CN117185319A - Method for recovering lithium iron phosphate battery through sulfate air roasting - Google Patents
Method for recovering lithium iron phosphate battery through sulfate air roasting Download PDFInfo
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- CN117185319A CN117185319A CN202310028848.4A CN202310028848A CN117185319A CN 117185319 A CN117185319 A CN 117185319A CN 202310028848 A CN202310028848 A CN 202310028848A CN 117185319 A CN117185319 A CN 117185319A
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- Prior art keywords
- iron phosphate
- sulfate
- lithium
- lithium iron
- battery
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- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 81
- 238000000034 method Methods 0.000 title claims abstract description 47
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 title claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- AWRQDLAZGAQUNZ-UHFFFAOYSA-K sodium;iron(2+);phosphate Chemical compound [Na+].[Fe+2].[O-]P([O-])([O-])=O AWRQDLAZGAQUNZ-UHFFFAOYSA-K 0.000 claims abstract description 27
- 239000000843 powder Substances 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 12
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 11
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 11
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 17
- 229910052744 lithium Inorganic materials 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 15
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 14
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 14
- 235000011152 sodium sulphate Nutrition 0.000 claims description 14
- 238000002386 leaching Methods 0.000 claims description 12
- 238000004064 recycling Methods 0.000 claims description 9
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 7
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 7
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 7
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 7
- 235000011151 potassium sulphates Nutrition 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 238000007654 immersion Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- 239000002033 PVDF binder Substances 0.000 claims description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 229910000358 iron sulfate Inorganic materials 0.000 claims description 2
- 239000002699 waste material Substances 0.000 abstract description 40
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 17
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 14
- 238000007599 discharging Methods 0.000 abstract description 4
- NCZYUKGXRHBAHE-UHFFFAOYSA-K [Li+].P(=O)([O-])([O-])[O-].[Fe+2].[Li+] Chemical compound [Li+].P(=O)([O-])([O-])[O-].[Fe+2].[Li+] NCZYUKGXRHBAHE-UHFFFAOYSA-K 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 238000002791 soaking Methods 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 239000010405 anode material Substances 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 238000001035 drying Methods 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910001415 sodium ion Inorganic materials 0.000 description 5
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 3
- 229940044175 cobalt sulfate Drugs 0.000 description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 3
- 238000009831 deintercalation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229940099596 manganese sulfate Drugs 0.000 description 3
- 239000011702 manganese sulphate Substances 0.000 description 3
- 235000007079 manganese sulphate Nutrition 0.000 description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 239000005955 Ferric phosphate Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 206010027439 Metal poisoning Diseases 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- 208000010501 heavy metal poisoning Diseases 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- ATEAWHILRRXHPW-UHFFFAOYSA-J iron(2+);phosphonato phosphate Chemical compound [Fe+2].[Fe+2].[O-]P([O-])(=O)OP([O-])([O-])=O ATEAWHILRRXHPW-UHFFFAOYSA-J 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- 229960003390 magnesium sulfate Drugs 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229940053662 nickel sulfate Drugs 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229940093914 potassium sulfate Drugs 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Secondary Cells (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to a method for recovering a lithium iron phosphate battery by roasting sulfate air, which comprises the following specific steps: firstly, carrying out pretreatment such as discharging, disassembling and separating on waste lithium iron phosphate batteries to obtain lithium iron phosphate powder, mixing the lithium iron phosphate powder with sulfate, roasting in air, then soaking in water to obtain a lithium ion solution and sodium iron phosphate, adding carbonate into the lithium ion solution to obtain precipitated lithium carbonate, and finally, mixing and reacting the sodium iron phosphate with a reducing agent to prepare the battery-grade sodium iron phosphate. According to the treatment method provided by the invention, not only is the environmental pollution generated by the waste lithium iron phosphate lithium ion battery effectively prevented, but also the waste materials in the waste lithium iron phosphate lithium ion battery can be completely recovered and made into battery-level sodium iron phosphate for use.
Description
Technical Field
The invention relates to the field of waste lithium ion battery recovery, in particular to a method for recovering a lithium iron phosphate battery by roasting sulfate air.
Background
The innovation in low cost, safety and the like of the lithium iron phosphate battery is increasingly remarkable in characteristics, and particularly, the lithium iron phosphate battery is widely applied in the field of public transportation. Compared with the traditional battery, the lithium iron phosphate battery has the characteristics of wide raw material sources, outstanding safety performance, good cycle performance, good thermal stability and the like, the assembly proportion of the lithium iron phosphate battery is continuously increased, and the market share of the lithium iron phosphate battery is expected to be continuously increased in the future.
The service life of the lithium iron phosphate power battery is generally 3-5 years. The waste battery is a battery which is discarded after long-time use, has a larger drop in the existing capacity than the initial capacity or has a larger damage to the battery structure, and cannot meet the normal use. Therefore, in the next few years, the explosive lithium iron phosphate battery retired tide is the key point of the next research on how to recycle the lithium iron phosphate battery in an efficient, green and environment-friendly way
Taking an electric automobile as an example, the service life of the power battery is about 3-5 years. When the capacity of the power battery is reduced to less than 80% of the initial capacity, the power battery can be considered as incapable of meeting the daily use, and a new battery needs to be replaced. The current general recovery method is as follows: the waste lithium iron phosphate battery is regenerated after discharging, disassembling, separating, recycling and other processes. The conventional acid leaching recovery process can transfer most of lithium and iron into solution, but further separation and purification are difficult to be completed efficiently, and the subsequent waste liquid containing acid and heavy metal ions is extremely difficult to be disposed of due to the use of a large amount of inorganic acid. Therefore, a green and efficient method is needed to solve the above problems.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides a method for recovering waste lithium iron phosphate batteries by roasting sulfate air, which has the advantages of simple process flow, easiness in implementation, high recovery efficiency, environmental friendliness and great significance for recovering waste lithium iron phosphate.
In order to solve the problems, the inventor provides a method for recovering waste lithium iron phosphate batteries by roasting sulfate air, which specifically comprises the following steps: firstly, carrying out pretreatment such as discharging, disassembling and separating on a waste lithium iron phosphate battery to obtain lithium iron phosphate powder, mixing the lithium iron phosphate powder with sulfate, carrying out air roasting, then soaking with water to obtain a lithium ion solution and sodium iron phosphate, adding carbonate into the lithium ion solution to obtain precipitated lithium carbonate, and finally, mixing and reacting the sodium iron phosphate with a reducing agent to prepare the battery-grade sodium iron phosphate. According to the method for recovering the lithium iron phosphate battery by roasting the sulfate air, provided by the invention, the recovery flow of the waste lithium iron phosphate lithium ion battery can be effectively shortened, and the recovered material can be fully utilized to prepare the battery-grade sodium iron phosphate.
The invention aims to provide the following technical scheme: a method for recovering lithium iron phosphate batteries by roasting sulfate air is characterized in that the lithium iron phosphate batteries are recovered by roasting sulfate air.
Preferably, the method comprises the steps of,
mixing lithium iron phosphate and sulfate, and performing air roasting to obtain solid powder;
leaching the solid powder in water to obtain a solid-liquid mixture, and filtering and separating to obtain sodium iron phosphate and lithium-containing solution;
carbonate is added to the lithium-containing solution to form a lithium carbonate precipitate.
Preferably, the sulfate is one or more of ammonium sulfate, sodium sulfate, potassium sulfate or magnesium sulfate.
Preferably, the air calcination reaction temperature is 400-800 ℃ and the time is 4-6 h.
Preferably, the water immersion time is 30-60 min.
Preferably, the reaction temperature used in water immersion is 20 to 90 ℃.
Preferably, the molar ratio of the lithium iron phosphate to the sulfate is 1: 1-3:1.
Preferably, the mass ratio of water to baked materials in the water leaching process is 50:1-100:1.
Preferably, the method further comprises the step of mixing and reacting the sodium iron phosphate with a reducing agent to obtain the battery grade sodium iron phosphate.
Preferably, the reducing agent is one or more of glucose, ascorbic acid, hydrogen amine hydrochloride, ammonium dihydrogen phosphate, carbon black and polyvinylidene fluoride.
Has the following beneficial effects:
(1) The method for treating the waste lithium iron phosphate has the advantages of simple flow, simple and convenient operation, and sodium sulfate is used as the metal sulfate with the lowest price, the most stable property and the most extensive source, and can be used as a roasting agent to remarkably reduce the industrial cost, have no side reaction, improve the overall safety of the process, greatly reduce the recovery treatment cost and bring great economic benefit;
(2) The lithium iron phosphate treated by the method has no harmful substance emission, reduces environmental pollution and saves resources;
(3) According to the method for recycling the waste lithium iron phosphate battery through sulfate air roasting, the lithium extraction effect is obvious, the sodium iron phosphate is fully utilized, and the metal resource can be well recycled.
Drawings
FIG. 1 shows a flow chart for recovering waste lithium iron phosphate batteries by roasting sulfate air;
FIG. 2 is a morphology diagram of lithium carbonate prepared by roasting at 800 ℃ for 5 hours in example 1 of the invention.
Detailed Description
The features and advantages of the present invention will become more apparent and clear from the following detailed description of the invention.
The waste lithium iron phosphate battery does not contain heavy metal pollutants such as lead, mercury and the like, but the scrapped lithium iron phosphate battery still has certain harm to the environment. The waste lithium iron phosphate anode material contains abundant metals such as iron, lithium and the like, wherein the element with the most recovery value is lithium, and the iron also has a certain recovery value. The recovery value of the lithium iron phosphate is lower than that of ternary materials because the lithium iron phosphate does not contain high-value metals such as cobalt, nickel and the like. Therefore, the lithium iron phosphate battery has higher requirements on the efficiency and low cost of the recycling process.
At present, the main recovery mode of lithium iron phosphate is wet recovery, namely, leaching of elements such as lithium, iron and the like by using a leaching agent. And removing impurities and purifying the leaching solution, and separating and recovering lithium and iron elements. The leaching agent mainly comprises sulfuric acid, nitric acid, hydrochloric acid and the like. However, a large amount of wastewater containing acid and metal ions is inevitably generated in the wet recycling process, a large amount of funds are consumed in the subsequent purification process, the cost is increased, and the environment is greatly influenced.
In order to solve the problems, the invention provides a method for recycling waste lithium iron phosphate batteries by roasting sulfate air, which comprises the steps of carrying out pretreatment such as discharging, disassembling and separating on the waste lithium iron phosphate batteries to obtain lithium iron phosphate powder, mixing and roasting the lithium iron phosphate powder and sulfate to obtain solid powder, leaching the solid powder into lithium ion solution and sodium iron phosphate, precipitating lithium ions, and mixing and reacting the ferric phosphate with a reducing agent to obtain battery-grade sodium iron phosphate. The method provided by the invention is simple to operate, has short steps, can effectively treat the waste lithium iron phosphate, can fully recycle the waste lithium iron phosphate, and tightly combines environmental protection and economic benefits.
The invention provides a method for recycling waste lithium iron phosphate batteries by roasting sulfate air, which comprises the steps of recycling waste lithium iron phosphate by roasting sulfate air and preparing the waste lithium iron phosphate into battery-level sodium iron phosphate;
wherein the oxidation and calcination temperature is 400-800 ℃, preferably 800 ℃;
wherein the oxidation and calcination reaction time is 4-6 h, preferably 5h;
wherein, the water immersion time is 30-60 min, preferably 60min;
wherein the water immersion temperature is 20-90 ℃, preferably 50 ℃;
according to the method, the lithium iron phosphate and the sulfate can undergo a displacement reaction at high temperature, so that lithium sulfate which is easy to dissolve in water and sodium iron phosphate which is difficult to dissolve in water are generated, and the lithium and the iron can be separated through a simple water leaching process. The lithium-containing solution is separated out in the form of lithium carbonate under the action of carbonate, and the sodium iron phosphate and the reducing agent react to prepare the battery-grade sodium iron phosphate.
The invention is further described below by means of specific examples. These examples are merely exemplary and are not intended to limit the scope of the present invention in any way.
Example 1
Firstly, putting the waste lithium iron phosphate battery into saturated saline water to fully discharge the waste lithium iron phosphate battery for 30 min. And (3) drying the discharged battery in an oven, disassembling the battery shell to obtain a battery inner core, and sorting the anode, the cathode and the diaphragm to obtain the lithium iron phosphate anode material. And burning the anode material for 2 hours at 500 ℃ in an argon atmosphere to obtain waste lithium iron phosphate powder.
7.89g of waste lithium iron phosphate powder and 14.2g of sodium sulfate are weighed and ground uniformly. And (3) heating the mixed sample to 800 ℃ at a speed of 5 ℃/min under the air atmosphere, roasting for 5 hours, and then cooling at a speed of 10 ℃/min. The baked slag is fully placed in 150ml of water solution, the temperature in a water bath kettle is adjusted to 80 ℃ and stirred for 1h, the mixture is filtered, and filter residues are dried for 12h at 80 ℃ to obtain 11.625g of sodium iron phosphate. After adding sodium carbonate, 1.820g of lithium carbonate precipitate was obtained, and the recovery rate was 98.93%.
To determine the optimum reaction temperature of sodium sulfate, experiments were also conducted at different temperatures in this example, and the results (mass ratio) of the test result of the leachate element i cp are shown in table 1 below.
Grinding sodium iron phosphate obtained by roasting at 800 ℃ for 5 hours, and mixing the ground sodium iron phosphate with carbon black and polyvinylidene fluoride according to the mass ratio of 8:1:1 to prepare the electrode. Adding proper amount of N-methyl-2-pyrrolidone, and stirring uniformly. And then coating the slurry on an aluminum foil, drying for 10 hours at 80 ℃, and assembling the aluminum foil into a button cell for electrochemical performance test. At a voltage of 10 mA.g in the range of 2.2 to 4.0V -1 Constant current circulation is carried out on the current density of the lithium ion battery, and the first discharge capacity is 103 mAh.g -1 The coulomb efficiency was 86%, and the discharge capacity after 100 cycles was 61 mA.g -1 。
Example 2
Firstly, putting the waste lithium iron phosphate battery into saturated saline water to fully discharge the waste lithium iron phosphate battery for 30 min. And (3) drying the discharged battery in an oven, disassembling the battery shell to obtain a battery inner core, and sorting the anode, the cathode and the diaphragm to obtain the lithium iron phosphate anode material. And burning the anode material for 2 hours at 500 ℃ in an argon atmosphere to obtain waste lithium iron phosphate powder.
7.89g of waste lithium iron phosphate powder and 14.2g of sodium sulfate are weighed and ground uniformly. And (3) heating the mixed sample to 800 ℃ at a speed of 5 ℃/min under the air atmosphere, roasting for 5 hours, and then cooling at a speed of 10 ℃/min. All the baked slag is placed in 150ml of water solution, the temperature in a water bath kettle is regulated to 80 ℃ and stirred for 1h, the mixture is filtered, and filter residues are dried for 12h at 80 ℃ to obtain 11.609g of sodium iron phosphate. The filtrate was added with sodium carbonate to give 1.815g of lithium carbonate precipitate, and the recovery rate was 98.65% (obtained by calculating the ratio of the lithium content in the recovered lithium carbonate to the lithium content in the filtrate).
Mixing the obtained sodium iron phosphate, ammonium dihydrogen phosphate and glucose according to the mass ratio of 1:0.5:0.2, grinding uniformly, placing into an argon tube furnace, heating to 750 ℃ at the speed of 5 ℃/min, and preserving heat for 5 hours. And (3) placing the roasting product into 150mL of aqueous solution, adjusting the temperature in a water bath to 80 ℃, stirring for 1h, and filtering to obtain filtrate and filter residues. Drying the filter residue at 80 ℃ for 12 hours to obtain 7.125g of ferrous pyrophosphate; the filtrate was dried in an oven at 100deg.C for 12 hours to give 6.627g of sodium pyrophosphate.
Example 3
Firstly, putting the waste lithium iron phosphate battery into saturated saline water to fully discharge the waste lithium iron phosphate battery for 30 min. And (3) drying the discharged battery in an oven, disassembling the battery shell to obtain a battery inner core, and sorting the anode, the cathode and the diaphragm to obtain the lithium iron phosphate anode material. And burning the anode material for 2 hours at 500 ℃ in an argon atmosphere to obtain waste lithium iron phosphate powder.
7.89g of waste lithium iron phosphate powder and 8.71g of potassium sulfate are weighed and ground uniformly. And (3) heating the mixed sample to 700 ℃ at a speed of 5 ℃/min under the air atmosphere, roasting for 5 hours, and then cooling at a speed of 10 ℃/min. The baked slag is fully placed in 150ml of water solution, the temperature in a water bath kettle is adjusted to 80 ℃ and stirred for 1h, the mixture is filtered, and filter residues are dried for 12h at 80 ℃ to obtain 14.88g of baked products. After adding sodium carbonate, 0.31g of lithium carbonate precipitate was obtained, and the recovery rate was 17.04%.
To determine the optimum reaction temperature of potassium sulfate, experiments were also conducted at different temperatures in this example, and the results (mass ratio) of the test of the leachate element i cp are shown in table 2 below.
TABLE 2
Example 4
Firstly, putting the waste lithium iron phosphate battery into saturated saline water to fully discharge the waste lithium iron phosphate battery for 30 min. And (3) drying the discharged battery in an oven, disassembling the battery shell to obtain a battery inner core, and sorting the anode, the cathode and the diaphragm to obtain the lithium iron phosphate anode material. And burning the anode material for 2 hours at 500 ℃ in an argon atmosphere to obtain waste lithium iron phosphate powder.
7.89g of waste lithium iron phosphate powder and 6.02g of magnesium sulfate are weighed and ground uniformly. And (3) heating the mixed sample to 800 ℃ at a speed of 5 ℃/min under the air atmosphere, roasting for 5 hours, and then cooling at a speed of 10 ℃/min. The baked slag is fully placed in 150ml of water solution, the temperature in a water bath kettle is adjusted to 80 ℃ and stirred for 1h, the mixture is filtered, and filter residues are dried for 12h at 80 ℃ to obtain 11.53g of baked products. After adding sodium carbonate, 1.19g of lithium carbonate precipitate was obtained, and the recovery rate was 64.27%.
In order to determine the optimal reaction temperature of magnesium sulfate, experiments at different temperatures were also performed in this example, and the results (mass ratio) of the leaching solution element i cp were as shown in table 3 below.
TABLE 3 Table 3
In the research process of the invention, different sulfates are found to have different physicochemical properties, so that the reactivity of the sulfates to lithium iron phosphate is different at different temperatures, and in order to determine which sulfate has the best effect on recycling lithium iron phosphate, various attempts are made, and common sulfates are as follows: sodium sulfate, potassium sulfate, magnesium sulfate, cobalt sulfate, nickel sulfate, manganese sulfate, ammonium bisulfate, and the like. Finally sodium sulfate is preferred.
In addition, with respect to the regeneration of sodium iron phosphate, sodium sulfate and lithium iron phosphate undergo a substitution reaction of sodium and lithium during the calcination process, i.e., lithium ions are extracted from the crystal lattice, and sodium ions replace lithium ions to enter the crystal lattice. The reaction is carried out under the conditions of air and high temperature, so that the structure of the original deintercalatable metal ions of the lithium iron phosphate is changed, and sodium ions replace lithium ions, but lose the capability of deintercalating ions, so that the lithium iron phosphate cannot be directly used as a positive electrode material. In order to improve the profit level of the whole process, the material structure is regenerated by adopting a high-temperature repair method, so that the deintercalation capability of sodium ions is recovered, and the reusable sodium-electricity positive electrode material is obtained.
To determine what metal sulfate works best for recovering lithium iron phosphate, we have made various attempts, common metal sulfates are: potassium sulfate, magnesium sulfate, cobalt sulfate, nickel sulfate, manganese sulfate, and the like.
1. Safety properties. Among the above-listed metal sulfates, sodium sulfate is the most preferred choice from the viewpoint of safety because it is chemically stable, but it has some toxicity to the human body in addition to sodium sulfate and may cause heavy metal poisoning reaction when exposed for a long period of time.
2. Physical properties. The reaction of lithium iron phosphate and metal sulfate needs to be carried out under high temperature, and the reaction temperature is 500-800 ℃. The melting temperature of the metal sulfate is sequentially as follows from big to small: magnesium sulfate > potassium sulfate >1000 ℃ sodium sulfate > manganese sulfate >800 ℃ 500 ℃ cobalt sulfate > nickel sulfate. Because the solid-solid reaction rate is far smaller than the solid-liquid reaction rate, the molten metal sulfate can obviously accelerate the reaction rate so as to improve the lithium extraction effect.
3. The metal sulfate and lithium iron phosphate can undergo a displacement reaction between metal ions and lithium in the roasting process, namely lithium ions are removed from the crystal structure, and the metal ions in the metal sulfate replace the lithium ions to enter the crystal structure to supplement vacancies. Taking sodium sulfate as an example, ferrous iron is converted into ferric iron due to the participation of oxygen in the high-temperature roasting process 6 The octahedron is destroyed, and the space structure of the lithium iron phosphate is changed from an orthorhombic system to a monoclinic system. In this process, sodium ions replace lithium ions, but lose the ability to deintercalate ions, and cannot be directly used as a positive electrode material. In order to improve the profit level of the whole process, the material structure is regenerated by adopting a high-temperature repair method, so that the deintercalation capability of sodium ions is recovered, and the reusable sodium-electricity positive electrode material is obtained.
In view of the above, sodium sulfate is a suitable metal sulfate.
The invention has been described in detail in connection with the specific embodiments and exemplary examples thereof, but such description is not to be construed as limiting the invention. It will be understood by those skilled in the art that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, and these fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (10)
1. A method for recovering lithium iron phosphate batteries by sulfate air roasting is characterized by comprising the following steps: and roasting and recycling the lithium iron phosphate battery by adopting sulfate air.
2. The method according to claim 1, characterized in that: comprises the steps of,
mixing lithium iron phosphate and sulfate, and performing air roasting to obtain solid powder;
leaching the solid powder in water to obtain a solid-liquid mixture, and filtering and separating to obtain sodium iron phosphate and lithium-containing solution;
carbonate is added to the lithium-containing solution to form a lithium carbonate precipitate.
3. The method according to claim 1 or 2, wherein the sulfate is one or more of ammonium sulfate, sodium sulfate, potassium sulfate, or magnesium sulfate.
4. The method according to claim 1 or 2, wherein the air calcination reaction temperature is 400 to 800 ℃ for 4 to 6 hours.
5. The method according to claim 1, characterized in that: the water immersion time is 30-60 min.
6. The method according to claim 5, wherein: the reaction temperature used in water immersion is 20-90 ℃.
7. The method according to claim 1, characterized in that: the molar ratio of the lithium iron phosphate to the sulfate is 1: 1-3:1.
8. The method according to claim 5, wherein: the mass ratio of water to baked materials in the water leaching process is 50:1-100:1.
9. The method according to claim 1, characterized in that: and mixing and reacting the sodium iron phosphate and a reducing agent to obtain the battery-grade sodium iron phosphate.
10. The method according to claim 9, wherein: the reducing agent is one or more of glucose, ascorbic acid, hydrogen amine hydrochloride, ammonium dihydrogen phosphate, carbon black and polyvinylidene fluoride.
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| CN118221089B (en) * | 2024-05-23 | 2024-09-13 | 深圳市杰成镍钴新能源科技有限公司 | Recycling method of waste lithium iron phosphate battery |
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