CN113913615A - Method for selectively recovering valuable metals of waste lithium iron phosphate batteries - Google Patents
Method for selectively recovering valuable metals of waste lithium iron phosphate batteries Download PDFInfo
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- CN113913615A CN113913615A CN202111116403.9A CN202111116403A CN113913615A CN 113913615 A CN113913615 A CN 113913615A CN 202111116403 A CN202111116403 A CN 202111116403A CN 113913615 A CN113913615 A CN 113913615A
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- Prior art keywords
- iron phosphate
- lithium iron
- waste lithium
- organic acid
- valuable metals
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- 238000000034 method Methods 0.000 title claims abstract description 44
- 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 36
- 239000002699 waste material Substances 0.000 title claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 34
- 239000002184 metal Substances 0.000 title claims abstract description 34
- 150000002739 metals Chemical class 0.000 title claims abstract description 26
- 238000002386 leaching Methods 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 23
- 150000007524 organic acids Chemical class 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 21
- -1 organic acid salt Chemical class 0.000 claims abstract description 19
- 238000001354 calcination Methods 0.000 claims abstract description 15
- 238000000227 grinding Methods 0.000 claims abstract description 15
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011888 foil Substances 0.000 claims abstract description 8
- 230000003213 activating effect Effects 0.000 claims abstract description 5
- 239000012535 impurity Substances 0.000 claims abstract description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical group OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical group OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 239000002738 chelating agent Substances 0.000 claims description 9
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical group OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 8
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical group OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 4
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 claims description 4
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Chemical group OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical group OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Chemical group [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 4
- 239000000783 alginic acid Substances 0.000 claims description 4
- 235000010443 alginic acid Nutrition 0.000 claims description 4
- 229960001126 alginic acid Drugs 0.000 claims description 4
- 229920000615 alginic acid Polymers 0.000 claims description 4
- 150000004781 alginic acids Chemical group 0.000 claims description 4
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Chemical group OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 4
- 235000015165 citric acid Nutrition 0.000 claims description 4
- WPUMTJGUQUYPIV-JIZZDEOASA-L disodium (S)-malate Chemical compound [Na+].[Na+].[O-]C(=O)[C@@H](O)CC([O-])=O WPUMTJGUQUYPIV-JIZZDEOASA-L 0.000 claims description 4
- 235000012208 gluconic acid Nutrition 0.000 claims description 4
- 239000000174 gluconic acid Chemical group 0.000 claims description 4
- 239000001630 malic acid Chemical group 0.000 claims description 4
- 235000011090 malic acid Nutrition 0.000 claims description 4
- 235000019265 sodium DL-malate Nutrition 0.000 claims description 4
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 claims description 4
- 239000000661 sodium alginate Substances 0.000 claims description 4
- 235000010413 sodium alginate Nutrition 0.000 claims description 4
- 229940005550 sodium alginate Drugs 0.000 claims description 4
- 239000001509 sodium citrate Substances 0.000 claims description 4
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 4
- 229960001790 sodium citrate Drugs 0.000 claims description 4
- 235000011083 sodium citrates Nutrition 0.000 claims description 4
- 239000000176 sodium gluconate Substances 0.000 claims description 4
- 235000012207 sodium gluconate Nutrition 0.000 claims description 4
- 229940005574 sodium gluconate Drugs 0.000 claims description 4
- 239000001394 sodium malate Substances 0.000 claims description 4
- 239000001433 sodium tartrate Substances 0.000 claims description 4
- 229960002167 sodium tartrate Drugs 0.000 claims description 4
- 235000011004 sodium tartrates Nutrition 0.000 claims description 4
- 239000011975 tartaric acid Chemical group 0.000 claims description 4
- 235000002906 tartaric acid Nutrition 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 3
- 229940039790 sodium oxalate Drugs 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 2
- 230000009920 chelation Effects 0.000 claims 2
- 238000011084 recovery Methods 0.000 abstract description 21
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000008569 process Effects 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 238000001994 activation Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009854 hydrometallurgy Methods 0.000 description 2
- 238000010303 mechanochemical reaction Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000009853 pyrometallurgy Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005280 amorphization Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 229940116315 oxalic acid Drugs 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
- C22B1/005—Preliminary treatment of scrap
-
- 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
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Environmental & Geological Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Secondary Cells (AREA)
Abstract
The invention aims to provide a method for selectively recovering valuable metals of waste lithium iron phosphate batteries, which has the advantages of low cost, low energy consumption, environmental friendliness and high valuable metal recovery efficiency. The method for selectively recovering valuable metals of waste lithium iron phosphate batteries comprises the steps of calcining a waste lithium iron phosphate positive plate, removing aluminum foils and organic impurities in the aluminum foils, and obtaining a positive powder material; adding a certain amount of organic acid salt or organic acid with a chelating function into the obtained powder material as a grinding aid, adding the powder material and the grinding aid into a ball mill together, grinding and activating the powder material and the organic acid salt or organic acid with the chelating function, and simultaneously realizing selective leaching of valuable metals in the powder material.
Description
Technical Field
The invention relates to a method for selectively recovering valuable metals of waste lithium iron phosphate batteries.
Background
The recovery of the lithium iron phosphate battery mainly refers to the recovery of valuable metals of a positive electrode material (lithium). The lithium iron phosphate battery has the advantages of high safety, long service life, low cost, no toxicity and the like, and plays an important role in the market of electric automobiles. China is the largest producing country and consuming country of lithium iron phosphate, and in 2015, the yield of the electric automobile battery is 15.7GWH, wherein the lithium iron phosphate battery accounts for about 69%, and is expected to reach 25GWH in 2020. Although it is considered to be relatively environmentally friendly, the disposal of used lithium iron phosphate batteries results in the waste of valuable resources such as lithium and the like, and also causes environmental pollution problems because they contain toxic organic electrolytes. Therefore, it is necessary to recover the waste lithium iron phosphate batteries in an efficient and environmentally friendly manner.
In the recovery process of lithium iron phosphate batteries, hydrometallurgy, pyrometallurgy and mechanochemical methods are widely used. Since lithium iron phosphate has a stable olivine structure, hydrometallurgy generally requires the use of H2SO4、HCl、H3PO4When the strong acid is used as a leaching agent, secondary pollution such as acidic or alkaline waste water, waste gas and waste residue can be caused; pyrometallurgy consumes a lot of energy, generates greenhouse gases, and has a complicated process. Therefore, there is a need to improve the original recovery method or develop an efficient, green and cost-effective method for recovering the waste lithium iron phosphate batteries.
The existing waste lithium ion battery recovery process uses less mechanochemical method and organic acid leaching method, and has certain technical defects. In some processes, the anode material and the active additive are mixed and ground firstly, and then the ground material is mixed with the inorganic acid for leaching experiments, so that the steps are complex, the operation is complicated, and the process time is long; some processes directly adopt organic acid and reducing agent to leach valuable metals, the leaching efficiency is not high, and reducing agent needs to be added.
Disclosure of Invention
Aiming at the problems of high energy consumption, easy generation of pollutant toxic substances, low efficiency and high cost in the existing technology for recycling waste lithium iron phosphate batteries, the invention provides the method for selectively recycling the valuable metals of the waste lithium iron phosphate batteries, which has the advantages of low cost, low energy consumption, environmental friendliness and high valuable metal recycling efficiency, by utilizing organic acid and combining a mechanochemical method.
The method for selectively recovering valuable metals of waste lithium iron phosphate batteries comprises the following steps:
A. calcining the waste lithium iron phosphate positive plate, and removing aluminum foil and organic impurities in the aluminum foil to obtain a powder material;
B. adding a certain amount of chelating agent which is organic acid or organic acid salt with a chelating function into the powder material obtained in the step A, adding the powder material and the chelating agent into a ball mill together, grinding and activating the powder material, the organic acid salt or the organic acid, and simultaneously leaching valuable metals in the powder material;
C. washing the milled mixture from the ball mill pot with deionized water;
D. b, leaching the ground mixture obtained in the step B to obtain a leaching solution;
E. adding Na into the leaching solution2CO3To obtain Li2CO3And (4) precipitating.
Preferably, the calcining temperature of the waste lithium iron phosphate positive plate in the step A is 300-500 ℃, the calcining time is 0.5-3 hours, and the organic acid with the chelating function in the step B is alginic acid, gluconic acid, tartaric acid, citric acid, oxalic acid or malic acid; the organic acid salt with chelating function is sodium alginate, sodium gluconate, sodium tartrate, sodium citrate, oxalic acid or sodium malate.
Preferably, the calcining temperature of the waste lithium iron phosphate positive plate in the step A is 350-450 ℃, and the calcining time is 1-2 hours.
Preferably, in the step E, the leachate is stirred at 85-95 ℃ to evaporate water, and then saturated Na is added into the leachate2CO3Solution to obtain Li2CO3And (4) precipitating.
Compared with the prior art, the method for selectively recovering valuable metals of waste lithium iron phosphate batteries has the following beneficial effects:
1. the present invention has proven to be an effective recovery method by promoting leaching of valuable metals by means of mechanochemical methods. The mechanochemical method is a method of applying mechanical energy to an object by compression, shearing, friction, extension and the like to induce physical and chemical changes including phase change, structural defects, strain, amorphization, and even direct reaction at normal temperature and normal pressure, which can recover metal at high extraction efficiency at room temperature and shorten the process flow.
2. The invention adopts a mechanical and chemical combination method, and uses natural degradable organic acid or organic acid salt with chelating function as a ball milling auxiliary agent, thereby improving the leaching efficiency of metal ions and avoiding the defect of secondary pollution of a recovery technology. The extraction process is intensified by adopting a mechanochemical method, so that the extraction process of metal ions is promoted, and the selective extraction, separation and recovery of iron and lithium are realized.
3. The method adopts the organic acid with the chelating function or the organic acid salt with the chelating function as the grinding aid and the leaching agent, does not cause secondary pollution to the environment, is green and environment-friendly, and has high recovery efficiency. The mechanochemical reaction can reduce the particle size, destroy the crystal structure of a substance, facilitate the recovery of valuable metals, improve the recovery efficiency, reduce the process cost, integrate the mechanochemical activation process and the acid leaching process, have simple operation and great industrial application potential. Therefore, the method for selectively recovering valuable metals from the waste lithium iron phosphate batteries has the characteristics of low cost, low energy consumption, environmental friendliness and high valuable metal recovery efficiency.
The present invention is described in further detail below.
Detailed Description
The method for selectively recovering valuable metals of waste lithium iron phosphate batteries comprises the following steps:
the method for selectively recovering valuable metals of the waste lithium iron phosphate batteries comprises the following steps:
A. calcining the waste lithium iron phosphate positive plate, and removing aluminum foil and organic impurities in the aluminum foil to obtain a powder material;
B. adding a certain amount of chelating agent into the powder material obtained in the step A as a grinding aid, wherein the chelating agent is organic acid with a chelating function or organic acid salt with a chelating function, the chelating agent can enable the powder material to be changed into paste suitable for grinding, adding the powder material and the chelating agent into a ball mill together, grinding and activating the powder material, the organic acid salt or the organic acid, and simultaneously leaching valuable metals in the powder material;
the chelating agent functions to form a complex with a valuable metal by a coordinate bond, dissolve in a solution, and separate from the remaining insoluble metal.
C. Washing the milled mixture from the ball mill pot with deionized water;
D. b, leaching the ground mixture obtained in the step B to obtain a leaching solution;
E. adding Na into the leaching solution2CO3To obtain Li2CO3And (4) precipitating.
As a further improvement of the invention, in the step a, the calcining temperature of the waste lithium iron phosphate positive plate is 300-500 ℃, the calcining time is 0.5-3 hours, and the organic acid with a chelating function in the step B is alginic acid, gluconic acid, tartaric acid, citric acid, oxalic acid or malic acid; the organic acid salt with chelating function is sodium alginate, sodium gluconate, sodium tartrate, sodium citrate, sodium oxalate or sodium malate. The organic acid or organic acid salt can also play a role of a grinding aid besides being used as an extracting agent;
as a further improvement of the invention, the calcining temperature of the waste lithium iron phosphate positive plate in the step A is 350-450 ℃, and the calcining time is 1-2 hours.
As a further improvement of the invention, in the step E, the leachate is stirred at 85-95 ℃ to evaporate water, and then saturated Na is added into the leachate2CO3Solution to obtain Li2CO3And (4) precipitating.
The existing waste lithium ion battery recovery technology has the disadvantages of large energy consumption, high cost, easy generation of waste water, waste residue and harmful gas which are not friendly to the environment, secondary pollution and complex flow. Aiming at the defects of the traditional recovery technology, the invention designs and develops the lithium ion battery anode material recovery technology with low cost, high efficiency and short flow, and achieves the purposes of improving the recovery rate of valuable metals, improving the defect of secondary pollution of the recovery technology, shortening the process flow and the like.
The invention adopts organic acid or organic acid salt with chelating function as grinding auxiliary agent, combines mechanochemical method to recover material, and utilizes precipitation method to recover valuable metal from waste lithium ion battery.
The grinding aid is organic acid with a chelating function, such as alginic acid, gluconic acid, tartaric acid, citric acid, oxalic acid and malic acid, or organic acid salt with a chelating function, such as one of sodium alginate, sodium gluconate, sodium tartrate, sodium citrate, sodium oxalate, sodium malate and the like; the organic acid or organic acid salt with chelating function can also play a role of a grinding aid besides being used as an extracting agent;
the invention carries out ball milling on the anode material, the activating agent, the organic acid or organic acid salt with chelating function and the like together to carry out mechanochemical activation, integrates the grinding activation process and the metal leaching process, shortens the process flow, reduces the operation steps and can ensure high-efficiency leaching rate.
The method adopts the organic acid with the chelating function or the organic acid salt with the chelating function as the grinding aid and the leaching agent, does not cause secondary pollution to the environment, is green and environment-friendly, and has high recovery efficiency. The mechanochemical reaction can reduce the particle size, destroy the crystal structure of a substance, facilitate the recovery of valuable metals, improve the recovery efficiency, reduce the process cost, integrate the mechanochemical activation process and the acid leaching process, have simple operation and great industrial application potential.
Claims (4)
1. The method for selectively recovering valuable metals of waste lithium iron phosphate batteries is characterized by comprising the following steps of: the method for selectively recovering valuable metals of the waste lithium iron phosphate batteries comprises the following steps:
A. calcining the waste lithium iron phosphate positive plate, and removing aluminum foil and organic impurities in the aluminum foil to obtain a powder material;
B. adding a certain amount of chelating agent which is organic acid or organic acid salt with a chelating function into the powder material obtained in the step A, adding the powder material and the chelating agent into a ball mill together, grinding and activating the powder material, the organic acid salt or the organic acid, and simultaneously leaching valuable metals in the powder material;
C. washing the milled mixture from the ball mill pot with deionized water;
D. b, leaching the ground mixture obtained in the step B to obtain a leaching solution;
E. adding Na into the leaching solution2CO3To obtain Li2CO3And (4) precipitating.
2. The method for selectively recovering valuable metals of waste lithium iron phosphate batteries according to claim 1, characterized in that: the calcining temperature of the waste lithium iron phosphate positive plate in the step A is 300-500 ℃, the calcining time is 0.5-3 hours, the organic acid with the chelation function in the step B is alginic acid, gluconic acid, tartaric acid, citric acid, oxalic acid or malic acid, and the organic acid salt with the chelation function is sodium alginate, sodium gluconate, sodium tartrate, sodium citrate, sodium oxalate or sodium malate.
3. The method for selectively recovering valuable metals of waste lithium iron phosphate batteries according to claim 2, characterized in that: and B, calcining the waste lithium iron phosphate positive plate in the step A at the temperature of 350-450 ℃ for 1-2 hours.
4. The method for selectively recovering valuable metals of waste lithium iron phosphate batteries according to any one of claims 1 to 3, characterized in that: in the step E, the leachate is stirred at 85-95 ℃ to evaporate water, and then saturated Na is added into the leachate2CO3Solution to obtain Li2CO3And (4) precipitating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111116403.9A CN113913615A (en) | 2021-09-23 | 2021-09-23 | Method for selectively recovering valuable metals of waste lithium iron phosphate batteries |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111116403.9A CN113913615A (en) | 2021-09-23 | 2021-09-23 | Method for selectively recovering valuable metals of waste lithium iron phosphate batteries |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113913615A true CN113913615A (en) | 2022-01-11 |
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| CN202111116403.9A Pending CN113913615A (en) | 2021-09-23 | 2021-09-23 | Method for selectively recovering valuable metals of waste lithium iron phosphate batteries |
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Application publication date: 20220111 |