([O-])[O-].[Fe+2].[Li+].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] AWYIAKPIDHLQNQ-UHFFFAOYSA-N 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 19
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 19
- 239000011343 solid material Substances 0.000 claims description 16
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 15
- 238000000926 separation method Methods 0.000 claims description 15
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229910001868 water Inorganic materials 0.000 claims description 10
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 9
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 8
- 239000002910 solid waste Substances 0.000 claims description 7
- 238000004064 recycling Methods 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 claims description 4
- 238000012216 screening Methods 0.000 claims description 4
- 239000005955 Ferric phosphate Substances 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 229940032958 ferric phosphate Drugs 0.000 claims description 3
- 230000005484 gravity Effects 0.000 claims description 3
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 3
- 238000007885 magnetic separation Methods 0.000 claims description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 239000003002 pH adjusting agent Substances 0.000 claims 2
- 229910052744 lithium Inorganic materials 0.000 abstract description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 5
- 229910017052 cobalt Inorganic materials 0.000 abstract description 5
- 239000010941 cobalt Substances 0.000 abstract description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052748 manganese Inorganic materials 0.000 abstract description 5
- 239000011572 manganese Substances 0.000 abstract description 5
- 229910052759 nickel Inorganic materials 0.000 abstract description 5
- 239000010405 anode material Substances 0.000 abstract description 4
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 abstract description 3
- 150000001768 cations Chemical class 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000007789 gas Substances 0.000 abstract description 2
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- 239000010926 waste battery Substances 0.000 abstract description 2
- 150000001805 chlorine compounds Chemical class 0.000 abstract 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 208000028659 discharge Diseases 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The scheme provides a recovery method of waste lithium iron phosphate batteries, and in the closed equipment, the electrolyte in the waste batteries is separated and collected in a low-temperature heating mode, and the battery diaphragm cannot be decomposed under the low-temperature heating condition, so that the recovery and utilization of the subsequent diaphragm are facilitated, and the generation of a large amount of toxic and harmful gases such as chlorides and dioxin due to high-temperature heating is avoided. According to the scheme, the nitric acid is used for selectively leaching iron and lithium in the lithium iron phosphate of the battery anode material, metal copper, metal iron and metal aluminum are not leached, the copper, the iron and the aluminum are effectively separated at one time, the concentrations of the copper, the aluminum and the iron in a leaching solution are all less than 0.1g/L, the leaching rates of the iron and the lithium in the lithium iron phosphate of the battery anode material are all more than 99.2%, the iron and the lithium can be efficiently recovered, and the used nitric acid can be recycled. The method does not bring in cation impurity elements in the recovery process, has short process flow and low energy consumption of auxiliary materials, and the obtained nickel, cobalt, manganese and lithium metal solution has high purity, and the recovery rate of nickel, cobalt, manganese and lithium is more than 99.0 percent.
Description
Technical Field
The invention relates to the field of lithium battery recovery, in particular to a recovery method of waste lithium iron phosphate batteries.
Background
The lithium iron phosphate battery has the advantages of low cost, high safety performance, good cycle performance and the like, and is widely applied to the field of new energy vehicles. With the rapid development of new energy industry, a large number of lithium iron phosphate batteries face the problem of scrapping treatment in the future. Untreated chemical substances such as battery positive and negative electrode materials, polyolefin diaphragms and the like can cause serious pollution to the ecological environment, so that the development of an efficient lithium iron phosphate battery recycling method is beneficial to environmental protection and can avoid resource waste.
The lithium iron phosphate battery mainly comprises four parts, namely a positive electrode, a negative electrode, electrolyte and a diaphragm, and at present, the recovery process of the lithium iron phosphate battery usually needs to disassemble and crush the lithium iron phosphate battery, and then obtain valuable metals such as lithium, cobalt, nickel, manganese and the like through processes such as chemical solvent leaching, extraction, precipitation and the like. In the prior art, the battery liquid and the diaphragm are mainly separated in a high-temperature heating mode in a disassembling link, and a large amount of flue gas containing harmful components such as chloride, dioxin and the like is generated in the heating process, so that secondary pollution is generated to the environment.
In addition, after crushing and screening, the content of copper, iron and aluminum in the positive battery powder is still high in the existing battery recovery process, aluminum, iron and copper are removed in a step-by-step removal mode in the subsequent lithium recovery process, the process flow is long, the efficiency is low, a large amount of waste residues are generated, and the recovery rate of valuable metals is influenced.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for recovering waste lithium iron phosphate batteries, which comprises the following steps:
step 1: crushing the pretreated waste lithium iron phosphate battery to obtain a crushed material;
step 2: placing the crushed materials in a closed environment for heating reaction, and collecting condensed electrolyte through negative pressure to obtain solid materials, wherein the reaction temperature is 100-250 ℃;
and step 3: carrying out physical separation on the solid material to obtain copper, iron, aluminum, a diaphragm and battery powder, wherein the content of copper in the battery powder is 0.2-6.0%, the content of aluminum is 0.2-6.0%, and the content of iron is 0.2-6.0%;
and 4, step 4: adding the battery powder obtained after physical separation into a nitric acid solution with the concentration of 10-60%, reacting for 2-15h at the reaction temperature of 30-80 ℃, and filtering to obtain a lithium iron nitrate leachate and solid waste residues;
and 5: adding water and a first pH regulator into the lithium iron nitrate leachate, regulating the pH value of the lithium iron nitrate leachate to 0.5-2.0, and filtering to obtain a lithium nitrate solution and ferric phosphate;
step 6: and adding a second pH regulator into the lithium nitrate solution, regulating the pH value of the lithium nitrate solution to 3.5-5.0, filtering out impurities, adding sodium carbonate into the lithium nitrate solution after the impurities are removed, and filtering to obtain lithium carbonate.
Preferably, the step 3 further comprises the following steps: carrying out secondary crushing on the solid material, wherein the diameter of the material after secondary crushing is less than 1.5 cm; and screening the materials subjected to secondary crushing, and then carrying out magnetic separation and gravity separation to obtain copper, iron, aluminum, a diaphragm and battery powder.
Preferably, the step 4 further comprises: and spraying and absorbing nitrogen oxides generated in the reaction process by using water to form acidic substances for recycling.
Preferably, the heating temperature in the step 2 is 150-200 ℃.
Preferably, the concentration of the nitric acid solution in the step 4 is 30-50%, 6-10h, and the reaction temperature is more preferably 40-60 ℃.
Preferably, in the step 4, the concentrations of copper, aluminum and iron in the lithium iron nitrate leaching solution are all less than 0.1 g/L.
Preferably, the first PH regulator is one or more of lithium hydroxide, lithium carbonate, sodium hydroxide and sodium carbonate.
Preferably, the second PH regulator is one or more of lithium hydroxide, lithium carbonate, sodium hydroxide, sodium carbonate, sodium sulfide, and lithium sulfide.
Preferably, the pH of the lithium nitrate solution in the step 6 is 4.0 to 4.5.
The beneficial effect of this application is as follows:
1. in the sealing equipment, the electrolyte in the waste battery is separated and collected by adopting a low-temperature heating mode, the battery diaphragm cannot be decomposed under the low-temperature heating condition, the recycling of the subsequent diaphragm is facilitated, and meanwhile, the generation of a large amount of toxic and harmful gases such as chloride, dioxin and the like by high-temperature heating is avoided.
2. According to the scheme, the nitric acid is used for selectively leaching iron and lithium in the lithium iron phosphate of the battery anode material, metal copper, metal iron and metal aluminum are not leached, the copper, the iron and the aluminum are effectively separated at one time, the concentrations of the copper, the aluminum and the iron in a leaching solution are all less than 0.1g/L, the leaching rates of the iron and the lithium in the lithium iron phosphate of the battery anode material are all more than 99.2%, the iron and the lithium can be efficiently recovered, and the used nitric acid can be recycled.
3. The recovery process does not bring in cation impurity elements, the process flow is short, the energy consumption of auxiliary materials is low, the purity of the obtained nickel, cobalt, manganese and lithium metal solution is high, and the recovery rate of nickel, cobalt, manganese and lithium is more than 99.0 percent.
Drawings
For a clearer explanation of the embodiments or technical solutions in the prior art of the present invention, the drawings used in the description of the embodiments or prior art will be briefly described below, and it is obvious for those skilled in the art that other drawings can be obtained based on these drawings without creative efforts.
Fig. 1 is a flowchart of a method for recovering a waste lithium iron phosphate battery according to an embodiment of the present invention.
Detailed Description
In order to make those skilled in the art better understand the technical solutions in the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making creative efforts based on the embodiments of the present invention, shall fall within the protection scope of the present invention.
Aiming at the existing defects, the scheme provides a method for recovering waste lithium iron phosphate batteries. Referring to fig. 1, a flow chart of a method for recycling waste lithium iron phosphate batteries according to an embodiment of the present invention is shown. The method comprises the following specific steps:
s100: crushing the pretreated waste lithium iron phosphate battery to obtain a crushed material;
s200: placing the crushed materials in a closed environment for heating reaction, and collecting condensed electrolyte through negative pressure to obtain solid materials, wherein the reaction temperature is 100-250 ℃;
s300: carrying out physical separation on the solid material to obtain copper, iron, aluminum, a diaphragm and battery powder, wherein the content of copper in the battery powder is 0.2-6.0%, the content of aluminum is 0.2-6.0%, and the content of iron is 0.2-6.0%;
s400: adding the battery powder obtained after physical separation into a nitric acid solution with the concentration of 10-60%, reacting for 2-15h at the reaction temperature of 30-80 ℃, and filtering to obtain a lithium iron nitrate leachate and solid waste residues;
s500: adding water and a first pH regulator into the lithium iron nitrate leachate, regulating the pH value of the lithium iron nitrate leachate to 0.5-2.0, and filtering to obtain a lithium nitrate solution and ferric phosphate;
s600: and adding a second pH regulator into the lithium nitrate solution, regulating the pH value of the lithium nitrate solution to 3.5-5.0, filtering out impurities, adding sodium carbonate into the lithium nitrate solution after the impurities are removed, and filtering to obtain lithium carbonate.
Example 1
Step 1: crushing the pretreated waste lithium iron phosphate battery to obtain a crushed material;
step 2: placing the crushed materials in a closed environment for heating reaction, collecting condensed electrolyte through negative pressure to obtain solid materials, wherein the reaction temperature is 150 ℃, and the collected electrolyte can be reused as the electrolyte of a battery through purification;
and step 3: carrying out physical separation on the solid material to obtain copper, iron, aluminum, a diaphragm and battery powder, wherein the content of copper in the battery powder is 0.2-6.0%, the content of aluminum is 0.2-6.0%, and the content of iron is 0.2-6.0%;
and 4, step 4: adding the battery powder obtained after physical separation into a nitric acid solution with the concentration of 30%, reacting for 6 hours at the reaction temperature of 40 ℃, and filtering to obtain a lithium iron nitrate leachate and solid waste residues;
and 5: adding water, lithium hydroxide and lithium carbonate into the lithium iron nitrate leachate, adjusting the pH value of the lithium iron nitrate leachate to 1.0, filtering to obtain a lithium nitrate solution and iron phosphate, and washing and drying the iron phosphate to prepare lithium iron phosphate;
step 6: adding sodium hydroxide and sodium carbonate into the lithium nitrate solution, adjusting the pH value of the lithium nitrate solution to 4.0, filtering out impurities, adding the sodium carbonate into the lithium nitrate solution without the impurities, filtering to obtain lithium carbonate, and washing, drying and crushing the lithium carbonate to reach the industrial standard of battery-grade lithium carbonate.
Example 2
Step 1: firstly, carrying out discharge treatment on waste lithium iron phosphate batteries, and then crushing to obtain a crushed material;
step 2: putting the crushed materials in a closed environment for heating reaction, and collecting condensed electrolyte through negative pressure to obtain solid materials, wherein the reaction temperature is 200 ℃;
and step 3: carrying out secondary crushing on the solid material, wherein the diameter of the material after secondary crushing is less than 1.5 cm; screening the materials after secondary crushing, and then carrying out magnetic separation and gravity separation to obtain copper, iron, aluminum, a diaphragm and battery powder, wherein the content of copper in the battery powder is 0.2-6.0%, the content of aluminum in the battery powder is 0.2-6.0%, and the content of iron in the battery powder is 0.2-6.0%;
and 4, step 4: adding the sorted battery powder into a nitric acid solution with the concentration of 50%, reacting for 10 hours at the reaction temperature of 60 ℃, filtering to obtain a lithium iron nitrate leaching solution and solid waste residues, and spraying and absorbing nitrogen oxides generated in the reaction process by using water to form acidic substances for recycling;
and 5: adding water, lithium carbonate and sodium hydroxide into the lithium iron nitrate leaching solution, adjusting the pH value of the lithium iron nitrate leaching solution to 2.0, and filtering to obtain a lithium nitrate solution and iron phosphate;
step 6: adding sodium hydroxide, sodium carbonate and sodium sulfide into the lithium nitrate solution, adjusting the pH value of the lithium nitrate solution to 4.5, filtering out impurities, adding sodium carbonate into the lithium nitrate solution after the impurities are removed, and filtering to obtain lithium carbonate.
Example 3
Step 1: crushing the pretreated waste lithium iron phosphate battery to obtain a crushed material;
step 2: putting the crushed materials in a closed environment for heating reaction, and collecting condensed electrolyte through negative pressure to obtain solid materials, wherein the reaction temperature is 250 ℃;
and step 3: carrying out physical separation on the solid material to obtain copper, iron, aluminum, a diaphragm and battery powder, wherein the content of copper in the battery powder is 0.2-6.0%, the content of aluminum is 0.2-6.0%, and the content of iron is 0.2-6.0%;
and 4, step 4: adding the battery powder obtained after physical separation into a 10% nitric acid solution, reacting for 15 hours at the reaction temperature of 80 ℃, and filtering to obtain a lithium iron nitrate leachate and solid waste residues;
and 5: adding water and sodium carbonate into the lithium iron nitrate leachate, adjusting the pH value of the lithium iron nitrate leachate to 0.5, and filtering to obtain a lithium nitrate solution and iron phosphate;
step 6: adding lithium sulfide into the lithium nitrate solution, adjusting the pH value of the lithium nitrate solution to 5, filtering out impurities, adding sodium carbonate into the lithium nitrate solution from which the impurities are removed, filtering to obtain lithium carbonate, and washing, drying and crushing the lithium carbonate to reach the industrial standard of battery-grade lithium carbonate.
Example 4
Step 1: crushing the pretreated waste lithium iron phosphate battery to obtain a crushed material;
step 2: putting the crushed materials in a closed environment for heating reaction, and collecting condensed electrolyte through negative pressure to obtain solid materials, wherein the reaction temperature is 100 ℃;
and step 3: carrying out physical separation on the solid material to obtain copper, iron, aluminum, a diaphragm and battery powder, wherein the content of copper in the battery powder is 0.2-6.0%, the content of aluminum is 0.2-6.0%, and the content of iron is 0.2-6.0%;
and 4, step 4: adding the battery powder obtained after physical separation into a nitric acid solution with the concentration of 20%, reacting for 2 hours at the reaction temperature of 30 ℃, and filtering to obtain a lithium iron nitrate leachate and solid waste residues;
and 5: adding water and sodium carbonate into the lithium iron nitrate leachate, adjusting the pH value of the lithium iron nitrate leachate to 0.5, and filtering to obtain a lithium nitrate solution and iron phosphate;
step 6: adding lithium sulfide into the lithium nitrate solution, adjusting the pH value of the lithium nitrate solution to 5, filtering out impurities, adding sodium carbonate into the lithium nitrate solution from which the impurities are removed, filtering to obtain lithium carbonate, and washing, drying and crushing the lithium carbonate to reach the industrial standard of battery-grade lithium carbonate.
In order to make those skilled in the art better understand the technical solutions in the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making creative efforts based on the embodiments of the present invention, shall fall within the protection scope of the present invention.
Claims (9)
1. A method for recovering waste lithium iron phosphate batteries is characterized by comprising the following steps:
step 1: crushing the pretreated waste lithium iron phosphate battery to obtain a crushed material;
step 2: placing the crushed materials in a closed environment for heating reaction, and collecting condensed electrolyte through negative pressure to obtain solid materials, wherein the reaction temperature is 100-250 ℃;
and step 3: carrying out physical separation on the solid material to obtain copper, iron, aluminum, a diaphragm and battery powder, wherein the content of copper in the battery powder is 0.2-6.0%, the content of aluminum is 0.2-6.0%, and the content of iron is 0.2-6.0%;
and 4, step 4: adding the battery powder obtained after physical separation into a nitric acid solution with the concentration of 10-60%, reacting for 2-15h at the reaction temperature of 30-80 ℃, and filtering to obtain a lithium iron nitrate leachate and solid waste residues;
and 5: adding water and a first pH regulator into the lithium iron nitrate leachate, regulating the pH value of the lithium iron nitrate leachate to 0.5-2.0, and filtering to obtain a lithium nitrate solution and ferric phosphate;
step 6: and adding a second pH regulator into the lithium nitrate solution, regulating the pH value of the lithium nitrate solution to 3.5-5.0, filtering out impurities, adding sodium carbonate into the lithium nitrate solution after the impurities are removed, and filtering to obtain lithium carbonate.
2. The method of claim 1, wherein the step 3 further comprises the steps of:
carrying out secondary crushing on the solid material, wherein the diameter of the material after secondary crushing is less than 1.5 cm;
and screening the materials subjected to secondary crushing, and then carrying out magnetic separation and gravity separation to obtain copper, iron, aluminum, a diaphragm and battery powder.
3. The method of claim 1, wherein the step 4 further comprises: and spraying and absorbing nitrogen oxides generated in the reaction process by using water to form acidic substances for recycling.
4. The method as claimed in claim 1, wherein the heating temperature in step 2 is 150 ℃ to 200 ℃.
5. The method according to claim 1, wherein the concentration of the nitric acid solution in the step 4 is 30-50%, the reaction temperature is more preferably 40-60 ℃ for 6-10 h.
6. The method according to claim 1, wherein in the step 4, the concentrations of copper, aluminum and iron in the lithium iron nitrate leaching solution are less than 0.1 g/L.
7. The method of claim 1, wherein the first PH adjusting agent is one or more of lithium hydroxide, lithium carbonate, sodium hydroxide, and sodium carbonate.
8. The method of claim 1, wherein the second PH adjusting agent is one or more of lithium hydroxide, lithium carbonate, sodium hydroxide, sodium carbonate, sodium sulfide, and lithium sulfide.
9. The method of claim 1, wherein the lithium nitrate solution in step 6 has a pH of 4.0 to 4.5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111325110.1A CN113937339A (en) | 2021-11-10 | 2021-11-10 | Recovery method of waste lithium iron phosphate battery |
Applications Claiming Priority (1)
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