CN110828927A - Method for comprehensively recovering waste lithium ion batteries - Google Patents
Method for comprehensively recovering waste lithium ion batteries Download PDFInfo
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- CN110828927A CN110828927A CN201910994806.XA CN201910994806A CN110828927A CN 110828927 A CN110828927 A CN 110828927A CN 201910994806 A CN201910994806 A CN 201910994806A CN 110828927 A CN110828927 A CN 110828927A
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- 239000002699 waste material Substances 0.000 title claims abstract description 94
- 238000000034 method Methods 0.000 title claims abstract description 92
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 91
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 46
- 238000002386 leaching Methods 0.000 claims abstract description 43
- 238000010791 quenching Methods 0.000 claims abstract description 37
- 230000000171 quenching effect Effects 0.000 claims abstract description 37
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000843 powder Substances 0.000 claims abstract description 32
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 27
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 27
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 27
- 239000012535 impurity Substances 0.000 claims abstract description 25
- 239000007774 positive electrode material Substances 0.000 claims abstract description 22
- 238000011084 recovery Methods 0.000 claims abstract description 20
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 16
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 16
- 239000002893 slag Substances 0.000 claims abstract description 16
- 238000002425 crystallisation Methods 0.000 claims abstract description 13
- 230000008025 crystallization Effects 0.000 claims abstract description 13
- 150000001868 cobalt Chemical class 0.000 claims abstract description 12
- 150000002696 manganese Chemical class 0.000 claims abstract description 12
- 150000002815 nickel Chemical class 0.000 claims abstract description 12
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims description 44
- 238000004064 recycling Methods 0.000 claims description 41
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 25
- 238000000926 separation method Methods 0.000 claims description 23
- 239000002253 acid Substances 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 18
- 230000035484 reaction time Effects 0.000 claims description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 claims description 12
- 239000010405 anode material Substances 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 7
- 239000007773 negative electrode material Substances 0.000 claims description 7
- 238000004537 pulping Methods 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- 239000011780 sodium chloride Substances 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 238000005984 hydrogenation reaction Methods 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000010406 cathode material Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 abstract description 14
- 239000010941 cobalt Substances 0.000 abstract description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 14
- 229910052748 manganese Inorganic materials 0.000 abstract description 13
- 239000011572 manganese Substances 0.000 abstract description 13
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 12
- 239000007789 gas Substances 0.000 abstract description 11
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002912 waste gas Substances 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 abstract description 3
- 239000010970 precious metal Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 38
- 239000000047 product Substances 0.000 description 37
- 239000002184 metal Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000012043 crude product Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000009854 hydrometallurgy Methods 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
Images
Classifications
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- 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
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
- C22B3/3842—Phosphinic acid, e.g. H2P(O)(OH)
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
- C22B3/3846—Phosphoric acid, e.g. (O)P(OH)3
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining manganese
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
-
- 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
A method for comprehensively recovering waste lithium ion batteries relates to a method for efficiently, environmentally and comprehensively recovering the waste lithium ion batteries. The method is characterized in that the method comprises the steps of carrying out reduction roasting on fine powder of a positive electrode material of a waste lithium ion battery; and putting the anode and cathode fine powder subjected to reduction roasting into water for water quenching to obtain water quenching slag rich in precious metal elements such as nickel, cobalt, manganese and the like and a lithium-rich solution. Leaching the water quenching slag with inorganic acid, and preparing products such as battery-grade nickel salt, cobalt salt, manganese salt and the like by adopting an extraction-back extraction-evaporative crystallization mode. And introducing carbon dioxide gas into the lithium-rich solution to obtain a crude lithium carbonate product, and hydrogenating and purifying to obtain a battery-grade lithium carbonate product. The method has high leaching rate and comprehensive recovery rate of nickel, cobalt and manganese; and the lithium-rich solution has low impurity content, the prepared product has high purity, and the comprehensive recovery rate of lithium can reach more than 90%. The recovered and output products reach the battery level, the process flow is short and environment-friendly, no waste slag, waste water and waste gas are discharged, and the recovery cost is low.
Description
Technical Field
A method for comprehensively recovering waste lithium ion batteries relates to a method for efficiently, environmentally and comprehensively recovering the waste lithium ion batteries, and belongs to the field of waste battery recovery and precious metal recovery.
Background
The lithium ion battery (hereinafter referred to as lithium battery) has the obvious advantages of high voltage, large specific capacity, long service life, no memory effect and the like. With the vigorous popularization of new energy policies in China, the new energy automobile industry develops rapidly, the rapid development of the lithium ion power battery industry is driven, meanwhile, scientific and technological products such as 3C digital products, intelligent lithium ion products and the like are already integrated into daily life of the society, but the recycling problem of waste ternary lithium ion power batteries, lithium ion digital products and other 3C lithium ion batteries is more and more obvious while people enjoy scientific and technological intelligence. The nickel, cobalt and lithium resources contained in the anode material of the waste lithium ion battery are national strategic metals and are also national scarce resources, and the comprehensive recovery of the nickel, the cobalt, the manganese and the lithium in the anode material is significant.
At present, the recovery method of the anode material of the waste lithium ion battery mainly adopts a hydrometallurgical process of sulfuric acid leaching, the basic process of the recovery method is to leach metal in the waste lithium ion anode material by using sulfuric acid, separate and recover nickel, cobalt and manganese by hydrometallurgy, finally enrich lithium, and precipitate lithium ions in solution by using sodium carbonate to form lithium carbonate precipitate. Because the selectivity of the sulfuric acid leaching method is weak, lithium and metals such as aluminum, copper, iron, nickel, cobalt, manganese and the like in the anode material are synchronously leached, and the enrichment and recovery of lithium can be carried out only after a part of lithium is lost through the metal separation and recovery process of nickel, cobalt, manganese and the like. In order to obtain a qualified lithium carbonate product, the synchronous separation of the metals needs to be realized, and the difficulty is very high.
There are several methods for recycling spent lithium ion batteries, but these methods have the following disadvantages.
(1) In patent CN201810353418.9, waste nickel-hydrogen battery materials and waste lithium ion battery materials are mixed and then leached together, then valuable metals such as Ni, Co, Mn, etc. are recovered, and finally Li is recovered.
(2) In patent CN201810265725.1, firstly, an oxidizing agent is added into a positive electrode material of a waste lithium ion battery to perform an oxidation reaction, lithium is converted into a water-soluble lithium salt by an auxiliary agent, then the obtained water-soluble lithium salt is leached in water or an acidic solution, and a lithium-rich solution is obtained after filtration.
(3) In patent CN201810642765.3, the ternary positive electrode material is first leached with sulfuric acid, then the impurities are removed, and finally the precursor is extracted. The method can only recover nickel, cobalt and manganese, and the process is difficult to realize industrialization.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the method for comprehensively recovering the waste lithium ion battery, which has the advantages of high comprehensive recovery rate, high purity of the prepared product, short process flow, no waste slag, waste water and waste gas emission and low recovery cost.
The purpose of the invention is realized by the following technical scheme.
A method for comprehensively recovering waste lithium ion batteries is characterized in that the steps of the comprehensive recovery process comprise:
(1) after discharging the waste lithium ion battery, mechanically crushing and sorting the waste lithium ion battery to obtain fine powder of a positive electrode material;
(2) carrying out reduction roasting on the fine powder of the positive electrode material and a carbon source, and crushing the roasted material after cooling to obtain fine powder of the positive electrode material after reduction roasting;
(3) carrying out water quenching on the fine powder of the cathode material after reduction roasting, and carrying out solid-liquid separation to obtain water quenching slag and a lithium-rich solution;
(4) acid leaching the water quenching slag to obtain acid leaching liquid;
(5) removing impurities from the acid leaching solution, and then removing impurities by using P204、C272Preparing manganese salt and cobalt salt products in an extraction-back extraction-evaporative crystallization mode;
(6) c is to be272After the raffinate is subjected to nickel precipitation, preparing a nickel salt product in an acid dissolution, impurity removal and evaporative crystallization mode;
(7) introducing carbon dioxide gas into the lithium-rich solution for reaction, and performing solid-liquid separation to obtain a crude lithium carbonate product;
(8) adding water into the crude lithium carbonate product for pulping, then introducing carbon dioxide gas for hydrogenation, and obtaining a lithium bicarbonate solution after solid-liquid separation;
(9) and heating and decomposing the lithium bicarbonate solution, and carrying out solid-liquid separation to obtain a lithium carbonate product.
The method for comprehensively recovering the waste lithium ion batteries is characterized in that the discharge process in the step (1) is carried out in NaCl solution.
The method for comprehensively recovering the waste lithium ion batteries is characterized in that the concentration of the NaCl solution is 10-50 g/L.
The method for comprehensively recycling the waste lithium ion batteries is characterized in that the carbon source in the step (2) is one or a mixture of fine powder of a lithium ion battery negative electrode material, graphite, activated carbon and charcoal.
The method for comprehensively recovering the waste lithium ion batteries is characterized in that the adding amount of the carbon source is 15 wt% -100 wt% of the mass of the positive electrode material of the waste lithium batteries.
The method for comprehensively recovering the waste lithium ion batteries is characterized in that the reduction roasting temperature in the step (2) is 750-1300 ℃.
The method for comprehensively recovering the waste lithium ion batteries is characterized in that the reduction roasting time in the step (2) is 15-240 min.
The method for comprehensively recovering the waste lithium ion batteries is characterized in that the water quenching time in the step (3) is 5-60 min.
The method for comprehensively recycling the waste lithium ion batteries is characterized in that the water quenching solid-liquid ratio in the step (3) is 1: 1-1: 10.
The method for comprehensively recovering the waste lithium ion batteries is characterized in that the water quenching mode in the step (3) is one of hot material high-temperature water quenching and cold material normal-temperature water quenching.
The method for comprehensively recycling the waste lithium ion batteries is characterized in that the lithium-rich solution in the step (3) contains 5-25 g/L of lithium.
The method for comprehensively recovering the waste lithium ion batteries is characterized in that the leaching rate of lithium in the step (3) can reach more than 95%.
The method for comprehensively recovering the waste lithium ion batteries is characterized in that the acid dosage in the step (4) is 1.0-1.5 times of the theoretical dosage.
The method for comprehensively recovering the waste lithium ion batteries is characterized in that the inorganic acid in the step (4) is one or a mixture of sulfuric acid, hydrochloric acid, nitric acid and the like.
The method for comprehensively recycling the waste lithium ion batteries is characterized in that the solid-to-liquid ratio of the inorganic acid leaching in the step (4) is 1: 7-1: 20.
The method for comprehensively recovering the waste lithium ion batteries is characterized in that the acid leaching temperature in the step (4) is 70-100 ℃.
The method for comprehensively recovering the waste lithium ion batteries is characterized in that the acid leaching time in the step (4) is 30-300 min.
The method for comprehensively recovering the waste lithium ion batteries is characterized in that the leaching rate of nickel, cobalt and manganese in the step (4) can reach more than 99.9%.
The method for comprehensively recovering the waste lithium ion batteries is characterized in that one or more of sodium carbonate, sodium hydroxide, calcium carbonate and the like are mixed in the step (5) to remove impurities.
The method for comprehensively recycling the waste lithium ion batteries is characterized in that in the step (5), impurity removal pH is 4.0-5.5.
The method for comprehensively recycling the waste lithium ion batteries is characterized in that manganese salt and cobalt salt products in the step (5) reach a battery level.
The method for comprehensively recovering the waste lithium ion batteries is characterized in that the sodium hydroxide used in the step (6) is used for nickel precipitation.
The method for comprehensively recycling the waste lithium ion batteries is characterized in that in the step (6), the pH value of deposited nickel is 7.5-9.0.
The method for comprehensively recovering the waste lithium ion batteries is characterized in that the nickel salt product in the step (6) reaches the battery level.
The method for comprehensively recovering the waste lithium ion batteries is characterized in that the reaction temperature in the step (7) is 50-100 ℃.
The method for comprehensively recycling the waste lithium ion batteries is characterized in that the reaction time in the step (7) is 5-120 min.
The method for comprehensively recycling the waste lithium ion batteries is characterized in that the solid-to-liquid ratio in the step (8) is 1: 10-1: 30.
The method for comprehensively recovering the waste lithium ion batteries is characterized in that the reaction temperature in the step (8) is normal temperature.
The method for comprehensively recycling the waste lithium ion batteries is characterized in that the reaction time in the step (8) is 30-240 min.
The method for comprehensively recovering the waste lithium ion batteries is characterized in that the reaction temperature in the step (9) is 50-100 ℃.
The method for comprehensively recycling the waste lithium ion batteries is characterized in that the reaction time in the step (9) is 30-240 min.
The method for comprehensively recycling the waste lithium ion batteries is characterized in that the lithium carbonate product in the step (9) reaches the battery level.
The method for comprehensively recovering the waste lithium ion batteries has the advantages of short process flow, simple operation, industrial production fit and realization of recovery of all metal elements; in the recovery process, other chemical reagents except acid and alkali are not needed, so that the cost is low; by adopting the method, the recovery rate of lithium can reach more than 90 percent, the highest rate can reach 98 percent, the recovery rates of nickel, cobalt and manganese can reach more than 98 percent, and the product purity is high; the method has the advantages of environment-friendly recovery process and no discharge of waste residues, waste gases and waste water in the process.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The invention is further described with reference to the following drawings and detailed description.
A method for comprehensively recovering waste lithium ion batteries comprises the following specific operation steps:
a method for efficiently, greenly and comprehensively recovering waste lithium ion batteries is characterized by comprising the following specific steps:
step 1, placing a waste lithium ion battery into a NaCl solution for discharging, and then mechanically crushing and sorting to obtain fine powder of a positive electrode material; the concentration of the NaCl solution is 10-50 g/L;
step 2, mixing the fine powder of the positive electrode material and a carbon source in a certain proportion, putting the mixture into a muffle furnace for reduction roasting, and crushing the cooled material to 100 meshes after the roasting is finished and the material is cooled to room temperature to obtain fine powder of the positive electrode material after the reduction roasting; the carbon source can be one or more of lithium ion battery negative electrode material fine powder, graphite, activated carbon and charcoal; the adding amount of the carbon source is 15-100 wt% of the mass of the waste lithium battery anode material; the reduction roasting temperature is 750-1300 ℃; the reduction roasting time is 15-240 min.
Step 3, putting the anode material after reduction roasting into water with a certain solid-to-liquid ratio for water quenching, and obtaining water quenching slag and a lithium-rich solution after solid-liquid separation; the water quenching solid-liquid ratio is 1: 1-1: 10; the water quenching time is 5-60 min; the water quenching mode is one of hot material high-temperature water quenching and cold material normal-temperature water quenching; the obtained lithium-rich solution contains 5-25 g/L of lithium; the leaching rate of lithium can reach more than 95%.
Step 4, carrying out inorganic acid leaching on the water quenching slag to obtain inorganic acid leaching liquid; the inorganic acid is one or a mixture of sulfuric acid, hydrochloric acid, nitric acid and the like; the acid dosage is 1.0-1.5 times of the theoretical dosage; the solid-to-liquid ratio of the inorganic acid leaching is 1: 7-1: 20; the acid leaching temperature is 70-100 ℃; (ii) a The acid leaching time is 30 min-300 min; the leaching rate of nickel, cobalt and manganese can reach more than 99.9 percent.
Step 5, removing impurities from the inorganic acid leaching solution, and then removing impurities by using P204、C272Preparing manganese salt and cobalt salt products in an extraction-back extraction-evaporative crystallization mode; removing impurities by using one or more of sodium carbonate, sodium hydroxide, calcium carbonate and the like; the pH value after impurity removal is 4.0-5.5; the obtained manganese salt and cobalt salt products reach the battery level.
Step 6, adding C272After the raffinate is subjected to nickel precipitation, preparing a nickel salt product in an acid dissolution, impurity removal and evaporative crystallization mode; c272And (3) precipitating nickel in the raffinate by using sodium hydroxide, wherein the pH value of the precipitated nickel is 7.5-9.0, and the prepared nickel salt product reaches the battery level.
Step 7, introducing carbon dioxide gas into the lithium-rich solution for reaction, and performing solid-liquid separation after a period of time to obtain a crude lithium carbonate product; the reaction temperature is 50-100 ℃; the reaction time is 5-120 min.
Step 8, pulping the lithium carbonate crude product and water according to a certain solid-to-liquid ratio, wherein the solid-to-liquid ratio of pulping is 1: 10-1; then introducing carbon dioxide gas for hydrogenation, wherein the reaction temperature is normal temperature; the reaction time is 30-240 min; obtaining a lithium bicarbonate solution after solid-liquid separation;
step 9, heating and decomposing the lithium bicarbonate solution, wherein the reaction temperature is 50-100 ℃; the reaction time is 30-240 min; carrying out solid-liquid separation to obtain a lithium carbonate product; the lithium carbonate product reaches the battery level.
The invention is further described with reference to the following drawings and detailed description.
Example 1
As shown in fig. 1, a method for high-efficiency green comprehensive recovery of waste lithium batteries includes the following steps:
step 1, putting the waste lithium battery into a solution with the concentration of 10g/LNaCl for discharging, and then mechanically disassembling to obtain fine powder of a positive electrode material and fine powder of a negative electrode material;
step 2, adding 30% of negative electrode material fine powder into the positive electrode material fine powder according to the mass ratio, uniformly mixing, putting into a muffle furnace for high-temperature reduction roasting, wherein the roasting temperature is 1000 ℃, the roasting time is 90min, and after the roasting is finished and the material is cooled to room temperature, crushing the cooled material to 100 meshes to obtain the reduction roasted positive electrode material fine powder;
step 3, putting the reduced and roasted anode material fine powder into water according to the solid-to-liquid ratio of 1:2 for normal-temperature water quenching, wherein the water quenching time is 10min, and finally filtering to obtain water quenching slag and a lithium-rich solution containing 21g/L lithium;
step 4, leaching the water-quenched slag with sulfuric acid, wherein the dosage of the sulfuric acid is 1.2 times of the theoretical value, the solid-to-liquid ratio is 1:10, the leaching temperature is 90 ℃, and the leaching time is 90min, so that a sulfuric acid leaching solution is obtained, and the leaching rate of nickel, cobalt and manganese is 98%;
step 5, adjusting the pH value of the sulfuric acid leaching solution to 4.8 by using sodium carbonate to remove impurities, and then removing the impurities by using P204、C272Preparing manganese salt and cobalt salt products in an extraction-back extraction-evaporative crystallization mode;
step 6, adding C272Adjusting the pH value of the raffinate to 8.0 by using sodium hydroxide to precipitate nickel, and preparing a nickel salt product in an acid dissolution-impurity removal-evaporative crystallization mode;
step 7, introducing carbon dioxide gas into the lithium-rich solution for reaction, wherein the reaction temperature is 90 ℃, the reaction time is 20min, the introduction amount of the carbon dioxide is 1.3 times of the theoretical value, and after the reaction is finished, performing solid-liquid separation to obtain a crude lithium carbonate product;
step 8, pulping the lithium carbonate crude product and water according to a solid-liquid ratio of 1:20, then introducing carbon dioxide gas for hydrogenation, wherein the reaction time is 60min, and carrying out solid-liquid separation to obtain a lithium bicarbonate solution;
and 9, heating the lithium bicarbonate solution to 90 ℃ for heating decomposition, and carrying out solid-liquid separation to obtain a lithium carbonate product.
In the embodiment, the lithium carbonate, nickel salt, cobalt salt and manganese salt products can reach the battery level.
Example 2
As shown in fig. 1, a method for efficiently recycling waste lithium batteries includes the following steps:
step 1, putting the waste lithium battery into a 15g/LNaCl solution for discharging, and then mechanically disassembling to obtain fine powder of the positive electrode material;
step 2, adding 35% of graphite powder into the fine powder of the positive electrode material according to the mass ratio, uniformly mixing, putting the mixture into a muffle furnace for high-temperature reduction roasting at 1050 ℃, wherein the roasting time is 60min, and after the roasting is finished and the material is cooled to room temperature, crushing the cooled material to 100 meshes to obtain the fine powder of the positive electrode material after the reduction roasting;
step 3, putting the reduced and roasted anode material fine powder into water according to the solid-to-liquid ratio of 1:3 for normal-temperature water quenching, wherein the water quenching time is 20min, and finally filtering to obtain water quenching slag and a lithium-rich solution containing 17g/L lithium;
step 4, leaching the water-quenched slag with sulfuric acid, wherein the dosage of the sulfuric acid is 1.3 times of the theoretical value, the solid-to-liquid ratio is 1:10, the leaching temperature is 95 ℃, and the leaching time is 120min, so that a sulfuric acid leaching solution is obtained, and the leaching rate of nickel, cobalt and manganese is 98.5%;
step 5, sulfuric acid leachingThe pH of the effluent is adjusted to 4.9 by sodium carbonate for impurity removal, and then the effluent is treated by P204、C272Preparing manganese salt and cobalt salt products in an extraction-back extraction-evaporative crystallization mode;
step 6, adding C272Adjusting the pH value of the raffinate to 8.3 by using sodium hydroxide to precipitate nickel, and preparing a nickel salt product in an acid dissolution-impurity removal-evaporative crystallization mode;
step 7, introducing carbon dioxide gas into the lithium-rich solution for reaction, wherein the reaction temperature is 90 ℃, the reaction time is 25min, the introduction amount of the carbon dioxide is 1.3 times of the theoretical value, and after the reaction is finished, performing solid-liquid separation to obtain a crude lithium carbonate product;
step 8, pulping the lithium carbonate crude product and water according to a solid-liquid ratio of 1:20, then introducing carbon dioxide gas for hydrogenation, wherein the reaction time is 90min, and carrying out solid-liquid separation to obtain a lithium bicarbonate solution;
and 9, heating the lithium bicarbonate solution to 95 ℃ for heating decomposition, and carrying out solid-liquid separation to obtain a lithium carbonate product.
In the embodiment, the lithium carbonate, nickel salt, cobalt salt and manganese salt products can reach the battery level.
Example 3
As shown in fig. 1, a method for efficiently recycling waste lithium batteries includes the following steps:
step 1, putting waste lithium batteries into a 20g/L NaCl solution for discharging, and then mechanically disassembling to obtain fine powder of a positive electrode material and fine powder of a negative electrode material;
step 2, adding 40% of negative electrode material fine powder into the positive electrode material fine powder according to the mass ratio, uniformly mixing, putting into a muffle furnace for high-temperature reduction roasting, wherein the roasting temperature is 1100 ℃, the roasting time is 60min, and after the roasting is finished and the material is cooled to the room temperature, crushing the cooled material to 100 meshes to obtain the reduction roasted positive electrode material fine powder;
step 3, putting the reduced and roasted anode material fine powder into water according to the solid-to-liquid ratio of 1:3 for normal-temperature water quenching, wherein the water quenching time is 30min, and finally filtering to obtain water quenching slag and a lithium-rich solution containing 17g/L lithium;
step 4, leaching the water quenching slag with hydrochloric acid, wherein the amount of the hydrochloric acid is 1.2 times of the theoretical value, the solid-to-liquid ratio is 1:10, the leaching temperature is 95 ℃, and the leaching time is 120min, so that a sulfuric acid leaching solution is obtained, and the leaching rate of nickel, cobalt and manganese is 98.5%;
step 5, adjusting the pH value of the hydrochloric acid leaching solution to 4.6 by using sodium hydroxide and sodium carbonate to remove impurities, and then removing the impurities by using P204、C272Preparing manganese salt and cobalt salt products in an extraction-back extraction-evaporative crystallization mode;
step 6, adding C272Adjusting the pH value of the raffinate to 8.4 by using sodium hydroxide to precipitate nickel, and preparing a nickel salt product in an acid dissolution-impurity removal-evaporative crystallization mode;
step 7, introducing carbon dioxide gas into the lithium-rich solution for reaction, wherein the reaction temperature is 95 ℃, the reaction time is 30min, the introduction amount of the carbon dioxide is 1.4 times of the theoretical value, and after the reaction is finished, performing solid-liquid separation to obtain a crude lithium carbonate product;
step 8, pulping the lithium carbonate crude product and water according to a solid-liquid ratio of 1:20, then introducing carbon dioxide gas for hydrogenation, wherein the reaction time is 150min, and carrying out solid-liquid separation to obtain a lithium bicarbonate solution;
and 9, heating the lithium bicarbonate solution to 95 ℃ for heating decomposition, and carrying out solid-liquid separation to obtain a lithium carbonate product.
The lithium carbonate, nickel salt, cobalt salt and manganese salt products in the embodiment can reach the battery level.
While the present invention has been described in detail with reference to the embodiments shown in the drawings, the present invention is not limited to the embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (27)
1. A method for comprehensively recovering waste lithium ion batteries is characterized in that the steps of the comprehensive recovery process comprise:
(1) after discharging the waste lithium ion battery, mechanically crushing and sorting the waste lithium ion battery to obtain fine powder of a positive electrode material;
(2) carrying out reduction roasting on the fine powder of the positive electrode material and a carbon source, and crushing the roasted material after cooling to obtain fine powder of the positive electrode material after reduction roasting;
(3) carrying out water quenching on the fine powder of the cathode material after reduction roasting, and carrying out solid-liquid separation to obtain water quenching slag and a lithium-rich solution;
(4) acid leaching the water quenching slag to obtain acid leaching liquid;
(5) removing impurities from the acid leaching solution, and then removing impurities by using P204、C272Preparing manganese salt and cobalt salt products in an extraction-back extraction-evaporative crystallization mode;
(6) c is to be272After the raffinate is subjected to nickel precipitation, preparing a nickel salt product in an acid dissolution, impurity removal and evaporative crystallization mode;
(7) introducing carbon dioxide gas into the lithium-rich solution for reaction, and performing solid-liquid separation to obtain a crude lithium carbonate product;
(8) adding water into the crude lithium carbonate product for pulping, then introducing carbon dioxide gas for hydrogenation, and obtaining a lithium bicarbonate solution after solid-liquid separation;
(9) and heating and decomposing the lithium bicarbonate solution, and carrying out solid-liquid separation to obtain a lithium carbonate product.
2. The method for comprehensively recycling waste lithium ion batteries according to claim 1, characterized in that the discharging process in step (1) is performed in NaCl solution.
3. The method for comprehensively recycling the waste lithium ion batteries according to claim 2, characterized in that the concentration of the NaCl solution is 10-50 g/L.
4. The method for comprehensively recycling the waste lithium ion batteries according to claim 1, characterized in that the carbon source in the step (2) is one or more of lithium ion battery negative electrode material fine powder, graphite, activated carbon and charcoal.
5. The method for comprehensively recycling the waste lithium ion batteries according to claim 1, wherein the amount of the added carbon source is 15 wt% to 100 wt% of the mass of the anode materials of the waste lithium batteries.
6. The method for comprehensively recycling the waste lithium ion batteries according to claim 1, wherein the reduction roasting temperature in the step (2) is 750-1300 ℃.
7. The method for comprehensively recycling the waste lithium ion batteries according to claim 1, characterized in that the reduction roasting time in the step (2) is 15-240 min.
8. The method for comprehensively recycling the waste lithium ion batteries according to claim 1, characterized in that the water quenching time in the step (3) is 5-60 min.
9. The method for comprehensively recycling the waste lithium ion batteries according to claim 1, characterized in that the water quenching solid-liquid ratio in the step (3) is 1: 1-1: 10.
10. The method for comprehensively recycling the waste lithium ion batteries according to claim 1, wherein the water quenching manner in the step (3) is one of hot material high-temperature water quenching and cold material normal-temperature water quenching.
11. The method for comprehensively recycling the waste lithium ion batteries according to claim 1, wherein the lithium-rich solution in the step (3) contains 5-25 g/L of lithium.
12. The method for comprehensively recycling the waste lithium ion batteries according to claim 1, characterized in that the acid dosage in the step (4) is 1.0-1.5 times of the theoretical dosage.
13. The method for comprehensively recycling waste lithium ion batteries according to claim 1, characterized in that in the step (4), the inorganic acid is one or more of sulfuric acid, hydrochloric acid, nitric acid, etc.
14. The method for comprehensively recycling the waste lithium ion batteries according to claim 1, characterized in that the solid-to-liquid ratio of the inorganic acid leaching in the step (4) is 1:7 to 1: 20.
15. The method for comprehensively recycling the waste lithium ion batteries according to claim 1, wherein the acid leaching temperature in the step (4) is 70-100 ℃.
16. The method for comprehensively recycling the waste lithium ion batteries according to claim 1, characterized in that the acid leaching time in the step (4) is 30min to 300 min.
17. The method for comprehensively recycling waste lithium ion batteries according to claim 1, characterized in that in the step (5), one or more of sodium carbonate, sodium hydroxide, calcium carbonate, etc. are mixed for impurity removal.
18. The method for comprehensively recycling the waste lithium ion batteries according to claim 1, wherein in the step (5), the pH value after impurity removal is 4.0-5.5.
19. The method for comprehensively recovering the waste lithium ion batteries according to claim 1, characterized in that the sodium hydroxide used in the step (6) is used for nickel precipitation.
20. The method for comprehensively recycling the waste lithium ion batteries according to claim 1, wherein the pH of nickel deposited in the step (6) is 7.5-9.0.
21. The method for comprehensively recycling the waste lithium ion batteries according to claim 1, wherein the reaction temperature in the step (7) is 50-100 ℃.
22. The method for comprehensively recycling the waste lithium ion batteries according to claim 1, wherein the reaction time in the step (7) is 5-120 min.
23. The method for comprehensively recycling the waste lithium ion batteries according to claim 1, wherein the solid-to-liquid ratio in the step (8) is 1:10 to 1: 30.
24. The method for comprehensively recycling waste lithium ion batteries according to claim 1, characterized in that the reaction temperature in the step (8) is normal temperature.
25. The method for comprehensively recycling the waste lithium ion batteries according to claim 1, wherein the reaction time in the step (8) is 30-240 min.
26. The method for comprehensively recycling the waste lithium ion batteries according to claim 1, wherein the reaction temperature in the step (9) is 50-100 ℃.
27. The method for comprehensively recycling the waste lithium ion batteries according to claim 1, wherein the reaction time in the step (9) is 30-240 min.
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