CN113998680B - Method for preparing lithium iron phosphate anode material by taking high-iron Bayer process red mud as iron source - Google Patents
Method for preparing lithium iron phosphate anode material by taking high-iron Bayer process red mud as iron source Download PDFInfo
- Publication number
- CN113998680B CN113998680B CN202111228361.8A CN202111228361A CN113998680B CN 113998680 B CN113998680 B CN 113998680B CN 202111228361 A CN202111228361 A CN 202111228361A CN 113998680 B CN113998680 B CN 113998680B
- Authority
- CN
- China
- Prior art keywords
- iron
- red mud
- lithium
- solid
- liquid
- 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.)
- Active
Links
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 198
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 113
- 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 62
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000004131 Bayer process Methods 0.000 title claims abstract description 24
- 239000010405 anode material Substances 0.000 title claims abstract description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000007788 liquid Substances 0.000 claims abstract description 42
- 239000002002 slurry Substances 0.000 claims abstract description 34
- 238000002386 leaching Methods 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000007787 solid Substances 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000012065 filter cake Substances 0.000 claims abstract description 23
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 20
- 238000000926 separation method Methods 0.000 claims abstract description 18
- 238000005245 sintering Methods 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 16
- 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 abstract description 15
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims abstract description 15
- 239000008103 glucose Substances 0.000 claims abstract description 15
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 15
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 15
- 235000019837 monoammonium phosphate Nutrition 0.000 claims abstract description 15
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 claims abstract description 14
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims abstract description 14
- 239000000047 product Substances 0.000 claims abstract description 14
- 229960004887 ferric hydroxide Drugs 0.000 claims abstract description 12
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims abstract description 12
- 238000001694 spray drying Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000012216 screening Methods 0.000 claims abstract description 10
- 229910052979 sodium sulfide Inorganic materials 0.000 claims abstract description 9
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 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 abstract description 8
- 239000011734 sodium Substances 0.000 claims description 17
- 229910052708 sodium Inorganic materials 0.000 claims description 17
- 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 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000000706 filtrate Substances 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000011324 bead Substances 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 claims description 2
- 239000004576 sand Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims 2
- 229910052786 argon Inorganic materials 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 abstract description 6
- 239000002244 precipitate Substances 0.000 description 17
- 229910052782 aluminium Inorganic materials 0.000 description 15
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 12
- -1 iron ions Chemical class 0.000 description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 238000001556 precipitation Methods 0.000 description 9
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 8
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 7
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 description 5
- 235000011152 sodium sulphate Nutrition 0.000 description 5
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 4
- 239000011790 ferrous sulphate Substances 0.000 description 4
- 235000003891 ferrous sulphate Nutrition 0.000 description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 4
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 4
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 4
- 235000019341 magnesium sulphate Nutrition 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005955 Ferric phosphate Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000012612 commercial material Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000004574 high-performance concrete Substances 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000010446 mirabilite Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
- C01F7/06—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom by treating aluminous minerals or waste-like raw materials with alkali hydroxide, e.g. leaching of bauxite according to the Bayer process
- C01F7/066—Treatment of the separated residue
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
- C01F7/06—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom by treating aluminous minerals or waste-like raw materials with alkali hydroxide, e.g. leaching of bauxite according to the Bayer process
- C01F7/0693—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom by treating aluminous minerals or waste-like raw materials with alkali hydroxide, e.g. leaching of bauxite according to the Bayer process from waste-like raw materials, e.g. fly ash or Bayer calcination dust
-
- 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
-
- 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
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- 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
- C01P2006/11—Powder tap density
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Analytical Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a method for preparing a lithium iron phosphate anode material by taking high-iron Bayer process red mud as an iron source, which comprises the following steps: carrying out acid leaching reaction on the red mud and sulfuric acid, and then carrying out solid-liquid separation to obtain a first solid and a first liquid; the addition amount of the sulfuric acid and the red mud is (3-6) according to the weight ratio: 1, adding sodium sulfide into the first liquid to react, and then carrying out solid-liquid separation to obtain liquid for removing heavy metals; then adjusting the pH value to 7.0-9.5, and then carrying out solid-liquid separation to obtain a second solid and a second liquid; regulating the pH of the second solid to 12+/-0.5, and then carrying out solid-liquid separation to obtain a mixed filter cake of ferrous hydroxide and ferric hydroxide; washing the mixed iron-containing filter cake, adding water, and uniformly mixing to obtain slurry with the solid content of 10-15%; adding ammonium dihydrogen phosphate, lithium carbonate and glucose into the slurry, and performing sanding, spray drying, sintering, crushing and screening to obtain a finished product of lithium iron phosphate. The method realizes the resource utilization of the red mud.
Description
Technical Field
The invention relates to the technical field of lithium battery material preparation, in particular to a method for preparing a lithium iron phosphate anode material by taking high-iron Bayer process red mud as an iron source.
Background
The red mud is a pollution waste residue discharged when alumina is extracted in the aluminum production industry, and generally, 1.0-2.0 tons of red mud is additionally produced per 1 ton of alumina produced on average. China is the 4 th world of large alumina production, and emits red mud as high as millions of tons each year. At present, the comprehensive utilization of red mud still belongs to a worldwide problem, and the existing comprehensive utilization of red mud mainly comprises the extraction of valuable metals from red mud, the production of cement by compounding materials, bricks for building, mine cemented filling cementing materials, roadbed consolidation materials, high-performance concrete admixture, chemical Bonding Ceramic (CBC) composite materials, heat-insulating refractory materials, environment-friendly materials and the like. However, these studies are still in the laboratory stage and have not been industrialized yet.
In the present stage, sales of new energy automobiles are rapidly increased, and due to the advantages of low cost, high safety and the like of lithium iron phosphate, the installed quantity of the lithium iron phosphate battery also presents a explosive growth situation. At present, the main stream preparation process of the lithium iron phosphate adopts the ferric phosphate as an iron source, and the preparation process is complex, so that the manufacturing cost of the lithium iron is relatively high. Because the red mud contains higher content of iron, if the red mud can be applied to an iron source for preparing the lithium iron phosphate, the iron source path of the lithium iron phosphate can be enriched, the high-value utilization of the red mud is realized, and the manufacturing cost of the lithium iron phosphate can be reduced.
In the prior art, no report is provided about how to develop a method for preparing a lithium iron phosphate anode material by taking high-iron Bayer process red mud as an iron source, and a new way is provided for the high-value utilization of the huge-storage-amount solid waste, so that the method becomes a technical problem to be solved urgently.
Disclosure of Invention
Aiming at the technical problems existing in the prior art, the invention provides a method for preparing the lithium iron phosphate anode material by taking high-iron Bayer process red mud as an iron source, realizes the recycling utilization of the high-iron Bayer process red mud, prepares the superfine nano lithium iron phosphate, and can be used for preparing the high-rate lithium iron phosphate anode material.
The invention adopts the following technical scheme:
a method for preparing a lithium iron phosphate anode material by taking high-iron bayer process red mud as an iron source, comprising the following steps:
carrying out acid leaching reaction on the red mud and sulfuric acid, and then carrying out solid-liquid separation to obtain a first solid and a first liquid; wherein the addition of the sulfuric acid and the red mud is (3-6) according to the weight ratio: 1, the mass fraction of the sulfuric acid is 60-80%;
adding a heavy metal capturing agent into the first liquid for reaction, and then carrying out solid-liquid separation to obtain liquid for removing heavy metals;
adding a pH regulator into the heavy metal-removed liquid to regulate the pH to 7.0-9.5, and then carrying out solid-liquid separation to obtain a second solid and a second liquid;
adding alkali liquor into the second solid to adjust the pH value to 12+/-0.5, and then carrying out solid-liquid separation to obtain a ferrous hydroxide and ferric hydroxide mixed filter cake and sodium metaaluminate filtrate;
washing the mixed iron-containing filter cake by adopting alkali liquor with the pH value of 12+/-0.5 to obtain a washed mixed iron-containing filter cake;
adding water into the washed and mixed iron-containing filter cake, and uniformly mixing to obtain slurry with the solid content of 10-15%;
adding ammonium dihydrogen phosphate, lithium carbonate and glucose into the slurry, adding pure water, and fully stirring and uniformly mixing to obtain lithium iron phosphate precursor slurry; wherein, the addition amount of the ammonium dihydrogen phosphate and the lithium carbonate is according to the ratio Li of the amount of substances of lithium, iron and phosphorus: fe: p= (1.02-1.05): 1:1, adding; the addition amount of the glucose is 1.4-1.7 wt% of the carbon content in the final iron lithium product; the adding amount of the pure water is controlled to be 32-35% of solid content; the solid content refers to the ratio of the mass of the solid phase in the slurry to the total mass.
And (3) performing sanding, spray drying, sintering, crushing and screening on the lithium iron phosphate precursor slurry to remove iron so as to obtain a finished product of lithium iron phosphate.
In the technical scheme, the addition amount of the sulfuric acid and the red mud is (3-6) according to the weight ratio: 1, the mass fraction of the sulfuric acid is 60-80%;
preferably, the addition amount of the sulfuric acid and the red mud is (4-5) according to the weight ratio: 1, the mass fraction of the sulfuric acid is 65-75%.
The pH value of the solution is regulated to 7.0-9.5 so as to enable iron ions (ferrous iron and ferric iron) and aluminum ions to react to generate ferric hydroxide, ferrous hydroxide and aluminum hydroxide precipitate, if the pH value is less than 7.0, the precipitation reaction of the ferrous ions is unfavorable, and if the pH value is more than 9.5, the precipitation reaction of magnesium ions can also occur, so that magnesium ions as impurities are introduced, and meanwhile, the waste of a pH regulator can be caused.
Adjusting the pH to 12+/-0.5, fully stirring to dissolve the aluminum hydroxide to generate sodium metaaluminate solution, and if the pH is less than 11.5, the aluminum hydroxide is incompletely converted, and if the pH is more than 12.5, waste of alkali liquor is caused;
in the technical scheme, heavy metals (such as copper, lead, zinc, nickel, cadmium and the like) are removed, and a heavy metal capturing agent is added; the heavy metal trapping agent comprises at least one of sodium sulfide, ammonium sulfide and potassium sulfide. The adding amount (mass) of the heavy metal capturing agent is added according to the total volume (0.02-0.04) g/L of the solution, and stirring reaction is continued for 15-30min after the adding;
as an alternative technical scheme, the temperature of the acid leaching reaction is 20-30 ℃, and the time of the acid leaching reaction is 50-80min.
In the technical scheme, the temperature of the acid leaching reaction is at normal temperature, the acid leaching reaction time is 50-80min, the leaching rate of iron is improved to 90-93%, if the acid leaching time is too short, the leaching rate of iron is not improved, and if the acid leaching time is too long, the production efficiency is reduced;
preferably, the pH regulator comprises one of sodium hydroxide, sodium carbonate, sodium bicarbonate, ammonia water, ammonium carbonate and ammonium bicarbonate, and the mass fraction of the pH regulator is 25-35%.
Preferably, the second liquid contains sodium sulfate/ammonium sulfate and can be used for preparing byproduct mirabilite or ammonium sulfate fertilizer.
In the above-described aspect, in the washing, carbon dioxide is not precipitated until carbon dioxide is introduced into the washing water.
In the above technical scheme, the addition amount of the ammonium dihydrogen phosphate and the lithium carbonate is according to the ratio Li of the amounts of substances of lithium, iron and phosphorus: fe: p= (1.02-1.05): 1: the reason for 1 is: the lithium is slightly excessive, which is favorable for refining grains, relieving sintering fusion among the grains and improving the rate discharge performance of the lithium iron phosphate material.
The reason why the pure water is added is that the solid content is controlled to be 32-35 percent: if the solid content is too high, the viscosity of the slurry is too high, and the atomizer is easy to be blocked in the spray drying process; if the solid content is too low, the spraying productivity is lower and the energy consumption is higher.
Preferably, in the sanding, a sand mill is used for grinding, and zirconia beads with the diameter of 0.3mm are adopted as a grinding medium, so that the slurry particle size D50 is 350-500nm.
Preferably, in the spray drying, a centrifugal spray dryer is adopted, the linear speed of an atomizing wheel is controlled to be 7500-8500m/s, hot air is used as a heat source in the drying process, the temperature of the hot air is 240-250 ℃, the discharging temperature is 85-90 ℃, and the particle size D50 of the dried material is controlled: 4-8 μm, moisture <1.0%.
Preferably, in the sintering, an atmosphere roller furnace is adopted for sintering, inert gas adopts nitrogen, the temperature is kept for 8-10 hours at 750-780 ℃, the oxygen content in the furnace is controlled to be less than 1ppm, and the pressure in the furnace is controlled to be 10-15Pa.
The reactions that occur during sintering are as follows:
2Fe(OH) 2 +Li 2 CO 3 +2NH 4 H 2 PO 4 ＝2LiFePO 4 +2NH 3 ↑+CO 2 ↑+5H 2 O↑
2Fe(OH) 3 +Li 2 CO 3 +2NH 4 H 2 PO 4 +C＝2LiFePO 4 +2NH 3 ↑+CO 2 ↑+CO↑+6H 2 O↑
preferably, in the crushing and screening, the sintered material obtained by sintering is crushed by air flow until the particle diameter D50 is 0.6-1.5 mu m, then is screened by an ultrasonic vibration screen, the mesh number of the screen is 60-80 meshes, and is subjected to iron removal by a 2-level electromagnetic iron remover until the magnetic substance is less than 0.3ppm, and then is stopped.
Wherein, the components of the red mud comprise the following components in percentage by mass: fe (Fe) 2 O 3 ：25-60％，Al 2 O 3 ：10-30％，Si 2 O 2 ：5-25％，CaO：2-10％，Na 2 O：5-10％，TiO 2 ：2-6％，MgO：0.5-2％，FeO：2-5％。
Compared with the prior art, the invention has the beneficial effects that:
1. the method for preparing the lithium iron phosphate anode material by taking the high-iron Bayer process red mud as an iron source improves the leaching rate of iron by controlling the condition of acid leaching reaction (the adding amount of sulfuric acid and the red mud is (3-6): 1 according to the weight ratio, and the mass fraction of the sulfuric acid is 60-80 percent); removing heavy metal ions by adding a heavy metal capturing agent; the pH value of the solution is regulated to 7.0-9.5 so as to lead iron ions (ferrous iron and ferric iron) and aluminum ions to generate mixed precipitates of ferric hydroxide, ferrous hydroxide and aluminum hydroxide, the pH value of the mixed precipitates is regulated to 12+/-0.5, the mixed precipitates are fully stirred so as to dissolve the aluminum hydroxide precipitates to generate sodium metaaluminate solution, iron-containing precipitates are obtained, ammonium dihydrogen phosphate, lithium carbonate, glucose and pure water are added after washing, and the solution is uniformly mixed for reaction, so that lithium iron phosphate precursor slurry is obtained, and the finished product lithium iron phosphate is obtained through sanding, spray drying, sintering, crushing and screening; thereby realizing the recycling utilization of the red mud of the high-iron Bayer process.
2. The utilization rate of iron in the method reaches more than 90%, and iron resources in the red mud can be effectively utilized; meanwhile, as the iron (ii) hydroxide colloid particles are smaller, the superfine nano lithium iron phosphate is easy to prepare, and the battery-level nano anhydrous lithium iron phosphate obtained by the method has uniform particle size distribution and good dispersibility; can be used for preparing a multiplying power type lithium iron phosphate battery.
Drawings
FIG. 1 is a flow chart of a method for preparing a lithium iron phosphate anode material by taking high-iron Bayer process red mud as an iron source, which is provided by the embodiment of the invention;
FIG. 2 is an electron microscopic view of the lithium iron phosphate positive electrode material obtained in example 1 of the present invention at a 1 μm scale;
FIG. 3 is a graph showing the particle size distribution of a lithium iron phosphate positive electrode material obtained in example 1 of the present invention;
FIG. 4 is an electron microscopic view of the lithium iron phosphate positive electrode material obtained in example 1 of the present invention at a scale of 100 nm.
Detailed Description
The advantages and various effects of the embodiments of the present invention will be more clearly apparent from the following detailed description and examples. Those skilled in the art will appreciate that these specific implementations and examples are provided to illustrate, but not limit, examples of the present invention.
The technical scheme provided by the embodiment of the invention aims to solve the technical problems, and the overall thought is as follows:
firstly, carrying out acid leaching on red mud, and after solid-liquid separation, wherein the first liquid mainly contains aluminum sulfate, ferric sulfate, ferrous sulfate, magnesium sulfate and sodium sulfate, and the first solid mainly contains calcium sulfate, silicon dioxide and titanium dioxide; the leaching rate of iron is 90-93%;
then heavy metal ions are removed by adding a heavy metal capturing agent, and liquid for removing heavy metals is obtained after solid-liquid separation;
and then adding a pH regulator into the liquid for removing heavy metals to regulate the pH to 7.0-9.5 for extracting iron and aluminum. So that iron ions (ferrous iron and ferric iron) and aluminum ions are subjected to precipitation reaction to generate ferrous hydroxide, ferric hydroxide and aluminum hydroxide precipitates;
adding alkali liquor into the second solid to adjust the pH value to 12+/-0.5, and then carrying out solid-liquid separation to obtain a ferrous hydroxide and ferric hydroxide mixed iron-containing filter cake and sodium metaaluminate filtrate; sodium metaaluminate solution can be used for extracting aluminum;
washing the mixed iron-containing filter cake by adopting alkali liquor with the pH value of 12+/-0.5 to obtain a washed mixed iron-containing filter cake;
adding water into the washed and mixed iron-containing filter cake, and uniformly mixing to obtain slurry with the solid content of 10-15%;
adding ammonium dihydrogen phosphate, lithium carbonate, glucose and pure water into the slurry, and uniformly mixing and reacting to obtain lithium iron phosphate precursor slurry; wherein, the addition amount of the ammonium dihydrogen phosphate and the lithium carbonate is according to the ratio Li of the amount of substances of lithium, iron and phosphorus: fe: p= (1.02-1.05): 1:1, adding; the adding amount of glucose is 1.4-1.7 wt% according to the carbon content in the final iron lithium product; the adding amount of the pure water is controlled to be 32-35% of solid content;
and (3) sanding, spray drying, sintering, crushing and screening the lithium iron phosphate precursor slurry to obtain the finished lithium iron phosphate.
The method of forming a silicon carbide ramming mass of the present application will be described in detail below with reference to examples, comparative examples and experimental data.
The following examples are given for illustration of the invention only and are not intended to limit the scope of the invention. All other embodiments obtained by those skilled in the art without creative efforts are within the protection scope of the present invention based on the specific embodiments of the present invention.
In the examples of the present invention, all raw material components are commercially available products well known to those skilled in the art unless specified otherwise; in the embodiments of the present invention, unless specifically indicated, all technical means used are conventional means well known to those skilled in the art. In the examples of the present invention, the raw materials used were all conventional commercial products.
In the embodiment of the invention, the leaching rate of iron in the step S1 is multiplied by the iron yield in the later step to obtain the utilization rate (i.e. recovery rate) of the final iron.
Example 1
The embodiment of the invention provides a method for preparing a lithium iron phosphate anode material by taking high-iron Bayer process red mud as an iron source, which is shown in a figure 1 and comprises the following steps:
and S1, acid leaching. The red mud from the high-iron Bayer process and sulfuric acid undergo acid leaching reaction, the adding amount of sulfuric acid and red mud is 5:1 by weight, the sulfuric acid concentration is 70%, the reaction time is 60min, and the reaction temperature is normal temperature; filtering to obtain filtrate and residue; the filtrate mainly contains aluminum sulfate, ferric sulfate, ferrous sulfate, magnesium sulfate and sodium sulfate, and the filter residues mainly contain calcium sulfate, silicon dioxide and titanium dioxide; the leaching rate of the iron is 90-93%.
Step S2, heavy metal removal: adding sodium sulfide into the first liquid for reaction, and then carrying out solid-liquid separation to obtain liquid for removing heavy metals; wherein, the addition amount of sodium sulfide is added according to 0.03g/L of the total volume of the solution;
and S3, extracting iron and aluminum. The pH value of the solution is regulated to 8.5 so as to lead iron ions (ferrous iron and ferric iron) and aluminum ions to carry out precipitation reaction, thus generating mixed precipitation of ferrous hydroxide, ferric hydroxide and aluminum hydroxide;
and S4, extracting iron. Adjusting the pH value of the mixed precipitate to 12, and fully stirring to dissolve the aluminum hydroxide precipitate to generate a sodium metaaluminate solution to obtain a mixed iron-containing precipitate; sodium metaaluminate solution can be used for extracting aluminum;
and S5, washing. And (3) washing the mixed iron-containing filter cake by adopting a sodium hydroxide solution with the pH value of 12 to remove residual sodium metaaluminate in the filter cake, wherein white precipitation is not generated when carbon dioxide is introduced into washing water.
And S6, preparing lithium iron phosphate.
And (3) adding pure water into the ferrous hydroxide filter cake washed in the step (S5) to prepare slurry, wherein the solid content of the slurry is 12%, and sampling and testing the total iron content.
Adding ammonium dihydrogen phosphate, lithium carbonate and glucose into the slurry, adding pure water, and fully stirring and uniformly mixing to obtain lithium iron phosphate precursor slurry; wherein, the addition amount of the ammonium dihydrogen phosphate and the lithium carbonate is according to the ratio Li of the amount of substances of lithium, iron and phosphorus: fe: p=1.03: 1:1, wherein the addition amount of glucose is 1.5 weight percent according to the carbon content in the final lithium iron product; the adding amount of the pure water is controlled to be 33% of solid content;
and (3) sanding, spray drying, sintering, crushing and screening the lithium iron phosphate precursor slurry to obtain the finished lithium iron phosphate.
Example 2
The embodiment of the invention provides a method for preparing a lithium iron phosphate anode material by taking high-iron Bayer process red mud as an iron source, which comprises the following steps:
and S1, acid leaching. The red mud of the high-iron Bayer process and sulfuric acid undergo acid leaching reaction, the adding amount of the sulfuric acid and the red mud is 3:1 by weight, the sulfuric acid concentration is 60%, the reaction time is 50min, and the reaction temperature is normal temperature; filtering to obtain filtrate and residue; the filtrate mainly contains aluminum sulfate, ferric sulfate, ferrous sulfate, magnesium sulfate and sodium sulfate, and the filter residues mainly contain calcium sulfate, silicon dioxide and titanium dioxide; the leaching rate of the iron is 90-93%.
Step S2, heavy metal removal: adding sodium sulfide into the first liquid for reaction, and then carrying out solid-liquid separation to obtain liquid for removing heavy metals; wherein, the addition amount of sodium sulfide is added according to 0.02g/L of the total volume of the solution;
and S3, extracting iron and aluminum. The pH value of the solution is regulated to 7 so as to lead iron ions (ferrous iron and ferric iron) and aluminum ions to carry out precipitation reaction, and ferrous hydroxide, ferric hydroxide and aluminum hydroxide are generated to be mixed and precipitated;
and S4, extracting iron. Adjusting the pH value of the mixed precipitate to 11.5, and fully stirring to dissolve the aluminum hydroxide precipitate to generate a sodium metaaluminate solution to obtain a ferrous hydroxide and ferric hydroxide mixed ferric-containing precipitate; sodium metaaluminate solution can be used for extracting aluminum;
and S5, washing. And washing the mixed iron-containing filter cake by adopting a sodium hydroxide solution with the pH value of 11.5 to remove residual sodium metaaluminate in the filter cake, wherein white precipitation is not generated when carbon dioxide is introduced into washing water.
And S6, preparing lithium iron phosphate.
And (3) adding pure water into the mixed iron-containing filter cake washed in the step (S5) to prepare slurry, wherein the solid content of the slurry is 12%, and sampling and testing the iron content.
Adding ammonium dihydrogen phosphate, lithium carbonate and glucose into the slurry, adding pure water, and fully stirring and uniformly mixing to obtain lithium iron phosphate precursor slurry; wherein, the addition amount of the ammonium dihydrogen phosphate and the lithium carbonate is according to the ratio Li of the amount of substances of lithium, iron and phosphorus: fe: p=1.02: 1:1, wherein the addition amount of glucose is 1.4 weight percent according to the carbon content in the final lithium iron product; the adding amount of the pure water is controlled to be 32% of solid content;
and (3) sanding, spray drying, sintering, crushing and screening the lithium iron phosphate precursor slurry to obtain the finished lithium iron phosphate.
Example 3
The embodiment of the invention provides a method for preparing a lithium iron phosphate anode material by taking high-iron Bayer process red mud as an iron source, which comprises the following steps:
and S1, acid leaching. The red mud of the high-iron Bayer process and sulfuric acid undergo acid leaching reaction, the adding amount of the sulfuric acid and the red mud is 6:1 by weight, the sulfuric acid concentration is 80%, the reaction time is 80min, and the reaction temperature is normal temperature; filtering to obtain filtrate and residue; the filtrate mainly contains aluminum sulfate, ferric sulfate, ferrous sulfate, magnesium sulfate and sodium sulfate, and the filter residues mainly contain calcium sulfate, silicon dioxide and titanium dioxide; the leaching rate of the iron is 90-93%.
Step S2, heavy metal removal: adding sodium sulfide into the first liquid for reaction, and then carrying out solid-liquid separation to obtain liquid for removing heavy metals; wherein, the addition amount of sodium sulfide is added according to 0.04g/L of the total volume of the solution;
and S3, extracting iron and aluminum. Precipitating iron ions (ferrous and ferric iron) and aluminum ions by adjusting the pH of the solution to 9.5 to generate ferrous hydroxide, ferric hydroxide and aluminum hydroxide precipitates;
and S4, extracting iron. Adjusting the pH value of the mixed precipitate to 12.5, and fully stirring to dissolve the aluminum hydroxide precipitate to generate a sodium metaaluminate solution to obtain a ferrous hydroxide and ferric hydroxide mixed ferric-containing precipitate; sodium metaaluminate solution can be used for extracting aluminum;
and S5, washing. And (3) washing the mixed iron-containing filter cake by adopting a sodium hydroxide solution with the pH value of 12.5 to remove residual sodium metaaluminate in the filter cake, wherein white precipitation is not generated when carbon dioxide is introduced into washing water.
And S6, preparing lithium iron phosphate.
And (3) adding pure water into the mixed iron-containing filter cake washed in the step (S5) to prepare slurry, wherein the solid content of the slurry is 12%, and sampling and testing the iron content.
Adding ammonium dihydrogen phosphate, lithium carbonate and glucose into the slurry, adding pure water, and fully stirring and uniformly mixing to obtain lithium iron phosphate precursor slurry; wherein, the addition amount of the ammonium dihydrogen phosphate and the lithium carbonate is according to the ratio Li of the amount of substances of lithium, iron and phosphorus: fe: p=1.05: 1:1, adding; the glucose addition amount is 1.7wt% according to the carbon content in the final iron lithium product; the adding amount of the pure water is controlled to be 35% of solid content;
and (3) sanding, spray drying, sintering, crushing and screening the lithium iron phosphate precursor slurry to obtain the finished lithium iron phosphate.
Comparative example 1
In the comparative example, in the acid leaching reaction, the addition amount of the sulfuric acid and the red mud is 2:1, a step of; the other steps were the same as in example 1.
Experimental example 1
1. The iron utilization (i.e., recovery) statistics for each example and each comparative example are shown in table 1.
TABLE 1
| Group of | Iron utilization% |
| Example 1 | 92.03 |
| Example 2 | 91.95 |
| Example 3 | 92.27 |
| Comparative example 1 | 82.56 |
From the data in table 1, it can be seen that:
in comparative example 1, the amount of sulfuric acid used in the leaching process is low, so that the leaching rate of iron in the red mud is low, and the utilization rate of iron is low;
in examples 1 to 3, the iron utilization rate was 90% or more.
2. The lithium iron phosphate and the commercially available lithium iron phosphate materials of example 1 were tested, and the test results are shown in table 2;
TABLE 2
As can be seen from the comparison data in Table 2, compared with the commercial lithium iron phosphate product, each index of the lithium iron product obtained in the embodiment of the invention reaches the standard of battery-grade lithium iron phosphate, and the contents of part of impurity elements such as Ca, mg, na, al and the like are lower than those of commercial materials.
It should be noted that the above examples are only for further illustrating and describing the technical solution of the present invention, and are not intended to limit the technical solution of the present invention, and the method of the present invention is only a preferred embodiment and is not intended to limit the scope of the present invention. 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 (7)
1. The method for preparing the lithium iron phosphate anode material by taking the high-iron Bayer process red mud as an iron source is characterized by comprising the following steps of:
carrying out acid leaching reaction on the red mud and sulfuric acid, and then carrying out solid-liquid separation to obtain a first solid and a first liquid; wherein the addition of the sulfuric acid and the red mud is (3-6) according to the weight ratio: 1, the mass fraction of the sulfuric acid is 60-80%;
adding a heavy metal capturing agent into the first liquid for reaction, and then carrying out solid-liquid separation to obtain liquid for removing heavy metals;
adding a pH regulator into the heavy metal-removed liquid to regulate the pH to 7.0-9.5, and then carrying out solid-liquid separation to obtain a second solid and a second liquid;
adding alkali liquor into the second solid to adjust the pH value to 12+/-0.5, and then carrying out solid-liquid separation to obtain a mixed filter cake of ferrous hydroxide and ferric hydroxide and sodium metaaluminate filtrate;
washing the mixed iron-containing filter cake by adopting alkali liquor with the pH value of 12+/-0.5 to obtain a washed mixed iron-containing filter cake;
adding water into the washed and mixed iron-containing filter cake, and uniformly mixing to obtain slurry with the solid content of 10-15%;
adding ammonium dihydrogen phosphate, lithium carbonate and glucose into the slurry, adding pure water, and fully stirring and uniformly mixing to obtain lithium iron phosphate precursor slurry; wherein, the addition amount of the ammonium dihydrogen phosphate and the lithium carbonate is according to the ratio Li of the amount of substances of lithium, iron and phosphorus: fe: p= (1.02-1.05): 1:1, adding glucose, wherein the adding amount of the glucose is 1.4-1.7 wt% according to the carbon content in the final iron lithium product; the adding amount of the pure water is controlled to be 32-35% of solid content;
grinding, spray drying, sintering, crushing and screening the lithium iron phosphate precursor slurry to remove iron, so as to obtain a finished product lithium iron phosphate;
the temperature of the acid leaching reaction is 20-30 ℃, and the time of the acid leaching reaction is 50-80min;
the red mud comprises the following components in percentage by mass: fe (Fe) 2 O 3 ：25-60％，Al 2 O 3 ：10-30％，Si 2 O 2 ：5-25％，CaO：2-10％，Na 2 O：5-10％，TiO 2 ：2-6％，MgO：0.5-2％，FeO：2-5％；
In the sintering, an atmosphere roller way furnace is adopted for sintering, inert gas adopts nitrogen/argon, the temperature is kept for 8-10h at 750-800 ℃, the oxygen content in the furnace is controlled to be less than 3ppm, and the pressure in the furnace is controlled to be 10-15Pa.
2. The method for preparing a lithium iron phosphate anode material by taking high-iron bayer process red mud as an iron source, according to claim 1, wherein the heavy metal capturing agent comprises at least one of sodium sulfide, ammonium sulfide and potassium sulfide; the heavy metal capturing agent is added according to the total volume of the solution (0.02-0.04) g/L.
3. The method for preparing the lithium iron phosphate anode material by taking the high-iron bayer process red mud as an iron source, according to claim 1, wherein the pH regulator comprises one of sodium hydroxide, sodium carbonate, sodium bicarbonate, ammonia water, ammonium carbonate and ammonium bicarbonate, and the mass fraction of the pH regulator is 25-35%.
4. The method for preparing the lithium iron phosphate anode material by taking the high-iron Bayer process red mud as an iron source, which is characterized in that in the sanding, a sand mill is adopted for grinding, and a grinding medium adopts zirconia beads with the diameter of 0.3mm, so that the grain size D50 of slurry is 350-500nm.
5. The method for preparing the lithium iron phosphate anode material by taking the high-iron Bayer process red mud as an iron source according to claim 1, wherein in the spray drying, a centrifugal spray dryer is adopted, the linear speed of an atomizing wheel is controlled to be 7500-8500m/s, hot air is adopted as a heat source in the drying process, the temperature of the hot air is 240-250 ℃, the discharging temperature is 85-90 ℃, and the particle size D50 of the dried material is controlled: 4-8 μm, moisture <1.0%.
6. The method for preparing the lithium iron phosphate anode material by taking the high-iron Bayer process red mud as an iron source according to claim 1, wherein in the steps of crushing and screening for iron removal, the sintered material obtained by sintering is crushed by air flow until the particle size D50 is 0.6-1.5 mu m, then screened by an ultrasonic vibration sieve, the mesh number of the sieve is 60-80 meshes, and a 2-level electromagnetic iron remover is adopted for iron removal until the magnetic substance is less than 0.3ppm, and then the iron removal is stopped.
7. The method for preparing the lithium iron phosphate anode material by taking the high-iron Bayer process red mud as an iron source, which is characterized in that the addition amount of the sulfuric acid and the red mud is (4-5) according to the weight ratio: 1, the mass fraction of the sulfuric acid is 65-75%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111228361.8A CN113998680B (en) | 2021-10-21 | 2021-10-21 | Method for preparing lithium iron phosphate anode material by taking high-iron Bayer process red mud as iron source |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111228361.8A CN113998680B (en) | 2021-10-21 | 2021-10-21 | Method for preparing lithium iron phosphate anode material by taking high-iron Bayer process red mud as iron source |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113998680A CN113998680A (en) | 2022-02-01 |
| CN113998680B true CN113998680B (en) | 2023-08-01 |
Family
ID=79923480
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111228361.8A Active CN113998680B (en) | 2021-10-21 | 2021-10-21 | Method for preparing lithium iron phosphate anode material by taking high-iron Bayer process red mud as iron source |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113998680B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115432684A (en) * | 2022-09-09 | 2022-12-06 | 株洲冶炼集团股份有限公司 | Method for preparing lithium iron phosphate by sintering in atmosphere rotary kiln |
| CN116177515A (en) * | 2022-12-27 | 2023-05-30 | 昆明精粹工程技术有限责任公司 | Method for preparing battery-grade lithium iron phosphate by using pyrite cinder |
| CN116395695A (en) * | 2023-05-10 | 2023-07-07 | 昆明理工大学 | Method for preparing phosphate from red mud |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2098483A1 (en) * | 2008-03-05 | 2009-09-09 | High Power Lithium S.A. | Synthesis of lithium metal phosphate/carbon nanocomposites with phytic acid |
| CN107447113A (en) * | 2017-08-11 | 2017-12-08 | 中国科学院过程工程研究所 | A kind of method that iron and aluminium are separated from red mud and/or iron content solid waste |
| CN109987638A (en) * | 2019-03-10 | 2019-07-09 | 胡春宇 | Red mud produces ferric phosphate lithium cell pigment composite plate |
-
2021
- 2021-10-21 CN CN202111228361.8A patent/CN113998680B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113998680A (en) | 2022-02-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113998680B (en) | Method for preparing lithium iron phosphate anode material by taking high-iron Bayer process red mud as iron source | |
| CN102251119B (en) | Method for recycling vanadium extraction tailings | |
| CN113860278B (en) | Method for preparing battery-grade ferric phosphate by taking high-iron Bayer process red mud as iron source | |
| CN103276218B (en) | Method for recycling vanadium from vanadium-containing electrolysis aluminum slag ash | |
| CN112662896B (en) | Method for preparing titanium-rich material from titanium ore | |
| CN110028111B (en) | Preparation method of ternary positive electrode material precursor and lithium carbonate | |
| CN110438338B (en) | Device and method for recovering nickel and cobalt and co-producing magnesium oxide from nickel-cobalt-magnesium waste liquid | |
| CN106747497A (en) | The method for preparing corundum-mullite composite diphase material | |
| CN110433956B (en) | Method for recovering zinc, iron and/or carbon from blast furnace gas ash | |
| CN111893308A (en) | Method for comprehensively utilizing red mud without tailings | |
| CN101148268A (en) | Method for separating and extracting calcium tungstate and tin slag by utilizing tungsten-containing tin furnace residue or tungsten-tin middlings | |
| CN113979655B (en) | Modified steel slag based on steel dust mud and red mud, and preparation method and application thereof | |
| CN114752774A (en) | Method for separating iron and aluminum from red mud | |
| CN112095017B (en) | Method for recycling fly ash based on reduction roasting-acid leaching | |
| CN107557590A (en) | Zinc dross recoverying and utilizing method | |
| CN114150156B (en) | Low-grade zinc-containing dust zinc extraction and nano zinc oxide preparation process | |
| CN110950348B (en) | Process for producing ultra-pure nano white carbon black from high-silicon iron ore | |
| CN110980753B (en) | Process for producing high-quality sodium silicate by adopting high-silicon iron ore | |
| CN113430362B (en) | Separation method of lithium concentrate transformation roasting material before acidification or alkalization | |
| CN103553109B (en) | Comprehensive utilization method of magnesium-smelting slag from Pidgeon process | |
| CN102126735A (en) | Method for extracting tschermigite from coal gangue or stone coal | |
| CN113604663B (en) | Method for separating iron-aluminum symbiotic resources based on low-calcium reduction roasting | |
| CN115679127B (en) | Method for roasting and decomposing tungsten concentrate by using acid gas | |
| CN110436452B (en) | Method for enriching vanadium pentoxide and graphite from graphite type vanadium ore | |
| CN106367607A (en) | Method for stepwise recovering valuable metal in converter slag |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A method for preparing lithium iron phosphate cathode material using high-speed Bayer process red mud as iron source Granted publication date: 20230801 Pledgee: China Postal Savings Bank Co.,Ltd. Wuxue Branch Pledgor: Hubei Yunxiang Juneng New Energy Technology Co.,Ltd. Registration number: Y2024980004653 |