CN110994062A - Recovery method for removing fluorine at front section of waste lithium ion battery - Google Patents
Recovery method for removing fluorine at front section of waste lithium ion battery Download PDFInfo
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- CN110994062A CN110994062A CN201911179174.8A CN201911179174A CN110994062A CN 110994062 A CN110994062 A CN 110994062A CN 201911179174 A CN201911179174 A CN 201911179174A CN 110994062 A CN110994062 A CN 110994062A
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- fluorine
- lithium
- removal
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- defluorination
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- 239000011737 fluorine Substances 0.000 title claims abstract description 171
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 171
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 44
- 239000002699 waste material Substances 0.000 title claims abstract description 30
- 238000011084 recovery Methods 0.000 title claims abstract description 22
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 title 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 159
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 70
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 70
- 239000000843 powder Substances 0.000 claims abstract description 69
- 239000007788 liquid Substances 0.000 claims abstract description 51
- 238000005406 washing Methods 0.000 claims abstract description 35
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 34
- 238000006115 defluorination reaction Methods 0.000 claims abstract description 33
- 238000001914 filtration Methods 0.000 claims abstract description 28
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 27
- 238000003756 stirring Methods 0.000 claims abstract description 27
- 239000002893 slag Substances 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 238000004064 recycling Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000001556 precipitation Methods 0.000 claims abstract description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- 239000002351 wastewater Substances 0.000 claims description 17
- 238000000605 extraction Methods 0.000 claims description 16
- -1 fluorine ions Chemical class 0.000 claims description 13
- 238000002386 leaching Methods 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 9
- 229910017052 cobalt Inorganic materials 0.000 claims description 9
- 239000010941 cobalt Substances 0.000 claims description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 9
- 239000012535 impurity Substances 0.000 claims description 9
- 229910052748 manganese Inorganic materials 0.000 claims description 9
- 239000011572 manganese Substances 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 7
- 239000000920 calcium hydroxide Substances 0.000 claims description 7
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 7
- 230000001376 precipitating effect Effects 0.000 claims description 7
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 6
- 239000000347 magnesium hydroxide Substances 0.000 claims description 6
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 6
- 238000012216 screening Methods 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 159000000007 calcium salts Chemical class 0.000 claims description 3
- 159000000003 magnesium salts Chemical class 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 238000003672 processing method Methods 0.000 claims 2
- 125000004122 cyclic group Chemical group 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 14
- 229910000029 sodium carbonate Inorganic materials 0.000 description 7
- 239000001099 ammonium carbonate Substances 0.000 description 6
- 235000012501 ammonium carbonate Nutrition 0.000 description 6
- 229910001385 heavy metal Inorganic materials 0.000 description 6
- 239000011268 mixed slurry Substances 0.000 description 6
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 description 5
- 235000011152 sodium sulphate Nutrition 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000001488 sodium phosphate Substances 0.000 description 4
- 229910000162 sodium phosphate Inorganic materials 0.000 description 4
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 235000011181 potassium carbonates Nutrition 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- 239000010926 waste battery Substances 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- VQBIMXHWYSRDLF-UHFFFAOYSA-M sodium;azane;hydrogen carbonate Chemical compound [NH4+].[Na+].[O-]C([O-])=O VQBIMXHWYSRDLF-UHFFFAOYSA-M 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
- H01M10/05—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
-
- 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
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Processing Of Solid Wastes (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to a method for recycling front-section defluorination of waste lithium ion batteries and a defluorination treatment method for the front-section recycling of the waste lithium ion batteries, wherein the defluorination treatment method comprises the following steps: mixing fluorine-containing battery powder with a fluorine-dissolving auxiliary agent solution, heating, stirring and filtering to obtain defluorinated battery powder and fluorine-containing washing liquor; adding a lithium precipitation agent into fluorine-containing washing liquid, heating, stirring and filtering to obtain lithium-containing slag and a liquid after lithium removal; adding a fluorine removing agent into the liquid after lithium removal, stirring and filtering to obtain fluorine-containing slag and the liquid after fluorine removal; and (4) preparing the defluorinated solution into a fluorine dissolving auxiliary agent solution, and repeating the steps. By adopting the method, the fluorine content of the waste lithium ion battery can be reduced to be below 0.11 percent before entering the recovery process, and the fluorine removal rate is up to 90 percent, thereby being beneficial to solving a series of problems caused by fluorine in the battery recovery process; the washing liquid has high cyclic utilization rate, greatly reduces the using amount of water, saves the cost and has great application prospect.
Description
Technical Field
The invention belongs to the technical field of waste battery material recovery, and relates to a recovery method for removing fluorine at the front section of a waste lithium ion battery.
Background
Lithium ion batteries, which were successfully developed in 1990, were constructed by intercalating lithium ions into carbon to form a negative electrode, replacing the metallic lithium or lithium alloy negative electrode of conventional lithium batteries. The negative electrode material mainly comprises petroleum coke and graphite, so that the advantages of high specific energy and high specific power of the lithium battery are kept, and meanwhile, the deposition and dissolution process of lithium ions on a lithium electrode is replaced by the insertion-extraction process of the lithium ions in the carbon negative electrode, so that the problem of dendritic crystal penetration of lithium generated on the surface of the negative electrode is avoided, and the safety of the battery is ensured. The lithium ion battery is taken as a secondary battery with the greatest development prospect in the 21 st century and an energy storage power supply with rapid development, the recovery of the lithium ion battery material is one of the market demands increasingly, but with the rapid development of the lithium ion battery industry, the difficult problem in the recovery technology of the battery material is gradually revealed, and the research on the method for removing fluorine at the front section of the waste lithium ion battery has important significance for the subsequent recovery of valuable metals in the battery powder.
In the existing recovery process of waste batteries, after a lithium ion battery is crushed and screened, the obtained battery powder is leached, purified and extracted to recover valuable metals, and the defluorination is mainly carried out at the later stage of the recovery process. Disadvantages of back-end fluorine removal include: (1) in the valuable metal recovery process, the concentration of various ions in the wastewater can be gradually increased, so that the rear-section defluorination effect is poor, the consumption of auxiliary materials is increased, a large amount of salt is carried in defluorination residues, and the residue amount is increased; (2) fluorine in the lithium ion battery enters a solution along with various metals in a leaching process, so that equipment corrosion is accelerated; (3) the fluorine ions and other ions in the solution can form stable compounds, which easily causes pipeline blockage; (4) fluorine enters into the back extraction solution of P-204 in the extraction section, and is continuously enriched and circulated, so that fluorine enters into the product in the extraction process, and the product quality is influenced.
Disclosure of Invention
At present, valuable metals such as nickel, cobalt, manganese and the like in the lithium ion battery powder are recovered mainly by adopting a sulfuric acid leaching-extraction impurity removal mode, but fluorine in raw materials can completely enter a leaching solution in the leaching process, and can enter a back extraction solution of P-204 in an extraction section, and continuous enrichment circulation is carried out, so that fluorine in the extraction process enters a product, the product quality is influenced, and meanwhile, the requirement on the corrosion resistance of equipment can be improved due to the existence of fluorine.
The invention aims to provide a method for recycling front-section defluorination of waste lithium ion batteries, aiming at the disadvantages of the existing lithium ion battery recycling process. The fluorine-containing battery powder after heat treatment, crushing and screening is treated by adopting a fluorine-dissolving auxiliary agent solution, so that fluorine elements in the battery powder are removed, meanwhile, a washing solution is recycled after treatment, and the battery powder without the fluorine elements is subjected to acid leaching, impurity removal, extraction and other processes to obtain a product containing nickel, cobalt, manganese and lithium and fluorine-free wastewater, so that the influence of fluorine on each section of a lithium ion battery recovery process is reduced. The process has the characteristics of good fluorine removal effect, simplicity in operation, large treatment capacity, material recycling and the like.
In order to achieve the above object, one technical solution adopted by the present invention to solve the technical problem is:
a method for recovering fluorine removed from the front section of a waste lithium ion battery comprises the following steps:
discharging, heat treating, crushing and screening the waste lithium ion battery to obtain fluorine-containing battery powder;
carrying out defluorination treatment on the fluorine-containing battery powder to obtain defluorinated battery powder;
and (3) carrying out acid leaching, impurity removal and extraction on the battery powder after the fluorine removal, and recycling to obtain a product containing nickel, cobalt, manganese and lithium and fluorine-free wastewater.
Preferably, the obtained wastewater is discharged after being treated by heavy metal and reaching the standard.
The invention also provides a defluorination treatment method for the front recovery section of the waste lithium ion battery, which comprises the following steps:
(1) mixing fluorine-containing battery powder with a fluorine-dissolving auxiliary agent solution, heating, stirring and filtering to obtain defluorinated battery powder and fluorine-containing washing liquor;
(2) adding a lithium precipitation agent into fluorine-containing washing liquid, heating, stirring and filtering to obtain lithium-containing slag and a liquid after lithium removal;
(3) and adding the defluorinating agent into the solution after lithium removal, stirring and filtering to obtain fluorine-containing slag and the solution after defluorination.
The defluorination treatment method is used for defluorination treatment of fluorine-containing battery powder, so that the defluorinated battery powder is obtained, and the fluorine content in the defluorination treated battery powder is lower than 0.11%.
In order to reduce the water consumption, save the energy consumption and the raw material cost and improve the cyclic utilization rate of the washing liquid, preferably, the defluorinated solution is prepared into a fluorine-dissolving auxiliary agent solution for mixing with the fluorine-containing battery powder, and the steps (1) to (3) are repeated.
Preferably, the fluorine dissolving assistant is one or more of sodium salt, potassium salt or ammonium salt. More preferably, the fluorine dissolving assistant is one or more of sodium sulfate, sodium carbonate, potassium sulfate, potassium carbonate, ammonium sulfate and ammonium carbonate. Further preferably, the fluorine dissolving assistant is one or more of sodium sulfate, sodium carbonate and ammonium carbonate.
Preferably, the molar quantity of the fluorine dissolving auxiliary agent is 3.5-8.5 times of the theoretical molar quantity of fluorine ions in the fluorine-containing battery powder.
Preferably, the volume ratio of the mass of the fluorine-containing battery powder to the fluorine dissolving assistant solution is 1: 15-25.
Preferably, the fluorine-containing battery powder and the fluorine-dissolving auxiliary agent solution are mixed, heated to 70-90 ℃, stirred and filtered to obtain the fluorine-removed battery powder and the fluorine-containing washing liquid. More preferably, the fluorine-containing battery powder and the fluorine-dissolving auxiliary agent solution are mixed, heated to 70-90 ℃, stirred for 1-2h and filtered to obtain the battery powder after fluorine removal and the fluorine-containing washing liquid.
Preferably, the lithium precipitating agent is at least one of carbonate and phosphate. More preferably, the lithium precipitating agent is one or more of sodium carbonate, sodium phosphate, potassium carbonate, potassium phosphate, ammonium carbonate and ammonium phosphate. Further preferably, the lithium precipitating agent is at least one of sodium carbonate and sodium phosphate.
Preferably, the molar amount of the lithium precipitating agent is 1.1 to 1.4 times of the theoretical molar amount of lithium ions in the fluorine-containing washing liquid.
Preferably, the lithium precipitation agent is added into the fluorine-containing washing liquid, heated to 70-90 ℃, stirred and filtered to obtain the lithium-containing slag and the liquid after lithium removal. More preferably, the lithium precipitation agent is added into the fluorine-containing washing liquid, heated to 70-90 ℃, stirred for 1-2h and filtered to obtain the lithium-containing slag and the liquid after lithium removal. The lithium ion with high concentration in the solution is removed by adding the lithium precipitation agent, so that the situation that fluorine in the battery powder is inhibited from entering the solution when the fluorine dissolving auxiliary agent solution is recycled in the subsequent process is avoided.
Preferably, the defluorinating agent is one or more of calcium hydroxide, magnesium hydroxide, calcium salt and magnesium salt. More preferably, the defluorinating agent is one or more of calcium hydroxide, magnesium hydroxide, calcium sulfate, magnesium sulfate, calcium chloride, magnesium chloride, calcium nitrate and magnesium nitrate. Further preferably, the defluorinating agent is at least one of calcium hydroxide and magnesium hydroxide.
Preferably, the molar quantity of the fluorine removal agent is 2.0-5.0 times of the theoretical molar quantity of fluorine ions in the solution after lithium removal.
Preferably, the defluorinating agent is added into the solution after lithium removal, stirred for 0.5-2h and filtered to obtain the fluorine-containing slag and the solution after defluorination.
In the fluorine-containing battery powder obtained by overdischarging, heat treating, crushing and screening the waste lithium ion battery, fluorine mainly exists in the form of lithium fluoride, fluorine ions can enter fluorine-containing washing liquid under the action of a fluorine-dissolving auxiliary agent, but lithium ions can be introduced into the fluorine-containing washing liquid, the lithium ions existing in the fluorine-containing washing liquid can influence the recycling of the fluorine-removed liquid, the subsequent fluorine-dissolving effect is reduced, therefore, a lithium-precipitating agent is required to be added to precipitate lithium from the fluorine-containing washing liquid, and carbonate or phosphate radical introduced by the lithium-precipitating agent is removed by utilizing the fluorine-removing agent while removing fluorine.
Fluorine ions in the liquid after lithium removal are removed by using a fluorine removal agent, the liquid after fluorine removal obtained after filtration treatment can be recycled, and fluorine dissolving auxiliary agents are continuously supplemented to remove fluorine in the battery powder; and by controlling the adding amount of calcium hydroxide, magnesium hydroxide, calcium salt and magnesium salt, the solution basically does not contain calcium and magnesium ions, so that the additional calcium and magnesium removing process is not needed.
Specifically, the defluorination treatment method for the front recovery section of the waste lithium ion battery comprises the following steps:
(1) mixing fluorine-containing battery powder and fluorine-dissolving auxiliary agent solution according to the mass to volume ratio of 1: 15-25, heating to 70-90 ℃, stirring for 1-2h, and filtering to obtain defluorinated battery powder and fluorine-containing washing liquor;
(2) adding a lithium precipitation agent with the theoretical molar weight of lithium ions being 1.1-1.4 times of that of lithium ions into a fluorine-containing washing liquid, heating to 70-90 ℃, stirring for 1-2h, and filtering to obtain lithium-containing slag and a liquid after lithium removal;
(3) adding a defluorinating agent with 2.0-5.0 times of theoretical molar weight of fluoride ions into the liquid after lithium removal, stirring for 0.5-2h, and filtering to obtain fluorine-containing slag and the liquid after fluorine removal;
(4) and (3) preparing the defluorinated solution and a fluorine dissolving auxiliary agent into a fluorine dissolving auxiliary agent solution, wherein the molar weight of the fluorine dissolving auxiliary agent is 3.5-8.5 times of the theoretical molar weight of fluorine ions in the fluorine-containing battery powder, and repeating the steps (1) to (4).
More specifically, the method for recovering the fluorine removed from the front section of the waste lithium ion battery comprises the following steps:
(1) discharging, heat treating, crushing and screening the waste lithium ion battery to obtain fluorine-containing battery powder;
(2) mixing fluorine-containing battery powder and fluorine-dissolving auxiliary agent solution according to the mass to volume ratio of 1: 25, mixing, heating to 80 ℃, stirring for 1h, and filtering to obtain defluorinated battery powder and fluorine-containing washing liquor;
(3) adding a lithium precipitation agent with the theoretical molar weight of lithium ions being 1.3 times of that of the lithium ions into a fluorine-containing washing liquid, heating to 85 ℃, stirring for 1 hour, and filtering to obtain lithium-containing slag and a liquid after lithium removal;
(4) adding a fluorine removing agent with the theoretical molar weight of 2.5 times of that of fluorine ions into the liquid after lithium removal, stirring for 1h, and filtering to obtain fluorine-containing slag and the liquid after fluorine removal;
(5) preparing the defluorinated solution and a fluorine dissolving auxiliary agent into a fluorine dissolving auxiliary agent solution, wherein the molar weight of the fluorine dissolving auxiliary agent is 3.8 times of the theoretical molar weight of fluorine ions in the fluorine-containing battery powder, and repeating the steps (2) to (5);
(6) after the battery powder after the defluorination is subjected to acid leaching, impurity removal, extraction and other treatment, recycling to obtain a product containing nickel, cobalt, manganese and lithium and wastewater without fluorine;
(7) and the wastewater is discharged after reaching the standard through heavy metal treatment.
Fig. 1 is a process flow chart of the recovery method for removing fluorine at the front section of the waste lithium ion battery.
Compared with the prior art, the invention has the following advantages:
(1) the method can reduce the fluorine content of the waste lithium ion battery to be below 0.11 percent before the waste lithium ion battery enters the recovery process, and the fluorine removal rate is up to 90 percent, thereby being beneficial to solving a series of problems caused by fluorine in the battery recovery process.
(2) The fluorine washing process of the invention has the advantages of simple operation, low equipment requirement and high cyclic utilization rate of the washing liquid, greatly reduces the consumption of water, saves the energy consumption and the cost of raw materials, and has great application prospect.
Drawings
FIG. 1 is a process flow diagram of the recovery method of the front-stage defluorination of the waste lithium ion battery of the invention.
Detailed Description
The present invention is described in further detail below with reference to examples to facilitate understanding of the present invention by those skilled in the art. It should be particularly noted that the examples are given solely for the purpose of illustration and are not to be construed as limitations on the scope of the invention, as non-essential improvements and modifications to the invention may occur to those skilled in the art, which fall within the scope of the invention as defined by the appended claims. Meanwhile, the raw materials mentioned below are not specified in detail and are all commercial products; the concentrations of metal ions in the following examples were all measured by Atomic Absorption Spectrometry (AAS) or inductively coupled plasma atomic emission spectrometry (ICP-AES); the fluorine ion concentration is measured by a fluorine electrode potential method; the process steps or preparation methods not mentioned in detail are all process steps or preparation methods known to the person skilled in the art.
Specifically, the recovery method for removing fluorine at the front section of the waste lithium ion battery comprises the following steps:
(1) discharging, heat treating, crushing and screening the waste lithium ion battery to obtain fluorine-containing battery powder;
(2) mixing fluorine-containing battery powder and fluorine-dissolving auxiliary agent solution according to the mass to volume ratio of 1: 15-25, heating to 70-90 ℃, stirring for 1-2h, and filtering to obtain defluorinated battery powder and fluorine-containing washing liquor;
(3) adding a lithium precipitation agent with the theoretical molar weight of lithium ions being 1.1-1.4 times of that of lithium ions into a fluorine-containing washing liquid, heating to 70-90 ℃, stirring for 1-2h, and filtering to obtain lithium-containing slag and a liquid after lithium removal;
(4) adding a defluorinating agent with 2.0-5.0 times of theoretical molar weight of fluoride ions into the liquid after lithium removal, stirring for 0.5-2h, and filtering to obtain fluorine-containing slag and the liquid after fluorine removal;
(5) preparing the defluorinated solution and a fluorine dissolving auxiliary agent into a fluorine dissolving auxiliary agent solution, wherein the molar weight of the fluorine dissolving auxiliary agent is 3.5-8.5 times of the theoretical molar weight of fluorine ions in the fluorine-containing battery powder, and repeating the steps (2) to (5);
(6) after the battery powder after the defluorination is subjected to acid leaching, impurity removal, extraction and other treatment, recycling to obtain a product containing nickel, cobalt, manganese and lithium and wastewater without fluorine;
(7) and the wastewater is discharged after reaching the standard through heavy metal treatment.
Example 1
A method for recovering fluorine removed from the front section of a waste lithium ion battery comprises the following steps:
(1) discharging the waste lithium ion battery, carrying out heat treatment, crushing and sieving to obtain fluorine-containing lithium cobaltate battery powder;
(2) 50g of battery powder with a fluorine content of about 1.24 percent and 3.8 times of theoretical molar weight of fluorine of sodium sulfate solution are mixed according to the mass-to-volume ratio of 1: 25, mixing to obtain mixed slurry;
(3) stirring the mixed slurry obtained in the step (2) for 1h at the constant temperature of 80 ℃, and filtering to obtain defluorinated battery powder 1-1 and fluorine-containing washing liquor;
(4) adding sodium phosphate with the theoretical molar weight of 1.3 times of lithium into fluorine-containing washing liquid, stirring for 1h at the constant temperature of 85 ℃, and filtering to obtain lithium phosphate slag and a liquid after lithium removal;
(5) adding calcium hydroxide with 2.5 times of fluorine theoretical molar weight into the liquid after lithium removal, stirring for 1h, and filtering to obtain calcium fluoride slag and liquid after fluorine removal;
(6) adding sodium sulfate into the defluorinated solution obtained in the step (5) to prepare a sodium sulfate solution with the theoretical molar weight of 3.8 times of fluorine, and repeating the steps (2) to (6) to obtain defluorinated battery powder 1-2; after analysis, the fluorine content of the battery powder 1-1 and 1-2 is 0.0758 percent and 0.1041 percent respectively, and the fluorine removal rate is 93.9 percent and 91.6 percent respectively;
(7) after the battery powder after the defluorination is subjected to acid leaching, impurity removal, extraction and other treatment, a product containing nickel, cobalt, manganese and lithium and fluorine-free wastewater can be obtained by recycling; and the wastewater is discharged after reaching the standard through heavy metal treatment.
Example 2
A method for recovering fluorine removed from the front section of a waste lithium ion battery comprises the following steps:
(1) discharging the waste lithium ion battery, carrying out heat treatment, crushing and sieving to obtain fluorine-containing lithium cobaltate battery powder;
(2) 50g of battery powder with a fluorine content of about 1.24% and 7.6 times of the theoretical molar weight of sodium carbonate solution are mixed according to a mass-to-volume ratio of 1: 20, mixing to obtain mixed slurry;
(3) stirring the mixed slurry obtained in the step (2) for 2 hours at the constant temperature of 80 ℃, and filtering to obtain defluorinated battery powder 2-1 and fluorine-containing washing liquor;
(4) adding sodium carbonate with the theoretical molar weight of 1.2 times of lithium into fluorine-containing washing liquid, stirring for 2 hours at the constant temperature of 90 ℃, and filtering to obtain lithium carbonate slag and a liquid after lithium removal;
(5) adding magnesium hydroxide with 3.5 times of fluorine theoretical molar weight into the liquid after lithium removal, stirring for 2h, and filtering to obtain magnesium fluoride slag and liquid after fluorine removal;
(6) adding sodium carbonate into the defluorinated solution obtained in the step (5) to prepare a sodium carbonate solution with the theoretical molar weight of 7.6 times of fluorine, and repeating the steps (2) to (6) to obtain defluorinated battery powder 2-2; after analysis, the fluorine content of the battery powder 2-1 and 2-2 after fluorine removal is respectively 0.0605% and 0.0768%, and the fluorine removal rate is respectively 95.1% and 93.8%;
(7) after the battery powder after defluorination is subjected to acid leaching, impurity removal, extraction and other treatment, a product containing nickel, cobalt, manganese and lithium and fluorine-free wastewater can be obtained in a recoverable way; and (4) discharging the wastewater after the wastewater is treated by heavy metal and reaches the standard.
Example 3:
a method for recovering fluorine removed from the front section of a waste lithium ion battery comprises the following steps:
(1) discharging the waste lithium ion battery, carrying out heat treatment, crushing and sieving to obtain fluorine-containing ternary battery powder;
(2) 50g of battery powder with fluorine content of about 0.897 percent and 3.8 times of theoretical molar weight of ammonium carbonate solution are mixed according to the mass-to-volume ratio of 1: 25, mixing to obtain mixed slurry;
(3) stirring the mixed slurry obtained in the step (2) for 2 hours at a constant temperature of 90 ℃, and filtering to obtain defluorinated battery powder 3-1 and fluorine-containing washing liquor;
(4) adding sodium phosphate with the theoretical molar weight of 1.4 times of lithium into fluorine-containing washing liquid, stirring for 2 hours at the constant temperature of 80 ℃, and filtering to obtain lithium phosphate slag and a liquid after lithium removal;
(5) adding calcium hydroxide with the theoretical molar weight of 4.5 times of fluorine into the solution after lithium removal, stirring for 1h, and filtering to obtain calcium fluoride slag and the solution after fluorine removal;
(6) adding ammonium carbonate into the defluorinated solution obtained in the step (5) to prepare an ammonium carbonate solution with the molar weight 3.8 times of the theoretical molar weight of fluorine, and repeating the steps (2) to (6) to obtain defluorinated battery powder 3-2; after the fluorine removal of the 3-1 battery powder and the 3-2 battery powder is obtained by detection and analysis, the fluorine content is 0.0921 percent and 0.0729 percent, and the fluorine removal rate is 89.7 percent and 91.9 percent respectively;
(7) after the battery powder after defluorination is treated by acid leaching, impurity removal, extraction and the like, a product containing nickel, cobalt, manganese and lithium and fluorine-free wastewater can be obtained by recycling; and (4) discharging the wastewater after the wastewater is treated by heavy metal and reaches the standard.
The above embodiments are only preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and all changes, modifications, substitutions, combinations and simplifications made within the scope of the claims of the present invention should be replaced by equivalents, and all such changes, modifications, substitutions, combinations and simplifications should be made within the scope of the present invention.
Claims (10)
1. A defluorination treatment method for the front recovery section of a waste lithium ion battery is characterized by comprising the following steps:
(1) mixing fluorine-containing battery powder with a fluorine-dissolving auxiliary agent solution, heating, stirring and filtering to obtain defluorinated battery powder and fluorine-containing washing liquor;
(2) adding a lithium precipitation agent into fluorine-containing washing liquid, heating, stirring and filtering to obtain lithium-containing slag and a liquid after lithium removal;
(3) and adding the defluorinating agent into the solution after lithium removal, stirring and filtering to obtain fluorine-containing slag and the solution after defluorination.
2. The fluorine removal processing method according to claim 1, wherein the solution after fluorine removal is prepared as a fluorine-dissolving auxiliary solution.
3. The defluorination treatment method according to claim 1, wherein the fluorine dissolving aid is one or more of sodium salt, potassium salt and ammonium salt; the lithium precipitating agent is at least one of carbonate and phosphate; the defluorinating agent is one or more of calcium hydroxide, magnesium hydroxide, calcium salt and magnesium salt.
4. The fluorine removal processing method according to claim 1, wherein the molar amount of the fluorine-dissolving auxiliary agent is 3.5 to 8.5 times of the theoretical molar amount of fluorine ions in the fluorine-containing battery powder.
5. The defluorination treatment method according to claim 1, wherein the volume ratio of the mass of the fluorine-containing battery powder to the fluorine-dissolving auxiliary agent solution is 1: 15-25.
6. The method for defluorination process according to claim 1, wherein the fluorine-containing battery powder is mixed with the solution of fluorine-dissolving auxiliary agent, heated to 70-90 ℃, stirred and filtered to obtain the defluorinated battery powder and the fluorine-containing washing solution.
7. The defluorination treatment method according to claim 1, wherein the molar amount of the lithium precipitating agent is 1.1-1.4 times of the theoretical molar amount of lithium ions in the fluorine-containing washing liquid; the molar weight of the fluorine removing agent is 2.0-5.0 times of the theoretical molar weight of fluorine ions in the liquid after lithium removal.
8. The method for defluorination treatment according to claim 1, wherein the lithium precipitating agent is added into the fluorine-containing washing liquid, heated to 70-90 ℃, stirred and filtered to obtain the lithium-containing slag and the liquid after the removal of lithium.
9. The method for defluorination treatment according to claim 1, wherein the defluorination agent is added into the solution after lithium removal, stirred for 0.5-2h and filtered to obtain the slag containing fluorine and the solution after defluorination.
10. A recovery method for removing fluorine at the front section of a waste lithium ion battery is characterized by comprising the following steps:
discharging, heat treating, crushing and screening the waste lithium ion battery to obtain fluorine-containing battery powder;
carrying out defluorination treatment on the fluorine-containing battery powder by adopting the defluorination treatment method of any one of claims 1 to 9 to obtain defluorinated battery powder;
and (3) carrying out acid leaching, impurity removal and extraction on the battery powder after the fluorine removal, and recycling to obtain a product containing nickel, cobalt, manganese and lithium and fluorine-free wastewater.
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