CN117594897A - Recycling method of waste sodium ion battery anode - Google Patents
Recycling method of waste sodium ion battery anode Download PDFInfo
- Publication number
- CN117594897A CN117594897A CN202311573271.1A CN202311573271A CN117594897A CN 117594897 A CN117594897 A CN 117594897A CN 202311573271 A CN202311573271 A CN 202311573271A CN 117594897 A CN117594897 A CN 117594897A
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- China
- Prior art keywords
- sodium
- controlled
- source
- reaction
- phosphoric acid
- 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
- 238000000034 method Methods 0.000 title claims abstract description 61
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 34
- 239000002699 waste material Substances 0.000 title claims abstract description 26
- 238000004064 recycling Methods 0.000 title claims abstract description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 64
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 38
- 239000007774 positive electrode material Substances 0.000 claims abstract description 36
- 229910052751 metal Inorganic materials 0.000 claims abstract description 33
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims abstract description 33
- 229940039790 sodium oxalate Drugs 0.000 claims abstract description 33
- 238000001556 precipitation Methods 0.000 claims abstract description 32
- 238000011084 recovery Methods 0.000 claims abstract description 29
- 239000002244 precipitate Substances 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 27
- 230000008569 process Effects 0.000 claims abstract description 22
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 14
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 14
- 239000010452 phosphate Substances 0.000 claims abstract description 14
- 230000001376 precipitating effect Effects 0.000 claims abstract description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 72
- 238000006243 chemical reaction Methods 0.000 claims description 66
- 239000000463 material Substances 0.000 claims description 66
- 239000011734 sodium Substances 0.000 claims description 61
- 239000010949 copper Substances 0.000 claims description 50
- 239000000243 solution Substances 0.000 claims description 50
- 229910052708 sodium Inorganic materials 0.000 claims description 41
- 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 claims description 40
- 229910052698 phosphorus Inorganic materials 0.000 claims description 40
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 39
- 239000011574 phosphorus Substances 0.000 claims description 39
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 36
- 229910052802 copper Inorganic materials 0.000 claims description 36
- 239000011572 manganese Substances 0.000 claims description 35
- 238000005245 sintering Methods 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 229910052742 iron Inorganic materials 0.000 claims description 28
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 24
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 23
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 22
- 229910052748 manganese Inorganic materials 0.000 claims description 22
- 230000035484 reaction time Effects 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 18
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 17
- 238000003916 acid precipitation Methods 0.000 claims description 17
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 17
- 239000001632 sodium acetate Substances 0.000 claims description 17
- 235000017281 sodium acetate Nutrition 0.000 claims description 17
- 229940071125 manganese acetate Drugs 0.000 claims description 16
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 16
- 239000003960 organic solvent Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 238000004090 dissolution Methods 0.000 claims description 12
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 12
- -1 phosphoric acid compound Chemical class 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 9
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 9
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 9
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 9
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 8
- 239000010405 anode material Substances 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 7
- AWRQDLAZGAQUNZ-UHFFFAOYSA-K sodium;iron(2+);phosphate Chemical compound [Na+].[Fe+2].[O-]P([O-])([O-])=O AWRQDLAZGAQUNZ-UHFFFAOYSA-K 0.000 claims description 7
- DDAQLPYLBPPPRV-UHFFFAOYSA-N [4-(hydroxymethyl)-2-oxo-1,3,2lambda5-dioxaphosphetan-2-yl] dihydrogen phosphate Chemical compound OCC1OP(=O)(OP(O)(O)=O)O1 DDAQLPYLBPPPRV-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 6
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 6
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 claims description 6
- 239000004299 sodium benzoate Substances 0.000 claims description 6
- 235000010234 sodium benzoate Nutrition 0.000 claims description 6
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 6
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000001488 sodium phosphate Substances 0.000 claims description 6
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 6
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 6
- 235000019801 trisodium phosphate Nutrition 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 230000018044 dehydration Effects 0.000 claims description 5
- 238000006297 dehydration reaction Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 235000017550 sodium carbonate Nutrition 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 238000001514 detection method Methods 0.000 claims description 4
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 239000011656 manganese carbonate Substances 0.000 claims description 3
- 235000006748 manganese carbonate Nutrition 0.000 claims description 3
- 229940093474 manganese carbonate Drugs 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 3
- 239000011343 solid material Substances 0.000 claims description 3
- 230000001502 supplementing effect Effects 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- BYTVRGSKFNKHHE-UHFFFAOYSA-K sodium;[hydroxy(oxido)phosphoryl] phosphate;iron(2+) Chemical compound [Na+].[Fe+2].OP([O-])(=O)OP([O-])([O-])=O BYTVRGSKFNKHHE-UHFFFAOYSA-K 0.000 claims 1
- 229940039748 oxalate Drugs 0.000 abstract description 10
- 239000002253 acid Substances 0.000 abstract description 8
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 abstract description 3
- 229940062993 ferrous oxalate Drugs 0.000 abstract description 3
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 abstract description 3
- 150000003016 phosphoric acids Chemical class 0.000 abstract description 2
- 239000002245 particle Substances 0.000 description 36
- 238000001878 scanning electron micrograph Methods 0.000 description 34
- 230000000052 comparative effect Effects 0.000 description 28
- 239000011701 zinc Substances 0.000 description 22
- 239000013078 crystal Substances 0.000 description 17
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 14
- 229910052725 zinc Inorganic materials 0.000 description 14
- 238000005054 agglomeration Methods 0.000 description 10
- 230000002776 aggregation Effects 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000002585 base Substances 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 230000001276 controlling effect Effects 0.000 description 8
- 238000001000 micrograph Methods 0.000 description 8
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 239000004246 zinc acetate Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 238000002386 leaching Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 229910021385 hard carbon Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 230000000977 initiatory effect Effects 0.000 description 4
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 238000002791 soaking Methods 0.000 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 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 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920000447 polyanionic polymer Polymers 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000005955 Ferric phosphate Substances 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000011706 ferric diphosphate Substances 0.000 description 2
- 235000007144 ferric diphosphate Nutrition 0.000 description 2
- 229940032958 ferric phosphate Drugs 0.000 description 2
- CADNYOZXMIKYPR-UHFFFAOYSA-B ferric pyrophosphate Chemical compound [Fe+3].[Fe+3].[Fe+3].[Fe+3].[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O CADNYOZXMIKYPR-UHFFFAOYSA-B 0.000 description 2
- 229940036404 ferric pyrophosphate Drugs 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910000398 iron phosphate Inorganic materials 0.000 description 2
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229940085991 phosphate ion Drugs 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
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- 238000000926 separation method Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 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 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- GFORUURFPDRRRJ-UHFFFAOYSA-N [Na].[Mn] Chemical compound [Na].[Mn] GFORUURFPDRRRJ-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
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- 238000005520 cutting process Methods 0.000 description 1
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
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- 239000011229 interlayer Substances 0.000 description 1
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- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
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- 239000013049 sediment Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- VQBIMXHWYSRDLF-UHFFFAOYSA-M sodium;azane;hydrogen carbonate Chemical compound [NH4+].[Na+].[O-]C([O-])=O VQBIMXHWYSRDLF-UHFFFAOYSA-M 0.000 description 1
- XWQGIDJIEPIQBD-UHFFFAOYSA-J sodium;iron(3+);phosphonato phosphate Chemical compound [Na+].[Fe+3].[O-]P([O-])(=O)OP([O-])([O-])=O XWQGIDJIEPIQBD-UHFFFAOYSA-J 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Geology (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Metallurgy (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a method for recycling the positive electrode of a waste sodium ion battery, and relates to the technical field of battery recycling. The method comprises the steps of respectively carrying out a dissolving stage, a sodium oxalate precipitating stage and a phosphoric acid precipitating stage by optimizing a precipitating process of the positive electrode material, dissolving oxalic acid under the condition of strong acid, then reacting with oxalic acid to generate precipitates (such as ferric oxalate and ferrous oxalate), and finally reacting with phosphoric acid compounds, wherein the precipitates are changed from oxalate to phosphate precipitates due to lower Ksp of the phosphate precipitates. By optimizing the precipitation process, the metal can be more fully precipitated, and the recovery rate of each metal element is improved.
Description
Technical Field
The invention relates to the technical field of battery recovery, in particular to a recovery method of a positive electrode of a waste sodium ion battery.
Background
At present, the lithium ion battery has the characteristics of no harmful gas generated in the using process, portability, durability, high energy density, low self-discharge and the like, so that the application range and the depth of the lithium ion battery are increased increasingly. However, as the demand of lithium increases, the shortage of lithium reserves, the high price, and the like have led to awareness of the need to develop new batteries. The alkali metal sodium and lithium are in the same main group, have electrochemical properties similar to lithium, and sodium is quite widely distributed in the crust, being the sixth element of the reserve abundance, accounting for about 2.74%. The sodium ion battery consists of a hard carbon negative electrode and a sodium-manganese-based positive electrode, and the materials are nontoxic and 100% of the battery can be recycled.
The main recovery method of the sodium ion battery comprises an acid leaching multi-step precipitation method, namely, a weak acid solvent is adopted to dissolve the anode of the battery, after dissolution is completed, relevant parameters such as pH value and the like are adjusted by adding a proper precipitator, target elements are precipitated step by step, and then metal materials are recovered or prepared into other materials through means such as drying and calcining. If the positive plate is recovered, alkali liquor leaching is added before acid leaching, and the aluminum foil is dissolved and removed. In addition, the recovery method also comprises a multi-step calcination method, impurities are removed through different temperature control, and materials such as a sodium source, an additive and the like are added subsequently to resynthesize a target material; other recovery methods also comprise a special resin adsorption method, a wet ultrasonic recovery method and the like.
However, the current recovery method of sodium ion batteries generally has the following problems: (1) there is a large sodium loss during recovery; (2) the recovery rate of the whole metal is still to be improved.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a recovery method of a waste sodium ion battery anode, which aims to remarkably improve the recovery rate of metal elements.
The invention is realized in the following way:
in a first aspect, the invention provides a method for recycling a positive electrode of a waste sodium ion battery, comprising the steps of: pretreating a waste sodium ion battery to obtain a positive electrode material, and carrying out a step-by-step precipitation reaction on the positive electrode material, wherein the step-by-step precipitation reaction comprises a dissolution stage, a sodium oxalate precipitation stage and a phosphoric acid precipitation stage which are sequentially carried out;
wherein the dissolution phase comprises: mixing the anode material with an organic solvent and oxalic acid, and dissolving under the condition that the pH value is 0.5-1.5 to obtain a mixed solution;
the sodium oxalate precipitation stage comprises: mixing the mixed solution with sodium oxalate solution, and precipitating under the condition that the pH value is 3-5;
the phosphoric acid precipitation stage includes: mixing the mixed system obtained after the precipitation of the sodium oxalate precipitation stage with a phosphoric acid compound solution, and reacting under the condition that the pH value is 4.0-6.5.
In an alternative embodiment, the process of the dissolution stage comprises: introducing inert gas into the reactor, adding an organic solvent as a base solution, adding oxalic acid solution with the concentration of 0.1-0.5 mol/L into the base solution to enable the pH value to meet the requirement, dispersing the anode material into the solution, and stirring and reacting for 1-4 h.
In an alternative embodiment, the mass ratio of the positive electrode material to the organic solvent is controlled to be 1 (0.1-2.0);
preferably, the organic solvent is selected from at least one of ethylene glycol, polyethylene glycol, ethylene glycol phenyl ether and glycerol; more preferably glycerol.
In an alternative embodiment, in the sodium oxalate precipitation stage, the reaction temperature is controlled to be 50-80 ℃ and the reaction time is controlled to be 10-36 hours; preferably, the reaction temperature is controlled to be 50-60 ℃, the reaction time is controlled to be 10-12 h, and the pH value of the reaction is controlled to be 3.0-3.5.
In an alternative embodiment, the sodium oxalate solution has a concentration of 0.05mol/L to 0.25mol/L and an addition rate of 20mL/min to 100mL/min.
In an alternative embodiment, in the phosphoric acid precipitation stage, the reaction temperature is controlled to be 70-90 ℃ and the reaction time is controlled to be 48-96 hours; preferably, in the phosphoric acid precipitation stage, the reaction temperature is controlled to be 70-75 ℃, the reaction time is controlled to be 90-96 h, and the pH value of the reaction is controlled to be 6.0-6.5;
preferably, the phosphoric acid compound is at least one selected from phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, ammonium dihydrogen phosphate, sodium pyrophosphate and hydroxyethylidene diphosphate; preferably, the phosphoric acid compound is disodium hydrogen phosphate;
more preferably, the concentration of the phosphoric acid compound solution is 0.1mol/L to 1mol/L, and the addition rate is 20mL/min to 50mL/min.
In an alternative embodiment, the method further comprises: after the reaction in the phosphoric acid precipitation stage is finished, taking a precipitate, drying the precipitate, detecting the proportion of metal elements, then supplementing a sodium source, a phosphorus source, a copper source, a manganese source and an N metal source into a reaction kettle according to the detection result, regulating the molar ratio of sodium, iron, copper, manganese, N and phosphorus elements to be 4:x:y:z (1-x-y-z) to 2, then heating to 100-200 ℃ to react to remove a solvent, and then sintering the obtained solid material;
wherein, the value of x is 0.2-0.8, the value of y is 0.2-0.5, the value of z is 0-0.5, and x+y+z is less than or equal to 1;
preferably, the sodium source is selected from at least one of sodium pyrophosphate, sodium carbonate, sodium bicarbonate, sodium acetate, sodium oxalate, sodium ethoxide and sodium benzoate; more preferably, the sodium source is selected from at least one of sodium acetate, sodium ethoxide and sodium benzoate;
preferably, the phosphorus source is selected from at least one of phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, ammonium dihydrogen phosphate, sodium pyrophosphate, and hydroxyethylidene diphosphate; more preferably, the phosphorus source is disodium hydrogen phosphate;
preferably, the copper source is selected from at least one of copper sulfate, copper chloride and copper acetate; more preferably, the copper source is copper acetate;
preferably, the manganese source is selected from at least one of manganese sulfate, manganese chloride, manganese acetate and manganese carbonate; more preferably, the manganese source is manganese acetate;
preferably, the metal element in the N metal source is selected from at least one of Ni, zn, cr, al, mg, zr, la, sr, Y and W, and the N metal source is selected from at least one of sulfate, acetate, chloride, phosphate and nitrate;
in an alternative embodiment, the sintering temperature is 500 ℃ to 800 ℃ and the sintering time is 6 hours to 12 hours;
preferably, the sintering is performed under an inert atmosphere.
In an alternative embodiment, the pre-processing includes: discharging and disassembling the waste sodium ion battery, and crushing the positive plate to obtain a positive crushed material; washing and screening the broken positive electrode material to obtain a positive electrode material;
preferably, the type of the waste sodium ion battery is selected from at least one of sodium iron phosphate, ferric pyrophosphate, and layered oxide sodium ion battery;
preferably, when the waste sodium ion battery is discharged, the discharge current is controlled to be 0.08-0.12 ℃ and the discharge time is controlled to be 15-30 h.
In an alternative embodiment, when the positive electrode crushed material is washed with water, the mass ratio of the positive electrode crushed material to the water consumption is controlled to be 1: (5-20);
preferably, the temperature of the water washing is controlled to be between minus 30 ℃ and 0 ℃, the water washing time is 5min to 15min, and the dehydration time is 2min to 10min;
preferably, after the water washing is completed, the mixture is sieved through a 400-450 mesh sieve and then dried.
The invention has the following beneficial effects: the method comprises the steps of respectively carrying out a dissolving stage, a sodium oxalate precipitating stage and a phosphoric acid precipitating stage by optimizing a precipitating process of the positive electrode material, dissolving oxalic acid under the condition of strong acid, then reacting with oxalic acid to generate precipitates (such as ferric oxalate and ferrous oxalate), and finally reacting with phosphoric acid compounds, wherein the precipitates are changed from oxalate to phosphate precipitates due to lower Ksp of the phosphate precipitates. By optimizing the precipitation process, the metal can be more fully precipitated, and the recovery rate of each metal element is improved.
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 a battery recycling process;
FIG. 2 is an SEM image of an oxalate intermediate;
FIG. 3 is an SEM image of the polyanionic material of example 1;
FIG. 4 is an SEM image of the polyanionic material of example 2;
FIG. 5 is an SEM image of the polyanionic material of example 3;
FIG. 6 is an SEM image of the polyanionic material of example 4;
FIG. 7 is an SEM image of the polyanionic material of example 5;
FIG. 8 is an SEM image of the polyanionic material of example 6;
FIG. 9 is an SEM image of the polyanionic material of example 7;
FIG. 10 is an SEM image of the polyanionic material of example 8;
FIG. 11 is an SEM image of a polyanionic material of example 9;
FIG. 12 is an SEM image of a polyanionic material of example 10;
FIG. 13 is an SEM image of the polyanionic material of example 11;
FIG. 14 is an SEM image of the polyanionic material of example 12;
FIG. 15 is an SEM image of the polyanionic material of example 13;
FIG. 16 is an SEM image of the polyanionic material of example 14;
FIG. 17 is an SEM image of the polyanionic material of comparative example 1;
FIG. 18 is an SEM image of comparative example 2 polyanionic material;
FIG. 19 is an SEM image of the polyanionic material of comparative example 3;
FIG. 20 is an SEM image of the polyanionic material of comparative example 4;
FIG. 21 is an SEM image of the polyanionic material of comparative example 5;
FIG. 22 is an SEM image of the polyanionic material of comparative example 6.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The invention provides a method for recycling the positive electrode of a waste sodium ion battery, referring to fig. 1, comprising the following steps:
s1, discharge disassembly
Discharging and disassembling the waste sodium ion battery to obtain a positive plate and a negative plate respectively, wherein the negative plate is used for recycling the negative material, and hard carbon is recycled through other treatment procedures; the process in the embodiment of the invention mainly comprises the steps of recycling the positive electrode material in the positive electrode plate, and crushing the positive electrode plate to obtain a positive electrode crushed material, so that the positive electrode material can be separated conveniently.
All Na is enriched to the positive electrode through discharge, so that the negative electrode is in a sodium-deficiency state, the subsequent treatment is convenient, and the recovery rate of sodium is improved. The discharging equipment can adopt LAND equipment, and the discharging equipment is placed until the voltage is stable after discharging, so that the risk of battery disassembly is reduced.
In some embodiments, the type of waste sodium ion battery is selected from at least one of sodium iron phosphate, ferric pyrophosphate, and layered oxide sodium ion batteries, and the above several common waste sodium ion batteries are suitable for the recovery methods provided by embodiments of the present invention. The positive electrode material of the layered oxide sodium ion battery may be an iron-based layered oxide, but is not limited thereto.
In some embodiments, when discharging the waste sodium ion battery, the discharge current is controlled to be 0.08-0.12C, and the discharge time is controlled to be 15-30 h so as to fully discharge. The discharge current may be 0.1C, and the discharge time may be 15, 20h, 25h, 30h, etc.
In some embodiments, the method of breaking the positive electrode sheet is not limited, and the method of shearing can be adopted, and no special requirement is imposed on the particle size.
S2, washing and sieving
The positive electrode crushed material is washed with water and sieved to obtain a positive electrode material, the positive electrode material can be separated from the current collector after being immersed in water, the positive electrode material and the positive electrode material are all in micron level, the positive electrode material and the current collector can be separated through a screen, and the current collector cannot be changed into a oversize product through the screen. And after S1 and S2, finishing pretreatment operation on the waste sodium ion battery, and separating to obtain the anode material.
In some embodiments, when the positive electrode crushed material is washed with water, the mass ratio of the positive electrode crushed material to the water amount is controlled to be 1: (5-20), such as 1:5, 1:10, 1:15, 1:20, etc., and the water used in the water washing process is brine-free.
In some embodiments, the temperature of the water wash is controlled to be-30-0 ℃, the water wash time is 5-15 min, the dehydration time is 2-10 min, and the dehydrated filter cake is recovered. After the water washing is finished, the mixture is sieved by a 400-450 mesh sieve (such as a 425 mesh sieve) and then dried. The temperature and time in the drying process are not limited, so that the surface water can be sufficiently removed, the drying temperature can be about 80 ℃, the drying time can be about 24 hours, and the drying operation can be performed by adopting a blast drying device. The embodiment of the invention separates the current collector from the pole piece in a water washing mode, has high efficiency, simultaneously adopts extremely low temperature non-salt water for short time water washing by controlling the water washing strength, separates the current collector on the pole piece, reduces the loss of Na and realizes the full recovery of metal elements.
S3, fractional precipitation
The positive electrode material is subjected to a step-by-step precipitation reaction, wherein the step-by-step precipitation reaction comprises a dissolution stage, a sodium oxalate precipitation stage and a phosphoric acid precipitation stage which are sequentially carried out, namely, the controlled precipitation in the figure 1 is carried out to obtain an oxalate precursor, and then ion replacement is carried out to obtain a phosphate precursor. The embodiment of the invention adopts a secondary substitution method to synthesize, firstly generates an oxalate intermediate, utilizes the solubility difference of the precipitate and then uses PO 4 3- Substitution C 2 O 4 2- PO is added in wet environment 4 3- And the crystal lattice is embedded, so that the embedding efficiency is improved, and the purity of the reactant is improved.
The following describes three stages:
(1) Dissolution stage
The dissolution phase comprises: mixing the positive electrode material with an organic solvent and oxalic acid, dissolving under the condition that the pH value is 0.5-1.5 to obtain a mixed solution, and completely dissolving all metals in the positive electrode material under the strong acid condition. The pH value can be 0.5, 0.8, 1.0, 1.2, 1.5 and the like by regulating the dosage of oxalic acid to ensure that the pH value meets the requirement.
In actual operation, the dissolution phase process includes: introducing inert gas into the reactor, adding an organic solvent as a base solution, adding oxalic acid solution with the concentration of 0.1-0.5 mol/L into the base solution to enable the pH value to meet the requirement, dispersing the anode material into the solution, and stirring and reacting for 1-4 h to enable all metals to be completely dissolved. The reaction is carried out in an organic system, so that the solubility of inorganic matters can be improved, and meanwhile, a C source can be provided after sintering without additional carbon supplement.
Specifically, the oxalic acid solution can be an aqueous solution, the specific concentration can be 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L, 0.5mol/L and the like, and the reaction time can be 1h, 2h, 3h, 4h and the like. The inert gas is not limited in kind, and may be nitrogen, argon, or the like.
In some embodiments, the mass ratio of the positive electrode material to the organic solvent is controlled to be 1 (0.1-2.0) so that the metal in the positive electrode material can be completely dissolved. Specifically, the mass ratio of the positive electrode material to the organic solvent may be 1:0.1, 1:0.5, 1:1.0, 1:1.5, 1:2.0, etc.
In some embodiments, the organic solvent is at least one selected from ethylene glycol, polyethylene glycol, ethylene glycol phenyl ether and glycerol, and may be any one or more of the above, and more preferably glycerol. The high-temperature solvent is adopted, and the dissolution rate of the positive electrode material in weak acid is slower after the positive electrode material is sintered, so that the high-temperature environment can increase the reactivity. In addition, the embodiment of the invention reduces the influence of polar environment on the morphology of particles by adopting the low-polarity high-temperature solvent, so that the reaction environment is milder, and small particles are not easy to generate.
(2) Precipitation stage of sodium oxalate
The sodium oxalate precipitation stage comprises: mixing the mixed solution with sodium oxalate solution, precipitating at pH of 3-5, and precipitating at pH of 3-5 until the supernatant is clear after filtration. In this reaction, the dissociated ions react with the oxalate to produce a yellowish green precipitate, which is mainly iron oxalate, ferrous oxalate, and the like.
In some embodiments, in the sodium oxalate precipitation stage, the reaction temperature is controlled to be 50-80 ℃ and the reaction time is controlled to be 10-36 hours; preferably, the reaction temperature is controlled to be 50-60 ℃, the reaction time is controlled to be 10-12 h, and the pH value of the reaction is controlled to be 3.0-3.5. The reaction conditions are optimized to allow the reaction to proceed sufficiently.
Specifically, in the sodium oxalate precipitation stage, the pH value of the reaction may be 3.0, 3.2, 3.5, 4.0, 4.5, 5.0, etc., the reaction temperature may be 50 ℃, 55 ℃, 60 ℃, 70 ℃,80 ℃ and the like, the reaction time may be 10 hours, 11 hours, 12 hours, 15 hours, 18 hours, 20 hours, 25 hours, 30 hours, 36 hours and the like, and the stirring rate in the reaction process may be 500rpm, without limitation.
In some embodiments, the concentration of the sodium oxalate solution is 0.05mol/L to 0.25mol/L, the addition rate is 20mL/min to 100mL/min, and the specific addition rate is that the pH value meets the requirement. Specifically, the concentration of the sodium oxalate solution may be 0.05mol/L, 0.10mol/L, 0.15mol/L, 0.20mol/L, 0.25mol/L, etc., and the addition rate may be 20mL/min, 30mL/min, 50mL/min, 80mL/min, 100mL/min, etc.
(3) Phosphoric acid precipitation stage
The phosphoric acid precipitation stage includes: mixing the mixed system obtained after the precipitation of the sodium oxalate precipitation stage with a phosphoric acid compound solution, and reacting under the condition that the pH value is 4.0-6.5. Phosphate precipitates have a lower Ksp, which changes the precipitate from oxalate to phosphate.
In an alternative embodiment, in the phosphoric acid precipitation stage, the reaction temperature is controlled to be 70-90 ℃ and the reaction time is controlled to be 48-96 hours; preferably, in the phosphoric acid precipitation stage, the reaction temperature is controlled to be 70-75 ℃, the reaction time is controlled to be 90-96 h, and the pH value of the reaction is controlled to be 6.0-6.5. The conversion process needs to provide a sufficient reaction driving force, and therefore needs to be performed in a strong acid high-temperature environment to promote the reaction to proceed sufficiently. The reaction time is longer, the oxalate is gradually converted into phosphate by reducing the reaction pH, the substitution is more sufficient by slow reaction, meanwhile, the internal structure of the phosphate precursor is modified, when the system does not generate extra sediment any more, the supernatant becomes clear after filtration, and the reaction is complete.
Specifically, in the phosphoric acid precipitation stage, the reaction temperature may be 70 ℃, 75 ℃,80 ℃, 85 ℃, 90 ℃, etc., the reaction time may be 48h, 50h, 60h, 70h, 80h, 90h, 96h, etc., and the pH value of the reaction may be 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, etc. The stirring rate during the reaction is not limited and may be controlled to about 500rpm.
In some embodiments, the phosphate-based compound is selected from at least one of phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, ammonium dihydrogen phosphate, sodium pyrophosphate, and hydroxyethylidene diphosphate; preferably, the phosphoric acid compound is disodium hydrogen phosphate, and the phosphoric acid compound can be any one or more of the above. The concentration of the phosphoric acid compound solution is 0.1mol/L to 1mol/L (for example, 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L, 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L, 1.0mol/L, etc.), and the addition rate is 20mL/min to 50mL/min, specifically, 20mL/min, 30mL/min, 40mL/min, 50mL/min, etc.
The equipment used in the water washing process of S2 and the fractional precipitation process of S3 can be 50L reaction kettles, and the reaction temperature can be controlled by adjusting the water temperature of the water bath kettle by matching with stirring and interlayer water bath.
S4, wet sintering
After the reaction in the phosphoric acid precipitation stage is finished, taking a precipitate, drying the precipitate, detecting the proportion of metal elements, then supplementing a sodium source, a phosphorus source, a copper source, a manganese source and an N metal source into a reaction kettle according to the detection result, regulating the molar ratio of sodium, iron, copper, manganese, N and phosphorus elements to be 4:x:y:z (1-x-y-z) to 2, then heating to 100-200 ℃ to react to remove a solvent, and then sintering the obtained solid material. When the molar ratio of each metal element satisfies the above requirement, the sintered product is Na 4 Fe x Cu y Mn z N 1-x-y-z (PO 4 ) 2 A polyanion compound, wherein x has a value of 0.2 to 0.8, y has a value of 0.2 to 0.5, z has a value of 0 to 0.5, and x+y+z is less than or equal to 1.
It should be noted that the sintering process according to the embodiment of the present invention has the following advantages: according to the embodiment of the invention, the proportion of the early-stage product is detected, the elements are supplemented in a wet-process orientation mode, the process practicability is wider, and the proportion of the product is accurate and controllable. The wet calcination process is adopted, the solvent is directly evaporated at high temperature in the later stage, the viscosity of the product is increased, the elements are uniformly dispersed, the C coating layer is formed after sintering, under the condition of full stirring, the coating layer is uniform, the coating thickness is adjustable according to the content of the residual solvent, and the subsequent procedures are reduced.
Specifically, the molar quantity of the added sodium source, the phosphorus source, the copper source, the manganese source and the N metal source is determined according to the detection result of the metal elements in the precipitate and the chemical formula of the target sintering product, the specific proportion of the polyanion is adjustable according to the added metal quantity, and the diversity of the product is increased. In the product, the value of x can be 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 and the like, the value of y can be 0.2, 0.3, 0.4, 0.5 and the like, the value of z can be 0.0, 0.1, 0.2, 0.3, 0.4, 0.5 and the like, the value of x+y+z is less than or equal to 1, and when the value of x+y+z is 1, the addition amount of metal N is 0.
Specifically, after the raw materials are supplemented, the temperature is raised to 100-200 ℃ for reaction so as to remove most of the solvent, and the solvent is transferred to a calciner for sintering, and the sintering process can reduce the presintering dehydration process and improve the sintering efficiency because the high-temperature treatment is carried out in the early stage. Specifically, the operation temperature at the time of removing the solvent may be 100 ℃, 150 ℃, 200 ℃, or the like.
In some embodiments, the sodium source is selected from at least one of sodium pyrophosphate, sodium carbonate, sodium bicarbonate, sodium acetate, sodium oxalate, sodium ethoxide, and sodium benzoate, which may be any one or more of the above; preferably, the sodium source is selected from at least one of sodium acetate, sodium ethoxide and sodium benzoate. The phosphorus source is at least one selected from phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, ammonium dihydrogen phosphate, sodium pyrophosphate and hydroxyethylidene diphosphate, and can be any one or more of the above; preferably, the phosphorus source is disodium hydrogen phosphate. The copper source is at least one selected from copper sulfate, copper chloride and copper acetate, and can be any one or more of the above; preferably, the copper source is copper acetate. The manganese source is selected from at least one of manganese sulfate, manganese chloride, manganese acetate and manganese carbonate, and can be any one or more of the above; preferably, the manganese source is manganese acetate. Organic matters are adopted as raw materials of a sodium source, a phosphorus source, a copper source and a manganese source, and surface carbon coating is formed after sintering.
Further, the metal element in the N metal source is selected from at least one of Ni, zn, cr, al, mg, zr, la, sr, Y and W, and any one or more metal elements can be doped according to requirements. The N metal source is at least one selected from sulfate, acetate, chloride, phosphate and nitrate, and can be any one or more of the above.
In some embodiments, sintering is performed in an inert atmosphere at a temperature of 500-800 ℃ for a time of 6-12 hours to obtain a target product with better electrochemical properties. The inert gas may be nitrogen, argon, etc., and the sintering temperature may be 500 ℃, 600 ℃, 700 ℃, 800 ℃, etc.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
The positive electrode material of the waste sodium ion battery treated in the following examples and comparative examples was sodium ferric pyrophosphate Na 4 Fe 3 (PO 4 ) 2 (P 2 O 7 ) The positive current collector is aluminum foil.
Example 1
The embodiment provides a method for recycling the positive electrode of a waste sodium ion battery, which comprises the following steps:
(1) And (3) discharge disassembly: and (3) discharging the abandoned sodium ion battery for 20 hours according to the discharge current of 0.1C, standing for stabilizing the voltage, disassembling the battery, picking out the positive plate after disassembling, and cutting the positive plate for later use.
(2) Washing and sieving: the positive plate is arranged in the reaction vessel according to the weight ratio: no brine = 1:5, mixing, at this time, stirring to 500rpm, controlling the temperature in the kettle to minus 30 ℃, washing for 5min, filtering and dehydrating after washing, dehydrating for 2min, recovering a filter cake, drying at 80 ℃ for 24h, and sieving by using a 425-mesh screen to obtain the anode material.
(3) Step-by-step precipitation: adding enough nitrogen into a reactor, adding 40L of glycerol as a base solution, continuously adding 0.3mol/L oxalic acid solution to control the pH to be about 1, weighing 500g of positive electrode material (the weight ratio is about 1:0.1 at the moment), dispersing the positive electrode material in the base solution, stirring for 2 hours, continuously adding 0.2mol/L sodium oxalate solution, controlling the pH to be 3 at 50 ℃, the adding speed to be 20mL/min, reacting for 48 hours, slowly adding 0.5mol/L ammonium dihydrogen phosphate solution at the pH to be 4, the adding speed to be 100mL/min, reacting for 96 hours, drying the precipitate after the reaction is finished, sampling and detecting the element proportion in the precipitate.
(4) Wet sintering: according to the test result, sodium acetate, disodium hydrogen phosphate, copper acetate, manganese acetate and zinc acetate (the step replaces sintering supplementary metal and is uniformly dispersed) are supplemented in a reaction kettle, and the molar weight ratio of sodium to iron to copper to manganese to zinc to phosphorus is adjusted to be sodium: iron: copper: manganese: zinc: phosphorus=4: 0.2:0.2:0.5:0.1:2, make it form Na 4 Fe 0.2 Cu 0.2 Mn 0.5 Zn 0.1 (PO 4 ) 2 Mixing the proportional compounds at 500rpm for 4 hours, heating to 150 ℃, treating for 2 hours, removing most of the solvent, transferring to a muffle furnace for sintering at 500 ℃ for 12 hours under argon atmosphere, and finally obtaining Na 4 Fe 0.2 Cu 0.2 Mn 0.5 Zn 0.1( PO 4 ) 2 A polyanionic compound of the type.
Fig. 2 is an SEM image of the oxalate intermediate obtained in step (2), as can be seen: the oxalate intermediate presents a spinel structure, and the overall particle size is relatively large.
Fig. 3 is an SEM electron microscope image of the polyanionic material prepared in example 1, and it can be seen that: the monocrystalline particles are uniform, the crystal faces are clear, and the monocrystalline particles are large;
example 2
Example 2 differs from example 1 in that the positive electrode sheet is contained in the reaction vessel in step (2) in a weight ratio: no brine = 1:5 mixing and adjusting to 1:20, and other steps and parameters are consistent.
Fig. 4 is an SEM electron microscope image of the polyanionic material prepared in example 2, and it can be seen that: the monocrystalline particles are more uniform, part of monocrystalline particles are agglomerated, the monocrystalline particles are slightly smaller than those in the embodiment 1, and the polar solution has larger influence on material sintering;
example 3
Example 3 differs from example 1 in that the temperature in the control tank in step (2) was adjusted to-30℃to 0℃and the other steps and parameters were kept consistent.
Fig. 5 is an SEM electron microscope image of the polyanionic material prepared in example 3, and it can be seen that: the single crystal particles are more uniform, and the whole is not much different from that of the embodiment 2;
example 4
Example 4 differs from example 1 in that the washing time in step (2) was adjusted to 15min for 5min, and the other steps and parameters remained the same.
Fig. 6 is an SEM electron microscope image of the polyanionic material prepared in example 4, and it can be seen that: the monocrystalline particles are uniform, the crystal faces are clear, no agglomeration phenomenon exists, and the particles are smaller in impurity after washing, so that the monocrystalline particles are more beneficial to dispersion;
example 5
Example 5 differs from example 1 in that the dehydration time 2min in step (2) was adjusted to 10min, and the other steps and parameters remained the same.
Fig. 7 is an SEM electron microscope image of the polyanionic material prepared in example 5, and it can be seen that: the single crystal particles are more uniform, and the whole is not much different from that of the embodiment 2;
example 6
Example 6 differs from example 1 in that "500 g of the positive electrode material was weighed and dispersed in the base liquid" in the step (3) was adjusted as follows: 25g of positive electrode material is weighed and dispersed in the base solution, and other steps and parameters are kept consistent.
Fig. 8 is an SEM electron microscope image of the polyanionic material prepared in example 6, and it can be seen that: the monocrystal particles are more uniform, the agglomeration is reduced, the crystal face is clear, the base solution material is less, the material dispersion is better, and the monocrystal dispersion is better after sintering;
example 7
Example 7 differs from example 1 in that "control process pH 3, temperature 80 ℃, addition rate 20ml/min, reaction time 48h" in step (3) was adjusted as: controlling the pH value of the process to be 6, the temperature to be 50 ℃, the adding speed to be 100ml/min, the reaction time to be 10 hours, and keeping other steps and parameters consistent.
Fig. 9 is an SEM electron microscope image of the polyanionic material prepared in example 7, and it can be seen that: the pH is higher, the reaction time is reduced, the monocrystalline particles are larger, the agglomeration is more, the monocrystalline particles are more uniform, and the crystal face is clearer;
example 8
Example 8 differs from example 1 in that "slowly dropping ammonium dihydrogen phosphate in step (3), controlling the process pH to 4, the temperature to 70 ℃, the addition rate to 20ml/min, and the reaction time to 96h" were adjusted to: slowly dropping phosphoric acid, controlling pH at 3, temperature at 90 deg.C, adding speed at 50ml/min, reacting for 48 hr, and keeping other steps and parameters consistent.
FIG. 10 is an SEM image of the polyanionic material prepared in example 8, as can be seen: the reaction temperature is higher, the reaction time is reduced, monocrystalline particles are larger, and the agglomeration is more;
example 9
Example 9 differs from example 1 in that "it was supplemented with a certain amount of sodium acetate, disodium hydrogen phosphate, copper acetate, manganese acetate and zinc acetate in the reaction vessel in step (4), adjusted to the molar ratio of sodium, iron, copper, manganese, zinc and phosphorus as follows: iron: copper: manganese: zinc: phosphorus=4: 0.2:0.2:0.5:0.1:2, make it form Na 4 Fe 0.2 Cu 0.2 Mn 0.5 Zn 0.1 (PO 4 ) 2 The ratio of the compounds "adjusted to: the sodium acetate, the disodium hydrogen phosphate and the copper acetate are supplemented in a reaction kettle to be regulated to the molar weight ratio of sodium, iron, copper and phosphorus as follows: iron: copper: phosphorus=4: 0.8:0.2:2, make it form Na 4 Fe 0.8 Cu 0.2 (PO 4 ) 2 A compound of the proportional type.
FIG. 11 is an SEM image of the polyanionic material prepared in example 9, as can be seen: the Fe content is improved, and the agglomeration of single crystal particles is increased compared with that of the embodiment 1;
example 10
Example 10 differs from example 1 in that "in step (4)," it was supplemented with a certain amount of sodium acetate, disodium hydrogen phosphate, copper acetate, manganese acetate and zinc acetate in the reaction vessel, adjusted to the molar ratio of sodium, iron, copper, manganese, zinc and phosphorus as follows:iron: copper: manganese: zinc: phosphorus=4: 0.2:0.2:0.5:0.1:2, make it form Na 4 Fe 0.2 Cu 0.2 Mn 0.5 Zn 0.1 (PO 4 ) 2 The ratio of the compounds "adjusted to: adding a certain amount of sodium acetate, disodium hydrogen phosphate, copper acetate, manganese acetate and zinc acetate into a reaction kettle, and adjusting the molar ratio of sodium, iron, copper, manganese, zinc and phosphorus to sodium: iron: copper: manganese: zinc: phosphorus=4: 0.2:0.5:0.1:0.2:2, make it form Na 4 Fe 0.2 Cu 0.5 Mn 0.1 Zn 0.2 (PO 4 ) 2 A compound of the proportional type.
FIG. 12 is an SEM image of the polyanionic material prepared in example 10, as follows: increasing Cu content, single crystal particles increased agglomeration compared to example 1;
example 11
Example 11 differs from example 1 in that "in step (4)," it was supplemented with a certain amount of sodium acetate, disodium hydrogen phosphate, copper acetate, manganese acetate and zinc acetate in the reaction vessel, adjusted to the molar ratio of sodium, iron, copper, manganese, zinc and phosphorus as follows: iron: copper: manganese: zinc: phosphorus=4: 0.2:0.2:0.5:0.1:2, make it form Na 4 Fe 0.2 Cu 0.2 Mn 0.5 Zn 0.1 (PO 4 ) 2 The ratio of the compounds "adjusted to: adding a certain amount of sodium acetate, disodium hydrogen phosphate, copper acetate, manganese acetate and nickel acetate into a reaction kettle, and adjusting the molar ratio of sodium, iron, copper, manganese, nickel and phosphorus to be sodium: iron: copper: manganese: nickel: phosphorus=4: 0.2:0.2:0.5:0.1:2, make it form Na 4 Fe 0.2 Cu 0.2 Mn 0.5 Ni 0.1 (PO 4 ) 2 The proportional compounds, other steps and parameters remain the same.
FIG. 13 is an SEM image of the polyanionic material prepared in example 11, as follows: the Mn content is improved, the single crystal particles are better dispersed than those in the embodiment 1, the single crystal particles are larger, and the crystal faces are clear;
example 12
Example 12 differs from example 1 in that the "in reverse" in step (4)The reactor is supplemented with a certain amount of sodium acetate, disodium hydrogen phosphate, copper acetate, manganese acetate and zinc acetate, and the molar ratio of sodium, iron, copper, manganese, zinc and phosphorus is adjusted to be sodium: iron: copper: manganese: zinc: phosphorus=4: 0.2:0.2:0.5:0.1:2, make it form Na 4 Fe 0.2 Cu 0.2 Mn 0.5 Zn 0.1 (PO 4 ) 2 The ratio of the compounds "adjusted to: adding a certain amount of sodium acetate, disodium hydrogen phosphate, copper acetate, manganese acetate and ammonium paratungstate into a reaction kettle, and adjusting the molar ratio of sodium, iron, copper, manganese, tungsten and phosphorus to be sodium: iron: copper: manganese: tungsten: phosphorus=4: 0.2:0.2:0.5:0.1:2, make it form Na 4 Fe 0.2 Cu 0.2 Mn 0.5 W 0.1 (PO 4 ) 2 The proportional compounds, other steps and parameters remain the same.
Fig. 14 is an SEM electron microscope image of the polyanionic material prepared in example 12, and it can be seen that: doping W element, so that monocrystal particles are obviously reduced, and W has a larger influence on the development of materials in the sintering process;
example 13
Example 13 differs from example 1 in that "it was supplemented with a certain amount of sodium acetate, disodium hydrogen phosphate, copper acetate, manganese acetate and zinc acetate in the reaction vessel in step (4), adjusted to the molar ratio of sodium, iron, copper, manganese, zinc and phosphorus as follows: iron: copper: manganese: zinc: phosphorus=4: 0.2:0.2:0.5:0.1:2, make it form Na 4 Fe 0.2 Cu 0.2 Mn 0.5 Zn 0.1 (PO 4 ) 2 The ratio of the compounds "adjusted to: adding a certain amount of sodium acetate, disodium hydrogen phosphate, copper acetate, manganese acetate and zirconium oxychloride into a reaction kettle, and adjusting the molar ratio of sodium, iron, copper, manganese, zirconium and phosphorus to be sodium: iron: copper: manganese: zirconium: phosphorus=4: 0.2:0.2:0.5:0.1:2, make it form Na 4 Fe 0.2 Cu 0.2 Mn 0.5 Zr 0.1( PO 4 ) 2 The proportional compounds, other steps and parameters remain the same.
FIG. 15 is an SEM image of the polyanionic material prepared in example 13, as can be seen: zr element is doped, single crystal particles are larger, and the agglomeration of the particles is slightly improved compared with that of the particles in the embodiment 1;
example 14
Example 14 differs from example 1 in that in step (4), "sintering temperature 500 ℃, sintering time 12h, sintering atmosphere argon" was adjusted as follows: the sintering temperature is 800 ℃, the sintering time is 5 hours, the sintering atmosphere is argon, and other steps and parameters are kept consistent.
FIG. 16 is an SEM image of the polyanionic material prepared in example 14, as can be seen: the sintering temperature is increased, the grain development is further promoted, and monocrystalline grains are larger;
comparative example 1
Comparative example 1 differs from example 1 in that the temperature in the control vessel in step (2) was adjusted to-30℃to 50℃in the control vessel, and the other steps and parameters were kept the same.
FIG. 17 is an SEM image of the polyanionic material prepared in comparative example 1, as can be seen: the monocrystalline particles are uniformly dispersed, the agglomeration is less, and the influence of the temperature in the kettle on the final product is less;
comparative example 2
Comparative example 2 differs from example 1 in that the bottom liquid in step (3) was adjusted to be salt-free with glycerol, and other steps and parameters remained the same;
FIG. 18 is an SEM image of the polyanionic material prepared in comparative example 2, as can be seen: the monocrystalline particles are uniformly dispersed, the agglomeration is less, and the influence of changing the synthetic medium on the appearance of the final product is less;
comparative example 3 (technical source CN115058598A, fine tuning on the basis of this)
The comparative example provides a prior method for recycling sodium ion batteries, which comprises the following specific steps:
(1) Charging the recovered waste sodium iron phosphate ion battery under the current density of 0.5C, and continuously charging for 10 hours after full charge;
(2) Disassembling and sorting the waste sodium iron phosphate ion batteries in the full-electricity state to obtain a sodium-removed positive plate, a sodium-containing hard carbon negative plate and a diaphragm;
(3) The obtained sodium-containing hard carbon negative electrode sheet is put into oxalic acid solution with the mass fraction of 50%, and soaked for 1h at 25 ℃;
(4) Filtering after soaking to obtain sodium oxalate solution, hard carbon and current collector metal; adding a impurity removing agent into the sodium oxalate solution to remove impurities, filtering to obtain a sodium oxalate solution after impurity removal, and concentrating the sodium oxalate solution after impurity removal at 90 ℃ to obtain sodium oxalate solid;
(5) Crushing and screening the positive plate after sodium removal to obtain current collector metal and ferric phosphate powder, mixing sodium and sintering the ferric phosphate powder at 500 ℃ for 12 hours under argon atmosphere, and preparing the polyanion positive material.
FIG. 19 is an SEM image of the polyanionic material prepared in comparative example 3, as can be seen: the monocrystalline particles are not uniform, more agglomerates, smaller, and the crystal face is not clear.
Comparative example 4 (technical source CN114744165A, fine tuning on the basis of this)
The comparative example provides a prior method for recycling sodium ion batteries, which comprises the following specific steps:
(1) Crushing a sodium iron phosphate battery, collecting battery powder, adding a sulfuric acid solution with the mass concentration of 40% into the collected battery powder according to the liquid-solid ratio of 2mL to 1g, soaking for 8 hours, controlling the temperature at 40 ℃ during soaking, filtering after the reaction is finished, and carrying out solid-liquid separation to obtain leaching liquid and leaching slag;
(2) Adding iron powder into the leaching solution, and filtering to obtain copper-removed solution; then detecting the content of phosphorus, iron and aluminum elements in the copper-removed liquid, and adding soluble ferric salt, aluminum salt and phosphate to adjust the content ratio of the substances of iron, aluminum and phosphorus to be 0.95:0.05:1.00, obtaining a regulating solution;
(3) Adding hydrogen peroxide into the regulating solution, controlling the temperature to 75 ℃, and slowly adding sodium hydroxide solution to regulate the pH value to 2 to generate precipitate; filtering the precipitate, and performing solid-liquid separation to obtain a precipitate;
(4) Calcining the precipitate at 550 ℃ for 6 hours, and soaking the precipitate in a sodium hydroxide solution with the concentration of 0.1mol/L for 2 hours; the ratio of glucose, sodium carbonate and the amount of phosphorus element in the precipitate was then 1:0.5: and 1, adding the soaked precipitate, sodium carbonate and glucose into deionized water, fully mixing and stirring in a mixing stirring tank, spray-drying, sintering for 10 hours in a nitrogen atmosphere at 550 ℃, and crushing to obtain the polyanionic cathode material.
FIG. 20 is an SEM image of the polyanionic material prepared in comparative example 4, as can be seen: the monocrystalline particles are not uniform, more and more agglomerate, smaller, and the crystal face is not clear.
Comparative example 5 (technical source CN115818613A, fine tuning on the basis of this)
The comparative example provides a prior method for recycling sodium ion batteries, which comprises the following specific steps:
(1) Removing 10kg of waste sodium iron phosphate battery positive plates, shearing the positive plates, mixing the crushed positive plates with 100kg of sodium hydroxide solution with the molar concentration of 4mol/L, reacting to dissolve aluminum, ending the reaction until bubbles disappear (the reaction time is 3.5 h), and filtering to obtain first aluminum-containing filtrate and iron phosphate filter residues;
(2) Adding sodium chloride into the iron phosphate filter residue obtained in the step S1, uniformly mixing, and roasting at the vacuum degree of-0.065 MPa and the temperature of 500 ℃ for 5 hours to obtain a roasting material;
(3) Sodium carbonate and ammonium dihydrogen phosphate were added to the calcined seed to maintain a molar ratio of Na, fe, and P of 0.975:1:1.04, uniformly mixing to obtain a mixture. Then adding a carbon source and pure water into the mixture, stirring and slurrying. Wherein, the carbon source adopts the mass ratio of 1: glucose and sucrose of 0.3, the mass of the carbon source is 0.25 times of the mass of the roasting material;
(4) Grinding the slurry after stirring and pulping until the particle size of solid particles in the slurry is 285nm, and then spray-drying to obtain a spray-dried material with the particle size of 21.7 mu m; calcining the spray drying material to obtain a calcined material. Wherein the heating rate is 120 ℃/h, then the temperature is kept for 5h at 600 ℃, and the material is discharged after the temperature is reduced to be less than or equal to 100 ℃.
FIG. 21 is an SEM image of the polyanionic material prepared in comparative example 5, as can be seen: the monocrystalline particles are uneven, more and more agglomerated, smaller, the crystal face is not clear, and a small amount of fine powder is present.
Comparative example 6
The only difference from example 1 is that: and (3) directly adding ammonium dihydrogen phosphate for precipitation without adding sodium oxalate for precipitation.
FIG. 22 is an SEM image of the polyanionic material prepared in comparative example 5, as can be seen: the monocrystalline particles are not uniform, the agglomeration is serious and larger, the monocrystalline particles are larger, and the crystal face is unclear.
Test example 1
The positive electrode material and Na element recovery rate and electrical property data table are prepared in test examples and comparative examples;
table 1 results of performance tests of examples and comparative examples
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The results show that the average recovery rate of the recovered positive electrode material is 83.26%, the average recovery rate of Na element is 74.99%, the average recovery rate of the positive electrode material of the comparative example is 70.80%, the average recovery rate of Na element is 66.84%, the recovery rate of the positive electrode material is improved by 17.60%, the recovery rate of Na element is improved by 12.19%, and the improvement is obvious. The average discharge capacity is 98.93mAh/g, the average initial effect is 83.27%, the average discharge capacity of the comparative case is 90.12mAh/g, the average initial effect is 77.26%, the discharge capacity is improved by 9.78% by using the synthetic method of the case, the initial effect is improved by 7.78%, and the improvement is obvious; meanwhile, after W is doped, the initial effect is improved to 86.85 percent, which is higher than the average value by 4.30 percent, the Zr-doped discharge capacity is improved to 102.19mAh/g, which is higher than the average value by 3.30 percent, and the electrical property difference of the rest components is not obvious.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The method for recycling the positive electrode of the waste sodium ion battery is characterized by comprising the following steps of: pretreating a waste sodium ion battery to obtain a positive electrode material, and carrying out a step-by-step precipitation reaction on the positive electrode material, wherein the step-by-step precipitation reaction comprises a dissolution stage, a sodium oxalate precipitation stage and a phosphoric acid precipitation stage which are sequentially carried out;
wherein the dissolution phase comprises: mixing the positive electrode material with an organic solvent and oxalic acid, and dissolving under the condition that the pH value is 0.5-1.5 to obtain a mixed solution;
the sodium oxalate precipitation stage comprises: mixing the mixed solution with a sodium oxalate solution, and precipitating under the condition that the pH value is 3-5;
the phosphoric acid precipitation stage comprises: and mixing the mixed system obtained after the precipitation of the sodium oxalate precipitation stage with a phosphoric acid compound solution, and reacting under the condition that the pH value is 4.0-6.5.
2. The recovery method according to claim 1, wherein the process of the dissolution phase comprises: introducing inert gas into the reactor, adding the organic solvent as base solution, adding oxalic acid solution with the concentration of 0.1-0.5 mol/L into the base solution to enable the pH value to meet the requirement, dispersing the anode material into the solution, and stirring and reacting for 1-4 h.
3. The recovery method according to claim 2, wherein the mass ratio of the positive electrode material to the organic solvent is controlled to be 1 (0.1-2.0);
preferably, the organic solvent is selected from at least one of ethylene glycol, polyethylene glycol, ethylene glycol phenyl ether and glycerol; more preferably glycerol.
4. The recovery method according to claim 1, wherein in the sodium oxalate precipitation stage, the reaction temperature is controlled to be 50-80 ℃ and the reaction time is controlled to be 10-36 hours; preferably, the reaction temperature is controlled to be 50-60 ℃, the reaction time is controlled to be 10-12 h, and the pH value of the reaction is controlled to be 3.0-3.5.
5. The method according to claim 4, wherein the concentration of the sodium oxalate solution is 0.05mol/L to 0.25mol/L, and the addition rate is 20mL/min to 100mL/min.
6. The recovery method according to claim 1, wherein in the phosphoric acid precipitation stage, the reaction temperature is controlled to be 70-90 ℃ and the reaction time is controlled to be 48-96 hours; preferably, in the phosphoric acid precipitation stage, the reaction temperature is controlled to be 70-75 ℃, the reaction time is controlled to be 90-96 h, and the pH value of the reaction is controlled to be 6.0-6.5;
preferably, the phosphoric acid compound is at least one selected from phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, ammonium dihydrogen phosphate, sodium pyrophosphate and hydroxyethylidene diphosphate; preferably, the phosphoric acid compound is disodium hydrogen phosphate;
more preferably, the concentration of the phosphoric acid compound solution is 0.1mol/L-1mol/L, and the adding rate is 20mL/min-50mL/min.
7. The recycling method according to claim 1, further comprising: after the reaction in the phosphoric acid precipitation stage is finished, taking a precipitate, drying the precipitate, detecting the proportion of metal elements, then supplementing a sodium source, a phosphorus source, a copper source, a manganese source and an N metal source into a reaction kettle according to the detection result, regulating the molar ratio of sodium, iron, copper, manganese, N and phosphorus elements to be 4:x:y:z (1-x-y-z) to 2, then heating to 100-200 ℃ to react to remove a solvent, and then sintering the obtained solid material;
wherein, the value of x is 0.2-0.8, the value of y is 0.2-0.5, the value of z is 0-0.5, and x+y+z is less than or equal to 1;
preferably, the sodium source is selected from at least one of sodium pyrophosphate, sodium carbonate, sodium bicarbonate, sodium acetate, sodium oxalate, sodium ethoxide and sodium benzoate; more preferably, the sodium source is selected from at least one of sodium acetate, sodium ethoxide and sodium benzoate;
preferably, the phosphorus source is selected from at least one of phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, ammonium dihydrogen phosphate, sodium pyrophosphate, and hydroxyethylidene diphosphate; more preferably, the phosphorus source is disodium hydrogen phosphate;
preferably, the copper source is selected from at least one of copper sulfate, copper chloride and copper acetate; more preferably, the copper source is copper acetate;
preferably, the manganese source is selected from at least one of manganese sulfate, manganese chloride, manganese acetate and manganese carbonate; more preferably, the manganese source is manganese acetate;
preferably, the metal element in the N metal source is selected from at least one of Ni, zn, cr, al, mg, zr, la, sr, Y and W, and the N metal source is selected from at least one of sulfate, acetate, chloride, phosphate and nitrate.
8. The recovery method according to claim 7, wherein the sintering temperature is 500 ℃ to 800 ℃ and the sintering time is 6h to 12h;
preferably, the sintering is performed under an inert atmosphere.
9. The recycling method according to claim 1, wherein the pretreatment process comprises: discharging and disassembling the waste sodium ion battery, and crushing the positive plate to obtain a positive crushed material; washing and screening the anode crushed material to obtain an anode material;
preferably, the type of the waste sodium ion battery is selected from at least one of sodium iron phosphate, sodium iron pyrophosphate and layered oxide sodium ion battery;
preferably, when the waste sodium ion battery is discharged, the discharge current is controlled to be 0.08-0.12 ℃, and the discharge time is controlled to be 15-30 h.
10. The recovery method according to claim 9, wherein when the positive electrode crushed material is washed with water, a mass ratio of the positive electrode crushed material to the water amount is controlled to be 1: (5-20);
preferably, the temperature of the water washing is controlled to be between minus 30 ℃ and 0 ℃, the water washing time is 5min to 15min, and the dehydration time is 2min to 10min;
preferably, after the water washing is completed, the mixture is sieved through a 400-450 mesh sieve and then dried.
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