CN116750740A - Method for recycling waste lithium iron phosphate battery - Google Patents
Method for recycling waste lithium iron phosphate battery Download PDFInfo
- Publication number
- CN116750740A CN116750740A CN202310595271.5A CN202310595271A CN116750740A CN 116750740 A CN116750740 A CN 116750740A CN 202310595271 A CN202310595271 A CN 202310595271A CN 116750740 A CN116750740 A CN 116750740A
- Authority
- CN
- China
- Prior art keywords
- iron phosphate
- lithium iron
- powder
- acid
- leaching
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 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 133
- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000002699 waste material Substances 0.000 title claims abstract description 33
- 238000004064 recycling Methods 0.000 title claims description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000002243 precursor Substances 0.000 claims abstract description 48
- 238000002386 leaching Methods 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 239000007788 liquid Substances 0.000 claims abstract description 45
- 239000000843 powder Substances 0.000 claims abstract description 42
- 238000001556 precipitation Methods 0.000 claims abstract description 42
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 31
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000001914 filtration Methods 0.000 claims abstract description 23
- 239000008139 complexing agent Substances 0.000 claims abstract description 22
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 20
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 19
- 239000002002 slurry Substances 0.000 claims abstract description 19
- 239000010405 anode material Substances 0.000 claims abstract description 18
- 238000007599 discharging Methods 0.000 claims abstract description 18
- 239000010949 copper Substances 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 9
- 239000002893 slag Substances 0.000 claims abstract description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 39
- 230000001590 oxidative effect Effects 0.000 claims description 28
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 27
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000001354 calcination Methods 0.000 claims description 12
- 239000007774 positive electrode material Substances 0.000 claims description 12
- 150000007524 organic acids Chemical class 0.000 claims description 11
- 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 10
- 150000007522 mineralic acids Chemical class 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 235000006408 oxalic acid Nutrition 0.000 claims description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000010981 drying operation Methods 0.000 claims description 7
- 235000015165 citric acid Nutrition 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000013543 active substance Substances 0.000 claims description 5
- 239000011668 ascorbic acid Substances 0.000 claims description 5
- 235000010323 ascorbic acid Nutrition 0.000 claims description 5
- 229960005070 ascorbic acid Drugs 0.000 claims description 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- DZCAZXAJPZCSCU-UHFFFAOYSA-K sodium nitrilotriacetate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CC([O-])=O DZCAZXAJPZCSCU-UHFFFAOYSA-K 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 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 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 239000008103 glucose Substances 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- YHGREDQDBYVEOS-UHFFFAOYSA-N [acetyloxy-[2-(diacetyloxyamino)ethyl]amino] acetate Chemical compound CC(=O)ON(OC(C)=O)CCN(OC(C)=O)OC(C)=O YHGREDQDBYVEOS-UHFFFAOYSA-N 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 9
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 14
- 229910052744 lithium Inorganic materials 0.000 description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000001694 spray drying Methods 0.000 description 6
- 239000010406 cathode material Substances 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229910018119 Li 3 PO 4 Inorganic materials 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 2
- 229910052743 krypton Inorganic materials 0.000 description 2
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229910052754 neon Inorganic materials 0.000 description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 2
- -1 phosphorus compound Chemical class 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- LXAHHHIGZXPRKQ-UHFFFAOYSA-N 5-fluoro-2-methylpyridine Chemical compound CC1=CC=C(F)C=N1 LXAHHHIGZXPRKQ-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 1
- 239000005955 Ferric phosphate Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 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
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000185 sucrose group Chemical group 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention relates to the technical field of battery recovery, and discloses a method for recovering and treating waste lithium iron phosphate batteries, which comprises the following steps: discharging, disassembling, crushing and sorting the waste lithium iron phosphate batteries to obtain lithium iron phosphate powder; roasting the lithium iron phosphate powder to obtain roasting powder; mixing the roasted powder, adding mixed acid for leaching, and filtering to obtain leaching liquid and leaching slag; adding iron powder into the leaching solution for precipitation reaction, and filtering to obtain copper-removing liquid; adjusting the pH value of the copper removal liquid to carry out precipitation reaction, and filtering to obtain aluminum removal liquid; adding a complexing agent and a reducing agent into the aluminum removal liquid, and then adjusting the pH value to carry out precipitation reaction to obtain lithium iron phosphate precursor slurry; and drying the lithium iron phosphate precursor slurry, and then adding a carbon source for roasting to obtain the lithium iron phosphate anode material. The method has the characteristics of short flow, environmental protection and economy, and the prepared lithium iron phosphate anode material has good product consistency, uniform particles and excellent electrical property, and can realize industrial mass production.
Description
Technical Field
The invention relates to the technical field of battery recovery, in particular to a method for recovering and treating waste lithium iron phosphate batteries.
Background
In recent years, with the development of lithium ion battery technology and the increasing importance of people on safety, the commercial application scale of lithium iron phosphate batteries exceeds that of ternary batteries, and domestic lithium ion battery tap lead enterprises such as CATL, yi-Bu lithium energy, bidi and the like continuously produce lithium iron phosphate power batteries in large quantities, and are widely applied to the field of new energy automobiles. The service cycle of the lithium ion power battery is 6-8 years, so that the recycling problem of the lithium iron phosphate battery is increasingly caused. The most widely used field of battery recovery in China is wet recovery technology.
Chinese patent 202110978962.4 discloses a method for fully recovering lithium iron and phosphorus from a waste lithium iron phosphate positive electrode material, which comprises the steps of mixing the waste lithium iron phosphate material with a phosphorus compound, performing heat treatment, leaching with water or dilute acid, filtering and washing to obtain a filtrate, adding an iron-containing compound into the filtrate to regulate the iron-phosphorus ratio of the solution, adding an oxidant, adjusting the pH value of the solution to 1-4, precipitating iron phosphate, and adjusting the pH value of the obtained filtrate to 6-12 to prepare lithium carbonate. The process flow is long, the cost is high, and secondary pollution can be caused. Chinese patent 202111233873.3 discloses a short-process recovery method of waste lithium iron phosphate anode materials, which comprises the steps of repeatedly and alternately soaking the waste lithium iron phosphate battery anode materials in deionized water at 25 ℃ and 90 ℃ for three times to obtain a piece of waste lithium iron phosphate materials, drying, grinding in a ball mill to obtain a powdery active material, and then, magnetically stirring, filtering, centrifuging, washing and drying in an NMP solvent to obtain the regenerated anode materials. The NMP solvent is used in large quantity to easily cause environmental pollution, and the obtained anode material has high impurity content and obviously low electrochemical performance. Chinese patent 202111493938.8 discloses a recovery method of a lithium iron phosphate battery anode material, which adopts an organic solvent to dissolve a binder in lithium iron phosphate anode waste, and retains a conductive agent and a carbon coating layer on the surface of the lithium iron phosphate to obtain a lithium iron phosphate intermediate material; and (3) performing lithium supplementing operation on the lithium iron phosphate intermediate material to obtain the lithium iron phosphate repair material. The technology is still immature, is still in laboratory research stage at present, and is difficult to realize industrialized application. Chinese patent 202111593472.9 discloses a comprehensive wet recycling method of waste lithium iron phosphate positive plates, which comprises the steps of carrying out acid leaching, copper and aluminum removal on positive plate powder, adding an oxidant, regulating the pH of a solution by adopting ammonia water to precipitate ferric phosphate, and removing impurities from the obtained filtrate to prepare lithium carbonate. The wet treatment process has long and complex flow, consumes a large amount of acid and alkali, reducing agent, oxidant and other chemical reagents, has large pollution, generates a large amount of wastewater, has low resource recovery rate and poor technical economy and environmental protection, and influences the industrialized application and popularization of the wet treatment process.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a short-flow, environment-friendly and economic method for recycling waste lithium iron phosphate batteries, and the obtained lithium iron phosphate anode material has higher purity, excellent performance and better product consistency and can realize industrial application.
The aim of the invention is realized by the following technical scheme:
a method for recycling waste lithium iron phosphate batteries comprises the following steps:
(1) And discharging, disassembling, crushing and sorting the waste lithium iron phosphate batteries to obtain the shell, the diaphragm, the current collector and the lithium iron phosphate powder containing the active substances.
The discharging operation in the step (1) is a resistor discharging or a carbon powder conductor physical discharging.
(2) And roasting the lithium iron phosphate powder in a non-oxidizing atmosphere to obtain roasting powder.
The temperature of the roasting operation in the step (2) is 450-650 ℃, preferably 500-550 ℃; the time is 2 to 6 hours, preferably 3 to 4 hours. The non-oxidizing atmosphere is at least one of nitrogen, helium, neon, argon, krypton and xenon, and the purity is more than 99.9%.
Thus, step (2) causes the binder PVDF and the electrolyte LiPF to be subjected to a firing operation 6 And the organic solvent is decomposed into carbon substances at high temperature, and most of fluorine volatilizes in a gas form, so that a binder PVDF and an electrolyte LiPF in the lithium iron phosphate powder are removed 6 An organic solvent. At the same time, non-oxidizing atmosphere is introduced to prevent Fe 2+ Oxidation to Fe 3+ Avoiding the need of introducing a large amount of reduced iron powder in the subsequent copper removal link.
(3) Adding pure water into the roasted powder for size mixing, adding mixed acid to adjust the pH value to 2-5 for leaching, and filtering to obtain leaching liquid and leaching slag.
The ratio of liquid to solid obtained in the step (3) is (3-6): 1, preferably 3:1.
The mixed acid in the step (3) comprises inorganic acid and organic acid with the mass ratio of (1-5) to 1, wherein the inorganic acid is phosphoric acid, and the organic acid is at least one of tartaric acid, oxalic acid, malic acid, citric acid and ascorbic acid; the temperature of the leaching operation is 70-90 ℃ and the time is 3-6 h.
In this way, in the step (3), elements such as lithium, iron, phosphorus, copper, aluminum and the like in the baked powder are dissolved through size mixing and leaching operation, and leaching liquid and leaching slag are obtained through filtration. The leaching solution is rich in elements such as lithium, iron, phosphorus, copper, aluminum and the like, and the leaching slag is mainly graphite and can be used for regenerating carbon materials.
(4) And adding iron powder into the leaching solution to perform precipitation reaction, and filtering to obtain copper-removing liquid.
The addition amount of the iron powder in the step (4) is Cu in the leaching solution 2+ 1.0 to 1.5 times, preferably 1.1 to 1.2 times, the molar amount of (c). The temperature of the precipitation reaction is 30-85 ℃, and the time is 0.5-6 h, preferably 0.5-1.5 h.
In this way, in the step (4), iron powder is added for precipitation reaction, copper ions are removed, and the copper-removing liquid is obtained through filtration.
(5) And adding a pH regulator into the copper removal liquid to adjust the pH end point of the solution to 5-7 for precipitation reaction, and filtering to obtain aluminum removal liquid.
In the step (5), the pH regulator is at least one of lithium hydroxide, ammonia water, sodium hydroxide, sodium carbonate and active calcium oxide, preferably ammonia water, and the solute concentration is 1.0-2.5 mol/L. The temperature of the precipitation reaction is 30-90 ℃, preferably 45-55 ℃; the time is 0.5 to 3.0 hours, preferably 1.0 to 2.0 hours.
In this way, in the step (5), the pH value end point of the solution is adjusted to be 5-7 by adding a pH regulator to carry out precipitation reaction, aluminum ions are removed, and the aluminum removal liquid is obtained by filtering.
(6) Adding a complexing agent and a reducing agent into the aluminum removal liquid, adding a pH regulator to adjust the pH end point of the solution to 8-10, and carrying out precipitation reaction in a non-oxidizing atmosphere to obtain lithium iron phosphate precursor slurry.
In the step (6), the aluminum removal liquid is subjected to elemental analysis according to the element molar ratio of n Li :n Fe :n P =1:1:1, an insufficient amount of an element source (typically a lithium source, which is lithium hydroxide, lithium carbonate, etc.) is dosed, the molar amount of the monomer theoretically capable of generating the lithium iron phosphate precursor is calculated, and the theoretical total mass of the lithium iron phosphate precursor is calculated.
The complexing agent in the step (6) is at least one of sodium Nitrilotriacetate (NTA), ethylenediamine tetraacetate (EDTA disodium or tetrasodium) and diethylenetriamine pentacarboxylate (DTPA), and the adding amount of the complexing agent is Fe in the aluminum removal liquid 2+ 5% -15% of the molar quantity of the catalyst; the reducing agent is at least one of ascorbic acid, oxalic acid and hydrazine hydrate, and the addition amount of the reducing agent is 0.5-5.0% of the theoretical total mass of the lithium iron phosphate precursor.
In the step (6), the pH regulator is at least one of lithium hydroxide, ammonia water, sodium hydroxide, sodium carbonate and active calcium oxide, preferably ammonia water, and the solute concentration is 1.0-2.5 mol/L.
The non-oxidizing atmosphere in the step (6) is at least one of nitrogen, helium, neon, argon, krypton and xenon, and the purity is more than 99.9%.
The temperature of the precipitation reaction in the step (6) is 70-95 ℃ and the time is 2-6 h.
The reaction equation mainly occurring in the above step (6) is as follows:
pH＜8：
pH＞8：
3Li + +PO 4 3- →Li 3 PO 4 ↓
3Fe 2+ +2PO 4 3- +8H 2 O→Fe 3 (PO 4 ) 2 .8H 2 O↓
Li 3 PO 4 +Fe 3 (PO 4 ) 2 .8H 2 O→3LiFePO 4 +8H 2 O↑
thus, step (6) is due to Fe under alkaline conditions 2+ Is easily oxidized into Fe 3+ By utilizing the oxygen blocking effect of non-oxidizing atmosphere and the reduction effect of reducing agent, fe is effectively prevented by double effect 2+ Is oxidized to Fe 3+ . Due to Li 3 PO 4 And Fe (Fe) 3 (PO 4 ) 2 .8H 2 The Ksp of O is very different, and in order to ensure the balance of the coprecipitation reaction, fe is reacted by complexing agent at pH < 8 2+ Has complexation effect and slowly releases Fe at pH > 8 2+ Regulating Li 3 PO 4 And Fe (Fe) 3 (PO 4 ) 2 .8H 2 The precipitation speed of O is similar to that of Li in the reaction + ：Fe 2+ ：P 5+ The molar ratio of (2) is continuously close to 1:1:1, and the target product LiFePO is ensured to the maximum extent 4 And the generation of byproducts is reduced.
(7) And drying the lithium iron phosphate precursor slurry to obtain lithium iron phosphate precursor powder, adding a carbon source, and calcining under a non-oxidizing atmosphere to obtain the lithium iron phosphate anode material.
The drying operation in the above step (7) is preferably spray drying at a temperature of 200 to 400 ℃.
In the step (7), the carbon source is at least one of citric acid, oxalic acid, sucrose, glucose and polyethylene glycol, and the addition amount of the carbon source is 0.1-0.5% of the mass of the lithium iron phosphate precursor powder; the temperature of the calcination operation is 350-500 ℃ and the time is 2-6 h.
In this way, in the step (7), the loss of lithium, iron and phosphorus elements in the lithium iron phosphate precursor slurry can be reduced through spray drying, so that the enrichment of main elements is realized, the actual proportion of the lithium, iron and phosphorus elements in the product is more matched with the design proportion, the enrichment of useful elements is improved, the actual proportion error of the useful elements is reduced, and the purity and the electrochemical performance of the lithium iron phosphate positive electrode material are improved. Spray drying also has the function of granulating compared with ordinary drying.
(8) The lithium iron phosphate anode material is crushed until the D50 particle size is 1-16 mu m, preferably 1.5-5 mu m; and (5) sealing and storing.
In the step (8), the crushing operation is preferably air-jet crushing, and the air-jet is dry compressed air with dew point lower than-40 ℃.
Thus, the particle size distribution of the lithium iron phosphate material in the step (8) after being crushed by the air flow meets the national standard requirement of battery-grade lithium iron phosphate.
Compared with the prior art, the invention has at least the following advantages:
the method is a wet recovery process, and the recovery rate of lithium, iron and phosphorus elements is relatively high. Compared with the traditional wet process, the method has the advantages of simple process flow, less chemical reagent consumption, economy and environmental protection. Phosphoric acid and organic acid are adopted for leaching, so that the introduction of foreign impurities is reduced; lithium hydroxide is adopted to replace the traditional sodium hydroxide (which can introduce a large amount of sodium elements as impurities) and ammonia water (which can cause environmental pollution) as a pH regulator; the organic complexing agent (specifically an amino carboxylate complexing agent) is added, so that the complexing capacity is high, and the effective combination of lithium, iron and phosphorus compounds can be realized. Compared with the traditional wet process, the method has simple equipment, lower cost and short process flow, adopts mixed acid as an acid leaching reagent and lithium hydroxide to replace sodium hydroxide, can reduce the introduction of foreign matters, can also be used as a lithium source to reduce reagent cost, directly obtains lithium iron phosphate precursor slurry through the specified steps (1) - (8), and can obtain lithium iron phosphate precursor powder after drying, thus the traditional washing process is not needed, the pure water consumption is reduced, and the waste water amount is effectively reduced. The method has the characteristics of short flow, environmental protection and economy, the yield of the lithium iron phosphate precursor is higher, and the prepared lithium iron phosphate positive electrode material has good product consistency, uniform particles and excellent electrical property, and can realize industrial mass production.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a flow chart of steps of a method for recycling waste lithium iron phosphate batteries according to an embodiment of the invention.
Fig. 2 is a graph showing the first-turn charge and discharge performance of the lithium iron phosphate positive electrode material of example 3 of the present invention.
Fig. 3 is a ten thousand times scanning electron microscope image of the lithium iron phosphate cathode material of example 3 of the present invention.
Fig. 4 is a scanning electron microscope image of two ten thousand times of the lithium iron phosphate cathode material of example 3 of the present invention.
Detailed Description
In order that the invention may be readily understood, a more complete description of the invention will be rendered by reference to the appended drawings. The drawings illustrate preferred embodiments of the invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Example 1
A method for recycling waste lithium iron phosphate batteries comprises the following steps:
(1) And discharging, disassembling, crushing and sorting the waste lithium iron phosphate batteries to obtain metal shells, plastic diaphragms, aluminum foils, copper foils and lithium iron phosphate powder containing active substances.
The discharging operation in the step (1) is a resistor discharging or a carbon powder conductor physical discharging.
(2) And roasting the lithium iron phosphate powder in a non-oxidizing atmosphere to obtain roasting powder.
The temperature of the roasting operation in the step (2) is 450 ℃ and the time is 6 hours. The non-oxidizing atmosphere is nitrogen, and the purity is more than 99.9%.
(3) Adding pure water into the roasted powder for size mixing, adding mixed acid to adjust the pH value to 2 for leaching, and filtering to obtain leaching liquid and leaching slag.
And (3) the liquid-solid ratio obtained by the slurry mixing operation in the step (3) is 3:1. The mixed acid comprises inorganic acid and organic acid in a mass ratio of 1:1, wherein the inorganic acid is phosphoric acid, and the organic acid is tartaric acid; the temperature of the leaching operation is 70 ℃ and the time is 6 hours.
(4) And adding iron powder into the leaching solution to perform precipitation reaction, and filtering to obtain copper-removing liquid.
The addition amount of the iron powder in the step (4) is Cu in the leaching solution 2+ 1.0 times the molar amount of (c). The temperature of the precipitation reaction is 30 ℃ and the time is 6 hours.
(5) And adding a pH regulator into the copper removal liquid to adjust the pH end point of the solution to be 5 for precipitation reaction, and filtering to obtain aluminum removal liquid.
The pH regulator in the step (5) is ammonia water. The temperature of the precipitation reaction is 30 ℃ and the time is 3.0h.
(6) Adding a complexing agent and a reducing agent into the aluminum removal liquid, adding a pH regulator to adjust the pH end point of the solution to 8, and carrying out precipitation reaction in a non-oxidizing atmosphere to obtain lithium iron phosphate precursor slurry.
In the step (6), the aluminum removal liquid is subjected to elemental analysis according to the element molar ratio of n Li :n Fe :n P =1:1:1 of insufficient lithium source (i.e. lithium hydroxide) was dosed, the molar amount of monomer theoretically able to generate the lithium iron phosphate precursor was calculated, and the theoretical total mass of lithium iron phosphate precursor was calculated.
The complexing agent in the step (6) is sodium Nitrilotriacetate (NTA), and the adding amount of the complexing agent is Fe in the aluminum removal liquid 2+ 5% of the molar amount of (A); the reducing agent is oxalic acid, and the addition amount of the reducing agent is 0.5% of the theoretical total mass of the lithium iron phosphate precursor. The pH regulator is ammonia water. The non-oxidizing atmosphere is nitrogen, and the purity is more than 99.9%. The precipitation reaction is carried out at 70 ℃ for 6 hours.
(7) And drying the lithium iron phosphate precursor slurry to obtain lithium iron phosphate precursor powder, adding a carbon source, and calcining under a non-oxidizing atmosphere to obtain the lithium iron phosphate anode material.
The drying operation in the step (7) is spray drying, and the temperature is 200 ℃. The carbon source is citric acid, and the addition amount of the carbon source is 0.1% of the mass of the lithium iron phosphate precursor powder; the temperature of the calcination operation is 350 ℃ and the time is 6 hours.
(8) The lithium iron phosphate anode material is crushed until the D50 particle size is 1-16 mu m; and (5) sealing and storing.
In the step (8), the crushing operation is air current crushing, and the adopted air current is dry compressed air with the dew point lower than-40 ℃.
Example 2
A method for recycling waste lithium iron phosphate batteries comprises the following steps:
(1) And discharging, disassembling, crushing and sorting the waste lithium iron phosphate batteries to obtain metal shells, plastic diaphragms, aluminum foils, copper foils and lithium iron phosphate powder containing active substances.
The discharging operation in the step (1) is a resistor discharging or a carbon powder conductor physical discharging.
(2) And roasting the lithium iron phosphate powder in a non-oxidizing atmosphere to obtain roasting powder.
The temperature of the roasting operation in the step (2) is 650 ℃ and the time is 2h. The non-oxidizing atmosphere is argon, and the purity is more than 99.9%.
(3) Adding pure water into the roasted powder for size mixing, adding mixed acid to adjust the pH value to 5 for leaching, and filtering to obtain leaching liquid and leaching slag.
And (3) the liquid-solid ratio obtained by the slurry mixing operation in the step (3) is 6:1. The mixed acid comprises inorganic acid and organic acid in a mass ratio of 5:1, wherein the inorganic acid is phosphoric acid, and the organic acid is oxalic acid; the temperature of the leaching operation is 90 ℃ and the time is 3 hours.
(4) And adding iron powder into the leaching solution to perform precipitation reaction, and filtering to obtain copper-removing liquid.
The addition amount of the iron powder in the step (4) is Cu in the leaching solution 2+ 1.5 times the molar amount of (c). The temperature of the precipitation reaction is 85 ℃ and the time is 0.5h.
(5) And adding a pH regulator into the copper removal liquid to adjust the pH end point of the solution to 7 for precipitation reaction, and filtering to obtain aluminum removal liquid.
The pH regulator in the step (5) is lithium hydroxide. The temperature of the precipitation reaction is 90 ℃ and the time is 0.5h.
(6) Adding a complexing agent and a reducing agent into the aluminum removal liquid, adding a pH regulator to adjust the pH end point of the solution to 10, and carrying out precipitation reaction in a non-oxidizing atmosphere to obtain lithium iron phosphate precursor slurry.
In the step (6), the aluminum removal liquid is subjected to elemental analysis according to the element molar ratio of n Li :n Fe :n P =1:1:1 of insufficient lithium source (i.e. lithium hydroxide) was dosed, the molar amount of monomer theoretically able to generate the lithium iron phosphate precursor was calculated, and the theoretical total mass of lithium iron phosphate precursor was calculated.
The complexing agent in the step (6) is ethylenediamine tetraacetate (disodium EDTA or tetrasodium), and the adding amount of the complexing agent is Fe in the aluminum removal liquid 2+ 15% of the molar amount of (a); the reducing agent is hydrazine hydrate, and the reductionThe addition amount of the agent is 5% of the theoretical total mass of the lithium iron phosphate precursor. The pH regulator is lithium hydroxide. The non-oxidizing atmosphere is argon, and the purity is more than 99.9%. The precipitation reaction is carried out at 95 ℃ for 2 hours.
(7) And drying the lithium iron phosphate precursor slurry to obtain lithium iron phosphate precursor powder, adding a carbon source, and calcining under a non-oxidizing atmosphere to obtain the lithium iron phosphate anode material.
The drying operation in the above step (7) is preferably spray drying at a temperature of 400 ℃. The carbon source is sucrose, and the addition amount of the carbon source is 0.5% of the mass of the lithium iron phosphate precursor powder; the calcination operation was carried out at 500℃for 2 hours.
(8) The lithium iron phosphate anode material is crushed until the D50 particle size is 1-16 mu m, preferably 1.5-5 mu m; and (5) sealing and storing.
In the step (8), the crushing operation is air current crushing, and the adopted air current is dry compressed air with the dew point lower than-40 ℃.
Example 3
A method for recycling waste lithium iron phosphate batteries comprises the following steps:
(1) And discharging, disassembling, crushing and sorting the waste lithium iron phosphate batteries to obtain metal shells, plastic diaphragms, aluminum foils, copper foils and lithium iron phosphate powder containing active substances.
The discharging operation in the step (1) is a resistor discharging or a carbon powder conductor physical discharging.
(2) And roasting the lithium iron phosphate powder in a non-oxidizing atmosphere to obtain roasting powder.
The temperature of the roasting operation in the step (2) is 550 ℃ and the time is 4 hours. The non-oxidizing atmosphere is nitrogen, and the purity is more than 99.9%.
(3) Adding pure water into the roasted powder for size mixing, adding mixed acid to adjust the pH value to 3.5 for leaching, and filtering to obtain leaching liquid and leaching slag.
The slurry mixing operation in the step (3) is carried out to obtain a liquid-solid ratio of 4.5:1. The mixed acid comprises inorganic acid and organic acid in a mass ratio of 3:1, wherein the inorganic acid is phosphoric acid, and the organic acid is citric acid; the temperature of the leaching operation is 80 ℃ and the time is 4.5h.
(4) And adding iron powder into the leaching solution to perform precipitation reaction, and filtering to obtain copper-removing liquid.
The addition amount of the iron powder in the step (4) is Cu in the leaching solution 2+ 1.2 times the molar amount of (c). The temperature of the precipitation reaction is 58 ℃ and the time is 3h.
(5) And adding a pH regulator into the copper removal liquid to adjust the pH end point of the solution to 6 for precipitation reaction, and filtering to obtain aluminum removal liquid.
The pH regulator in the step (5) is lithium hydroxide. The temperature of the precipitation reaction is 60 ℃ and the time is 1.7h.
(6) Adding a complexing agent and a reducing agent into the aluminum removal liquid, adding a pH regulator to adjust the pH end point of the solution to 9, and carrying out precipitation reaction in a non-oxidizing atmosphere to obtain lithium iron phosphate precursor slurry.
In the step (6), the aluminum removal liquid is subjected to elemental analysis according to the element molar ratio of n Li :n Fe :n P =1:1:1 of insufficient lithium source (i.e. lithium hydroxide) was dosed, the molar amount of monomer theoretically able to generate the lithium iron phosphate precursor was calculated, and the theoretical total mass of lithium iron phosphate precursor was calculated.
The complexing agent in the step (6) is diethylenetriamine pentacarboxylate (DTPA), and the adding amount of the complexing agent is Fe in the aluminum removal liquid 2+ 10% of the molar amount of (a); the reducing agent is ascorbic acid, and the addition amount of the reducing agent is 2.5% of the theoretical total mass of the lithium iron phosphate precursor. The pH regulator is lithium hydroxide. The non-oxidizing atmosphere is nitrogen, and the purity is more than 99.9%. The precipitation reaction is carried out at a temperature of 85 ℃ for 4 hours.
(7) And drying the lithium iron phosphate precursor slurry to obtain lithium iron phosphate precursor powder, adding a carbon source, and calcining under a non-oxidizing atmosphere to obtain the lithium iron phosphate anode material.
The drying operation in the step (7) is spray drying, and the temperature is 300 ℃. The carbon source is oxalic acid, and the addition amount of the carbon source is 0.3% of the mass of the lithium iron phosphate precursor powder; the calcination operation was carried out at 425℃for 4 hours.
(8) The lithium iron phosphate anode material is crushed until the D50 particle size is 1.5-5 mu m; and (5) sealing and storing.
In the step (8), the crushing operation is air current crushing, and the adopted air current is dry compressed air with the dew point lower than-40 ℃.
Comparative example 1
Substantially the same as in example 3, except that:
the temperature of the roasting operation in the step (2) is 400 ℃ and the time is 7 hours.
And (3) the liquid-solid ratio obtained by the slurry mixing operation in the step (3) is 2:1. The mixed acid is phosphoric acid. The pH end point of the leaching operation was 1.5, the temperature was 60 ℃, and the time was 7h.
The addition amount of the iron powder in the step (4) is Cu in the leaching solution 2+ 0.5 times the molar amount of (c). The temperature of the precipitation reaction is 20 ℃ and the time is 7.0h.
The pH end point of the precipitation reaction in the step (5) is 4.5, the temperature is 20 ℃, and the time is 4.0h.
The addition amount of the complexing agent in the step (6) is Fe in the aluminum removal liquid 2+ 3% of the molar amount of (3); the addition amount of the reducing agent is 0.3% of the theoretical total mass of the lithium iron phosphate precursor. The pH end point of the precipitation reaction is 7.5, the temperature is 60 ℃, and the time is 7h.
The temperature of the drying operation in the above step (7) was 150 ℃. The addition amount of the carbon source is 0.05% of the mass of the lithium iron phosphate precursor powder; the calcination operation was performed at 300℃for 7 hours.
In the step (8), the crushing operation is air current crushing, and the adopted air current is dry compressed air with the dew point of-20 ℃.
Comparative example 2
Substantially the same as in example 3, except that:
the temperature of the roasting operation in the step (2) is 700 ℃ and the time is 1h.
And (3) the liquid-solid ratio obtained by the slurry mixing operation in the step (3) is 6:1. The mixed acid is phosphoric acid. The pH end point of the leaching operation was 5.5, the temperature was 100 ℃, and the time was 2h.
The addition amount of the iron powder in the step (4) is Cu in the leaching solution 2+ 2.0 times the molar amount of (c). The temperature of the precipitation reaction is 95 ℃ and the time is 0.2h.
The pH end point of the precipitation reaction in the step (5) is 7.5, the temperature is 100 ℃, and the time is 0.2h.
The addition amount of the complexing agent in the step (6) is Fe in the aluminum removal liquid 2+ 20% of the molar amount of (a); the addition amount of the reducing agent is 5.5% of the theoretical total mass of the lithium iron phosphate precursor. The pH end point of the precipitation reaction is 10.5, the temperature is 105 ℃, and the time is 1h.
The temperature of the drying operation in the above step (7) was 450 ℃. The addition amount of the carbon source is 1.0% of the mass of the lithium iron phosphate precursor powder; the calcination operation was carried out at 550℃for 1h.
In the step (8), the crushing operation is air current crushing, and the adopted air current is dry compressed air with the dew point of-30 ℃.
Comparative example 3
Substantially the same as in example 3, except that: no complexing agent is added in the step (6).
Comparative example 4
Substantially the same as in example 3, except that: no reducing agent is added in the step (6).
Through experimental tests, the yield of the lithium iron phosphate precursor in the embodiment 3 is more than 85%, and the purity of the lithium iron phosphate positive electrode material is more than 98%.
Key properties of the lithium iron phosphate cathode material of example 3:
a. key physical and chemical properties
Compact density 2.41g/cm 3 ，
The discharge gram capacity of the lithium iron phosphate positive electrode material is 156.3mAh/g under the conditions of 0.1C/0.1C and 2.5V-2.75V, and the discharge efficiency is 99.61%.
b. The first turn of electrical properties is shown in fig. 2. Wherein, the red curve represents the discharge curve, and the green curve represents the charge curve.
c. The structure of the lithium iron phosphate positive electrode material is shown in figures 3-4.
As can be seen from experimental data and fig. 2 to 4, the lithium iron phosphate cathode material of example 3 has uniform particles, good product consistency and good electrochemical performance.
In terms of data comparison: the lithium iron phosphate precursor yields, purity and electrochemical properties of the lithium iron phosphate cathode materials of examples 1 and 2 were similar to example 3 and slightly lower than example 3. The lithium iron phosphate precursor yields, the purity of the lithium iron phosphate positive electrode material, and the electrochemical properties of the lithium iron phosphate positive electrode materials of examples 1 to 3 are significantly better than those of comparative examples 1 to 2. The lithium iron phosphate precursor yields, the purity of the lithium iron phosphate positive electrode material, and the electrochemical properties of the lithium iron phosphate positive electrode materials of comparative examples 3 to 4 are all much lower than those of example 3.
Experiments prove that the method has synergistic effect among the steps, can achieve the effect only by adopting the reaction conditions of the type and the addition amount of the reagent, the pH value, the temperature, the time, the liquid-solid ratio and the like specified by the method, and has the advantages of obtaining the lithium iron phosphate precursor with the yield of more than 85 percent, the purity of the lithium iron phosphate anode material of more than 98 percent, the discharge efficiency of more than 99.61 percent and good electrochemical performance.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. The method for recycling the waste lithium iron phosphate battery is characterized by comprising the following steps of:
(1) Discharging, disassembling, crushing and sorting the waste lithium iron phosphate batteries to obtain a shell, a diaphragm, a current collector and lithium iron phosphate powder containing active substances;
(2) Roasting the lithium iron phosphate powder in a non-oxidizing atmosphere to obtain roasted powder;
(3) Adding mixed acid into the roasted powder to adjust the pH value for leaching, and filtering to obtain leaching liquid and leaching slag;
(4) Adding iron powder into the leaching solution to perform precipitation reaction, and filtering to obtain copper-removing liquid;
(5) Adding a pH regulator into the copper removal liquid to regulate pH for precipitation reaction, and filtering to obtain aluminum removal liquid;
(6) Adding a complexing agent and a reducing agent into the aluminum removal liquid, adding a pH regulator to regulate the pH value, and carrying out precipitation reaction in a non-oxidizing atmosphere to obtain lithium iron phosphate precursor slurry;
(7) And drying the lithium iron phosphate precursor slurry to obtain lithium iron phosphate precursor powder, adding a carbon source, and calcining under a non-oxidizing atmosphere to obtain the lithium iron phosphate anode material.
2. The method for recycling waste lithium iron phosphate batteries according to claim 1, wherein the roasting operation in the step (2) is performed at a temperature of 450-650 ℃ for 2-6 hours.
3. The method for recycling the waste lithium iron phosphate battery according to claim 1, wherein in the step (3), the pH value is adjusted to 2-5, the mixed acid comprises inorganic acid and organic acid with the mass ratio of (1-5): 1, the inorganic acid is phosphoric acid, and the organic acid is at least one of tartaric acid, oxalic acid, malic acid, citric acid and ascorbic acid; the temperature of the leaching operation is 70-90 ℃ and the time is 3-6 h.
4. The method for recycling waste lithium iron phosphate batteries according to claim 1 or 3, wherein in the step (3), pure water is added into the calcined powder for size mixing before adding the mixed acid, and the size mixing operation is performed to obtain a liquid-solid ratio of (3-6): 1.
5. The method for recycling waste lithium iron phosphate battery according to claim 1, wherein the adding amount of the iron powder in the step (4) is Cu in the leaching solution 2+ 1.0 to 1.5 times the molar quantity of the catalyst, wherein the temperature of the precipitation reaction is 30 to 85 ℃ and the time is 0.5 to 6 hours.
6. The method for recycling waste lithium iron phosphate batteries according to claim 1, wherein in the step (5), the pH value is adjusted to 5-7, and the pH regulator is at least one of lithium hydroxide, ammonia water, sodium hydroxide, sodium carbonate and active calcium oxide; the temperature of the precipitation reaction is 30-90 ℃ and the time is 0.5-3 h.
7. The method for recycling waste lithium iron phosphate battery according to claim 1, wherein in the step (6), the pH value is adjusted to 8-10, the complexing agent is at least one of sodium nitrilotriacetate, ethylenediamine tetraacetate and diethylenetriamine pentacarboxylate, and the addition amount of the complexing agent is Fe in the aluminum removal liquid 2+ 5% -15% of the molar quantity of the catalyst; the reducing agent is at least one of ascorbic acid, oxalic acid and hydrazine hydrate, and the addition amount of the reducing agent is 0.5-5.0% of the theoretical total mass of the lithium iron phosphate precursor; the temperature of the precipitation reaction is 70-95 ℃ and the time is 2-6 h.
8. The method for recycling waste lithium iron phosphate batteries according to claim 1, wherein in the step (7), the carbon source is at least one of citric acid, oxalic acid, sucrose, glucose and polyethylene glycol, and the addition amount of the carbon source is 0.1% -0.5% of the mass of the lithium iron phosphate precursor powder; the temperature of the calcination operation is 350-500 ℃ and the time is 2-6 h.
9. The method for recycling waste lithium iron phosphate battery according to claim 1 or 8, wherein the temperature of the drying operation in the step (7) is 200-400 ℃.
10. The method for recycling waste lithium iron phosphate batteries according to claim 1, further comprising the step of (8) crushing the lithium iron phosphate positive electrode material until the D50 particle size is 1-16 μm.
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| CN117230312B (en) * | 2023-11-13 | 2024-03-19 | 帕瓦(长沙)新能源科技有限公司 | Alkaline leaching process of waste lithium ion battery anode material |
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