CN116062726A - Lithium iron phosphate and continuous production method thereof - Google Patents
Lithium iron phosphate and continuous production method thereof Download PDFInfo
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- CN116062726A CN116062726A CN202310222914.1A CN202310222914A CN116062726A CN 116062726 A CN116062726 A CN 116062726A CN 202310222914 A CN202310222914 A CN 202310222914A CN 116062726 A CN116062726 A CN 116062726A
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- 238000000034 method Methods 0.000 title claims abstract description 33
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims description 11
- 238000010924 continuous production Methods 0.000 title abstract description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 71
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000008367 deionised water Substances 0.000 claims abstract description 46
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 46
- 239000011572 manganese Substances 0.000 claims abstract description 42
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 32
- 229910052742 iron Inorganic materials 0.000 claims abstract description 30
- 230000032683 aging Effects 0.000 claims abstract description 27
- 229910000616 Ferromanganese Inorganic materials 0.000 claims abstract description 26
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 24
- 239000010452 phosphate Substances 0.000 claims abstract description 24
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 24
- 239000007787 solid Substances 0.000 claims abstract description 18
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 16
- 239000011574 phosphorus Substances 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 238000001354 calcination Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 15
- 239000002002 slurry Substances 0.000 claims abstract description 14
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 8
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 8
- 230000001590 oxidative effect Effects 0.000 claims abstract description 6
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- 239000012066 reaction slurry Substances 0.000 claims abstract description 5
- 239000007790 solid phase Substances 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 44
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 40
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 26
- 238000001914 filtration Methods 0.000 claims description 26
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 22
- 235000010323 ascorbic acid Nutrition 0.000 claims description 20
- 239000011668 ascorbic acid Substances 0.000 claims description 20
- 229960005070 ascorbic acid Drugs 0.000 claims description 20
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 13
- 238000000926 separation method Methods 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 239000011790 ferrous sulphate Substances 0.000 claims description 10
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 10
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 10
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 229940099596 manganese sulfate Drugs 0.000 claims description 9
- 239000011702 manganese sulphate Substances 0.000 claims description 9
- 235000007079 manganese sulphate Nutrition 0.000 claims description 9
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 9
- 235000006708 antioxidants Nutrition 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- 229940062993 ferrous oxalate Drugs 0.000 claims description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 3
- 229960002089 ferrous chloride Drugs 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 3
- 229940071125 manganese acetate 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
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 239000001488 sodium phosphate Substances 0.000 claims description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 3
- 235000011008 sodium phosphates Nutrition 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- 235000010288 sodium nitrite Nutrition 0.000 claims description 2
- 235000010265 sodium sulphite Nutrition 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims 1
- AWKHTBXFNVGFRX-UHFFFAOYSA-K iron(2+);manganese(2+);phosphate Chemical compound [Mn+2].[Fe+2].[O-]P([O-])([O-])=O AWKHTBXFNVGFRX-UHFFFAOYSA-K 0.000 abstract description 16
- 238000010899 nucleation Methods 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 abstract description 3
- 229940116007 ferrous phosphate Drugs 0.000 abstract description 3
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 abstract description 3
- 229910000155 iron(II) phosphate Inorganic materials 0.000 abstract description 3
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
- 230000006911 nucleation Effects 0.000 abstract description 2
- 238000005191 phase separation Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 132
- 238000003786 synthesis reaction Methods 0.000 description 63
- 230000015572 biosynthetic process Effects 0.000 description 53
- 239000000463 material Substances 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 11
- 230000018044 dehydration Effects 0.000 description 10
- 238000006297 dehydration reaction Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000005056 compaction Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- -1 ferromanganese ions Chemical class 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 239000006012 monoammonium phosphate Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
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
- 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
- C01P2006/12—Surface area
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Iron (AREA)
Abstract
The invention discloses a method for continuously producing ferromanganese phosphate, which comprises the following steps: preparing manganese source and iron source solution A containing an antioxidant, preparing phosphorus source solution B and preparing pH regulator solution C; adding water into a reaction kettle, adjusting the pH value to 3-5, continuously flowing solution A, solution B, solution C and deionized water under a non-oxidizing atmosphere, stirring, and keeping the pH value of a system in the reaction kettle to 3-5 and the solid content to 10-100 g/L; along with the progress of the reaction, the reaction slurry flows out through an overflow port at the upper part of the reaction kettle; and aging and solid-liquid separating the overflow slurry, and drying and calcining the solid phase to obtain the ferromanganese phosphate. The phase separation of manganese phosphate or ferrous phosphate is avoided by the continuous production process and the control of the pH value and the solid content of the reaction system. The system is always in dynamic balance of nucleation, growth, re-nucleation and re-growth, and the particle size distribution of the generated manganese iron phosphate has a certain gradient and higher tap density.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a method for continuously producing ferromanganese phosphate.
Background
The lithium iron phosphate anode material has the advantages of low cost, high safety coefficient, long cycle life and the like, and is suitable for being used as a battery for an electric automobile. According to statistics, the domestic positive electrode material for the lithium ion battery still takes ternary materials and lithium iron phosphate as main materials. In the past few years, lithium iron phosphate has been advanced mainly by way of microinnovations such as increasing its compacted density, and the products of battery enterprises have not formed significant gaps. In recent two years, the lithium iron manganese phosphate material breaks through in the aspects of cycle stability, compaction density and the like, and is expected to start commercial application in a mode of being mixed with a ternary positive electrode material or a mode of being used independently by virtue of inherent advantages of high self energy density, good safety and the like. Iron manganese phosphate is a precursor material for synthesizing lithium iron manganese phosphate, and largely determines the properties of the latter. The shape and the phase difference of the manganese iron phosphate synthesized under different conditions are large, and the performance of the lithium manganese iron phosphate anode material is directly caused to be different. At present, the intermittent method is adopted in the industry to produce the manganese iron phosphate, so that the production efficiency is low, split phases are easy to occur, and the improvement of the performance of the sintered manganese iron phosphate is not facilitated.
Patent document publication No. CN110980682a discloses a method for preparing a lithium iron manganese phosphate precursor and a method for preparing lithium iron manganese phosphate, which comprises the steps of performing coprecipitation reaction of a ferric manganese sulfate solution and oxalic acid or a phosphoric acid solution in a hypergravity rotating bed, and filtering to obtain the lithium iron manganese phosphate precursor. The method has high cost and the synthesis process is not easy to control. Patent publication No. CN111908442A discloses a method for preparing manganese iron phosphate and lithium iron phosphate by reducing stoichiometric amounts of manganese dioxide, ferrous oxalate and phosphoric acidReacting in the presence of the agent to obtain a reaction mixture, filtering to obtain a filter cake, and then performing heat treatment to obtain amorphous ferromanganese phosphate powder. The method can not realize continuous production, has low production efficiency, has a plurality of interfaces such as manganese dioxide/liquid, manganese iron phosphate/liquid and the like in the reaction process, and is difficult to realize uniform mixing of manganese iron in an atomic layer. Patent document with publication number of CN113942990A discloses a lithium iron phosphate precursor, a lithium iron phosphate positive electrode material, a preparation method thereof, an electrode material, an electrode and a lithium ion battery, wherein a first mixed solution containing an iron source and a manganese source and a second mixed solution containing a phosphorus source and an ammonia source are added into a third mixed solution containing a complexing agent and a carbon source, solid-liquid separation is carried out after coprecipitation reaction, and the lithium iron phosphate precursor is obtained after washing. Fe in the synthetic process of the method 2+ The existence of the carbon source in the synthesized precursor can enhance the conductivity in the material, but after the later sintering, more hole defects can be generated instead, the compaction density of the material is directly affected, and continuous production is difficult to realize. Patent document with publication number of CN114940485A discloses a lithium iron manganese phosphate precursor, a preparation method and application thereof, ferric iron source, trivalent manganese source, phosphoric acid and water are mixed, alkali is added to adjust the pH value of the solution to 1.5-5, and the precursor of lithium iron manganese phosphate is prepared through stirring reaction. In the method, trivalent manganese has strong oxidizing property in solution in the synthesis process, other side reactions are easy to generate, and other cations are easy to be introduced into the solution to occupy the position of ferromanganese by adopting alkali liquor with different components.
How to simplify the production process, reduce the production cost, improve the compaction density of the ferromanganese phosphate, improve the production efficiency and stably produce the ferromanganese phosphate is the current problem to be solved urgently.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention aims to provide a method for continuously producing ferromanganese phosphate.
In order to achieve the above object, the present invention provides the following technical solutions.
A method for continuously producing ferromanganese phosphate, comprising the following steps:
step S1, dissolving a manganese source and an iron source in deionized water, adding an antioxidant, and filtering to obtain a solution A; dissolving a phosphorus source in deionized water, and filtering to obtain a solution B; preparing a pH regulator solution C;
s2, adding water into a reaction kettle, adjusting the pH value to 3-5, continuously flowing solution A, solution B, solution C and deionized water in a parallel flow manner under a non-oxidizing atmosphere, stirring, and keeping the pH value of a system in the reaction kettle to 3-5 and the solid content to 10-100 g/L; along with the progress of the reaction, the reaction slurry flows out through an overflow port at the upper part of the reaction kettle;
and S3, aging and solid-liquid separation are carried out on overflow slurry, and drying and calcining are carried out on a solid phase to obtain the ferromanganese phosphate.
Further, as a preferable scheme, the iron source is at least one of titanium white byproduct ferrous sulfate, industrial grade ferrous sulfate, ferrous nitrate, ferrous chloride, ferrous oxalate and ferrous acetate; the manganese source is at least one of manganese sulfate, manganese nitrate, manganese chloride, manganese oxalate and manganese acetate; the phosphorus source is at least one of phosphoric acid, diammonium hydrogen phosphate, ammonium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate and sodium phosphate.
Further, as a preferable scheme, in the solution A, the total molar concentration of manganese and iron is 0.2-2.0 mol/L, and the molar ratio of manganese to iron is 1-2: 1.
further, as a preferable scheme, the antioxidant is at least one of ascorbic acid, hydrazine hydrate, sodium sulfite and sodium nitrite.
Further, as a preferable scheme, the adding amount of the antioxidant in the solution A is 0.5-1.5 g/L.
Further, preferably, the molar concentration of the solution B is 0.2 to 2.0mol/L.
Further, as a preferable scheme, the pH regulator is at least one of ammonia water and sodium hydroxide, and the molar concentration of the solution C is 5-10mol/L.
Further, as a preferable scheme, the acid for adjusting the pH value of the water in the reaction kettle in the step S2 is one or more of phosphoric acid, sulfuric acid, hydrochloric acid, oxalic acid and acetic acid.
Further, in the step S2, the stirring speed is controlled to be 200-1200 rmp.
Further, in the step S2, the temperature of the system is preferably controlled to be 40-60 ℃.
Further, as a preferable scheme, in the step S2, the feeding flow rate of the solution A is controlled to be 50-500ml/min; solution B was determined from the flow rate of solution A and the molar ratio of (Mn+Fe)/P was 0.95-1.05.
Further, as a preferable scheme, the non-oxidizing atmosphere is a nitrogen atmosphere, and the nitrogen flow is 0.1-50ml/min.
Further, as a preferable scheme, the aging temperature is 60-80 ℃ and the aging time is 4-6h; the drying temperature is 100-150 ℃; the calcination temperature is 300-600 ℃.
Based on the same inventive concept, the invention further provides the lithium iron phosphate prepared by the method.
Compared with the prior art, the invention has the following obvious beneficial effects.
(1) The invention adopts a continuous production process, has simple operation and high synthesis efficiency, and is suitable for industrial production.
(2) The phase separation of manganese phosphate or ferrous phosphate is avoided by the continuous production process and the control of the pH value and the solid content of the reaction system.
(3) The reaction system is always in dynamic balance of nucleation, growth, re-nucleation and re-growth, and the particle size distribution of the generated manganese iron phosphate has a certain gradient and higher tap density. Meanwhile, the production continuity is ensured, and the production efficiency is improved.
(4) In the preparation process, an antioxidant is added from the beginning, so that the hydrolysis and oxidation of ferrous ions are prevented, and the precipitation of ferrous hydroxide and ferric hydroxide can not occur.
(5) The overflow slurry after the reaction is further aged, so that free ferromanganese ions in supernatant fluid are greatly consumed, the yield of products is increased, and the diameter distance of final ferromanganese phosphate is reduced.
(6) The technical scheme provided by the invention has the advantages of low cost, no need of surfactant, simple control mode, controllable Me/P ratio of the product and the like.
Drawings
FIG. 1 is an SEM image of iron manganese phosphate of example 1 according to the invention.
FIG. 2 is an SEM image of iron-manganese phosphate of example 2 according to the present invention.
Detailed Description
The present invention will be described more fully hereinafter with reference to the accompanying drawings, in which preferred embodiments are shown, for the purpose of illustrating the invention, but the scope of the invention is not limited to the specific embodiments shown.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
Example 1
Step S1, preparing a manganese source and iron source solution:
dissolving manganese sulfate and ferrous sulfate in deionized water to prepare a solution with total concentration of iron and manganese of 1.5mol/L and molar ratio of Mn to Fe of 1.5, adding ascorbic acid, and filtering to obtain a solution A; the concentration of ascorbic acid in solution A was 1.0g/L.
Step S2, preparing a phosphorus source solution:
dissolving phosphoric acid in deionized water to prepare a solution with the concentration of 1.5mol/L, and filtering to obtain a solution B;
step S3, preparing a pH regulator:
preparing an ammonia water solution C with the concentration of 6 mol/L;
step S4, synthesis reaction:
adding deionized water with one third of the volume of the reactor body into the synthesis reactor, heating to 50 ℃, stirring at the rotation speed of 800rmp, introducing nitrogen for 1h, adding sulfuric acid to adjust the pH value of the solution in the synthesis reactor to be 4.0+/-0.1, continuously injecting the solution A, B into the synthesis reactor at the flow rate of 160ml/min, maintaining the pH value in the synthesis reactor to be 4.0+/-0.1 by using the solution C, and maintaining the solid content in the reactor to be 50+/-10 g/L by using the deionized water. The nitrogen flow was 20ml/min. The materials after the reaction flow out through an overflow port at the upper part of the synthesis kettle.
Step S5, aging and dehydration:
aging the overflowed slurry for 5 hours at 70 ℃, drying at 120 ℃ and calcining at 500 ℃ after solid-liquid separation to obtain the anhydrous ferromanganese phosphate.
FIG. 1 is an SEM image of the iron manganese phosphate of example 1.
Example 2
Step S1, preparing a manganese source and iron source solution:
dissolving manganese sulfate and ferrous sulfate in deionized water to prepare a solution with the total concentration of iron and manganese of 2mol/L, adding ascorbic acid into the solution, and filtering the solution to obtain a solution A; the concentration of ascorbic acid in solution A was 1.5g/L.
Step S2, preparing a phosphorus source solution:
dissolving phosphoric acid in deionized water to prepare a solution with the concentration of 2mol/L, and filtering to obtain a solution B;
step S3, preparing a pH regulator:
preparing 10mol/L ammonia water solution C;
step S4, synthesis reaction:
adding deionized water with one third of the volume of the kettle body into the synthesis kettle, heating to 60 ℃, stirring at the rotation speed of 800rmp, introducing nitrogen for 1h, adding sulfuric acid to adjust the pH value of the solution in the synthesis kettle to be 4.9+/-0.1, continuously injecting the solution A, B into the synthesis kettle at the flow rate of 160ml/min, maintaining the pH value in the synthesis kettle to be 4.9+/-0.1, and maintaining the solid content in the kettle to be 90+/-10 g/L by using the deionized water and the nitrogen flow rate to be 20ml/min. The materials after the reaction flow out through an overflow port at the upper part of the synthesis kettle;
step S5, aging and dehydration:
aging the overflowed slurry for 5 hours at 70 ℃, drying at 120 ℃ and calcining at 500 ℃ after solid-liquid separation to obtain the anhydrous ferromanganese phosphate.
Fig. 2 is an SEM image of the iron manganese phosphate prepared in example 2.
Example 3
Step S1, preparing a manganese source and iron source solution:
dissolving manganese sulfate and ferrous sulfate in deionized water to prepare a solution with the total concentration of iron and manganese of 0.2mol/L, adding ascorbic acid into the solution, and filtering the solution to obtain solution A; the concentration of ascorbic acid in solution A was 0.5g/L.
Step S2, preparing a phosphorus source solution:
dissolving phosphoric acid in deionized water to prepare a solution of 0.2mol/L, and filtering to obtain a solution B;
step S3, preparing a pH regulator:
preparing an ammonia water solution C with the concentration of 4 mol/L;
step S4, synthesis reaction:
adding deionized water with one third of the volume of the reactor body into the synthesis reactor, heating to 40 ℃, stirring at the rotation speed of 800rmp, introducing nitrogen for 1h, adding sulfuric acid to adjust the pH value of the solution in the synthesis reactor to 3.1+/-0.1, continuously injecting the solution A, B into the synthesis reactor at the flow rate of 160ml/min, maintaining the pH value in the synthesis reactor to 3.1+/-0.1 by using the solution C, and maintaining the solid content in the reactor to 20+/-10 g/L by using the deionized water. The nitrogen flow was 20ml/min. The materials after the reaction flow out through an overflow port at the upper part of the synthesis kettle.
Step S5, aging and dehydration:
aging the overflowed slurry for 5 hours at 70 ℃, drying at 120 ℃ and calcining at 500 ℃ after solid-liquid separation to obtain the anhydrous ferromanganese phosphate.
Example 4
Step S1, preparing a manganese source and iron source solution:
dissolving manganese chloride and ferrous chloride in deionized water to prepare a solution with total concentration of iron and manganese of 1.5mol/L and molar ratio of Mn to Fe of 1.5, adding ascorbic acid, and filtering to obtain a solution A; the concentration of ascorbic acid in solution A was 1.0g/L.
Step S2, preparing a phosphorus source solution:
dissolving monoammonium phosphate into deionized water to prepare a solution with the concentration of 1.5mol/L, and filtering to obtain a solution B;
step S3, preparing a pH regulator:
preparing a sodium hydroxide solution C with the concentration of 6 mol/L;
step S4, synthesis reaction:
adding deionized water with one third of the volume of the reactor body into the synthesis reactor, heating to 40 ℃, stirring at the rotation speed of 800rmp, introducing nitrogen for 1h, adding sulfuric acid to adjust the pH value of the solution in the synthesis reactor to be 4.0+/-0.1, continuously injecting the solution A, B into the synthesis reactor at the flow rate of 160ml/min, maintaining the pH value in the synthesis reactor to be 4.0+/-0.1 by using the solution C, and maintaining the solid content in the reactor to be 60+/-10 g/L by using the deionized water. The nitrogen flow was 20ml/min. The materials after the reaction flow out through an overflow port at the upper part of the synthesis kettle.
Step S5, aging and dehydration:
aging the overflowed slurry for 5 hours at 70 ℃, drying at 120 ℃ and calcining at 500 ℃ after solid-liquid separation to obtain the anhydrous ferromanganese phosphate.
Example 5
Step S1, preparing a manganese source and iron source solution:
dissolving manganese oxalate and ferrous oxalate in deionized water to prepare a solution with total concentration of iron and manganese of 1.5mol/L, adding hydrazine hydrate and filtering to obtain a solution A, wherein the molar ratio of Mn to Fe is 1.5; the concentration of hydrazine hydrate in the solution A is 1.0g/L.
Step S2, preparing a phosphorus source solution:
dissolving ammonia phosphate in deionized water to prepare a solution with the concentration of 1.5mol/L, and filtering to obtain a solution B;
step S3, preparing a pH regulator:
preparing an ammonia water solution C with the concentration of 6 mol/L;
step S4, synthesis reaction:
adding deionized water with one third of the volume of the reactor body into the synthesis reactor, heating to 40 ℃, stirring at the rotation speed of 800rmp, introducing nitrogen for 1h, adding sulfuric acid to adjust the pH value of the solution in the synthesis reactor to be 4.0+/-0.1, continuously injecting the solution A, B into the synthesis reactor at the flow rate of 160ml/min, maintaining the pH value in the synthesis reactor to be 4.0+/-0.1 by using the solution C, and maintaining the solid content in the reactor to be 50+/-10 g/L by using the deionized water. The nitrogen flow was 20ml/min. The materials after the reaction flow out through an overflow port at the upper part of the synthesis kettle.
Step S5, aging and dehydration:
aging the overflowed slurry for 5 hours at 70 ℃, drying at 120 ℃ and calcining at 500 ℃ after solid-liquid separation to obtain the anhydrous ferromanganese phosphate.
Example 6
Step S1, preparing a manganese source and iron source solution:
dissolving manganese acetate and ferrous acetate in deionized water to prepare a solution with total concentration of iron and manganese of 1.5mol/L and molar ratio of Mn to Fe of 1.5, adding ascorbic acid, and filtering to obtain a solution A; the concentration of ascorbic acid in solution A was 1.0g/L.
Step S2, preparing a phosphorus source solution:
dissolving sodium phosphate in deionized water to prepare a solution with the concentration of 1.5mol/L, and filtering to obtain a solution B;
step S3, preparing a pH regulator:
preparing a sodium hydroxide solution C with the concentration of 4 mol/L;
step S4, synthesis reaction:
adding deionized water with one third of the volume of the reactor body into the synthesis reactor, heating to 40 ℃, stirring at the rotation speed of 800rmp, introducing nitrogen for 1h, adding sulfuric acid to adjust the pH value of the solution in the synthesis reactor to be 4.0+/-0.1, continuously injecting the solution A, B into the synthesis reactor at the flow rate of 160ml/min, maintaining the pH value in the synthesis reactor to be 4.0+/-0.1 by using the solution C, and maintaining the solid content in the reactor to be 80+/-10 g/L by using the deionized water. The nitrogen flow was 20ml/min. The materials after the reaction flow out through an overflow port at the upper part of the synthesis kettle.
Step S5, aging and dehydration:
aging the overflowed slurry for 5 hours at 70 ℃, drying at 120 ℃ and calcining at 500 ℃ after solid-liquid separation to obtain the anhydrous ferromanganese phosphate.
Comparative example 1
Step S1, preparing a manganese source and iron source solution:
dissolving manganese sulfate and ferrous sulfate in deionized water to prepare a solution with total concentration of iron and manganese of 1.5mol/L and molar ratio of Mn to Fe of 1.5, adding ascorbic acid, and filtering to obtain a solution A; the concentration of ascorbic acid in solution A was 1.0g/L.
Step S2, preparing a phosphorus source solution:
dissolving phosphoric acid in deionized water to prepare a solution with the concentration of 1.5mol/L, and filtering to obtain a solution B;
step S3, preparing a pH regulator:
preparing an ammonia water solution C with the concentration of 6 mol/L;
step S4, synthesis reaction:
adding deionized water with one third of the volume of the kettle body into the synthesis kettle, heating to 50 ℃, stirring at the rotation speed of 800rmp, introducing nitrogen for 1h, adding sulfuric acid to adjust the pH value of the solution in the synthesis kettle to be 4.0+/-0.1, continuously injecting the solution A, B into the synthesis kettle at the flow rate of 160ml/min, and maintaining the pH value in the synthesis kettle to be 4.0+/-0.1 by using the solution C. The solid content in the kettle is not regulated in the reaction process. The nitrogen flow was 20ml/min. The materials after the reaction flow out through an overflow port at the upper part of the synthesis kettle.
Step S5, aging and dehydration:
aging the overflowed slurry for 5 hours at 70 ℃, drying at 120 ℃ and calcining at 500 ℃ after solid-liquid separation to obtain the anhydrous ferromanganese phosphate.
Comparative example 2
Step S1, preparing a manganese source and iron source solution:
dissolving manganese sulfate and ferrous sulfate in deionized water to prepare a solution with total concentration of iron and manganese of 1.5mol/L and molar ratio of Mn to Fe of 1.5, adding ascorbic acid, and filtering to obtain a solution A; the concentration of ascorbic acid in solution A was 1.0g/L.
Step S2, preparing a phosphorus source solution:
dissolving phosphoric acid in deionized water to prepare a solution with the concentration of 1.5mol/L, and filtering to obtain a solution B;
step S3, preparing a pH regulator:
preparing an ammonia water solution C with the concentration of 6 mol/L;
step S4, synthesis reaction:
adding deionized water with one third of the volume of the reactor body into the synthesis reactor, heating to 50 ℃, stirring at the rotation speed of 800rmp, introducing nitrogen for 1h, adding sulfuric acid to adjust the pH value of the solution in the synthesis reactor to 6.0+/-0.1, continuously injecting the solution A, B into the synthesis reactor at the flow rate of 160ml/min, maintaining the pH value in the synthesis reactor to 6.0+/-0.1 by using the solution C, and maintaining the solid content in the reactor to 50+/-10 g/L by using the deionized water. The nitrogen flow was 20ml/min. The materials after the reaction flow out through an overflow port at the upper part of the synthesis kettle.
Step S5, aging and dehydration:
aging the overflowed slurry for 5 hours at 70 ℃, drying at 120 ℃ and calcining at 500 ℃ after solid-liquid separation to obtain the anhydrous ferromanganese phosphate.
Comparative example 3
Step S1, preparing a manganese source and iron source solution:
dissolving manganese phosphate and ferrous phosphate in deionized water to prepare a solution with total concentration of iron and manganese of 1.5mol/L and molar ratio of Mn to Fe of 1.5, adding ascorbic acid, and filtering to obtain a solution A; the concentration of ascorbic acid in solution A was 1.0g/L.
Step S2, preparing a phosphorus source solution:
dissolving phosphoric acid in deionized water to prepare a solution with the concentration of 1.5mol/L, and filtering to obtain a solution B;
step S3, preparing a pH regulator:
preparing an ammonia water solution C with the concentration of 6 mol/L;
step S4, synthesis reaction:
adding deionized water with one third of the volume of the reactor body into the synthesis reactor, heating to 50 ℃, stirring at the rotation speed of 800rmp, introducing nitrogen for 1h, adding sulfuric acid to adjust the pH value of the solution in the synthesis reactor to 2.0+/-0.1, continuously injecting the solution A, B into the synthesis reactor at the flow rate of 160ml/min, maintaining the pH value in the synthesis reactor to 2.0+/-0.1 by using the solution C, and maintaining the solid content in the reactor to 50+/-10 g/L by using the deionized water. The nitrogen flow was 20ml/min. The materials after the reaction flow out through an overflow port at the upper part of the synthesis kettle.
Step S5, aging and dehydration:
aging the overflowed slurry for 5 hours at 70 ℃, drying at 120 ℃ and calcining at 500 ℃ after solid-liquid separation to obtain the anhydrous ferromanganese phosphate.
Comparative example 4-1
Step S1, preparing a manganese source and iron source solution:
dissolving manganese sulfate and ferrous sulfate in deionized water to prepare a solution with total concentration of iron and manganese of 1.5mol/L and molar ratio of Mn to Fe of 1.5, adding ascorbic acid, and filtering to obtain a solution A; the concentration of ascorbic acid in solution A was 1.0g/L.
Step S2, preparing a phosphorus source solution:
dissolving phosphoric acid in deionized water to prepare a solution with the concentration of 1.5mol/L, and filtering to obtain a solution B;
step S3, preparing a pH regulator:
preparing an ammonia water solution C with the concentration of 6 mol/L;
step S4, synthesis reaction:
adding deionized water with one third of the volume of the reactor body into the synthesis reactor, heating to 50 ℃, stirring at the rotation speed of 800rmp, introducing nitrogen for 1h, adding sulfuric acid to adjust the pH value of the solution in the synthesis reactor to be 4.0+/-0.1, continuously injecting the solution A, B into the synthesis reactor at the flow rate of 160ml/min, maintaining the pH value in the synthesis reactor to be 4.0+/-0.1 by using the solution C, and maintaining the solid content in the reactor to be 50+/-10 g/L by using the deionized water. The nitrogen flow was 20ml/min. And discharging the reaction slurry after the granularity D50 of the reaction slurry in the synthesis kettle reaches 18+/-2 mu m.
Step S5, aging and dehydration:
aging the slurry at 70 ℃ for 5 hours, drying at 120 ℃ and calcining at 500 ℃ after solid-liquid separation to obtain the anhydrous ferromanganese phosphate.
Comparative example 4-2
Comparative example 4-2 is the same as 4-1.
The properties of the iron manganese phosphate obtained in each of the examples and comparative examples were measured, and the results are shown in Table 1.
TABLE 1
As can be seen from Table 1, in examples 1-6, the continuous method of the invention is used for producing the manganese iron phosphate, and under the condition that the pH value is controlled to be 3-5 and the solid content is controlled to be 10-100 g/L, the obtained manganese iron phosphate has relatively uniform specific surface area, larger tap density and controllable granularity. Comparative examples 1 to 3 still used a continuous process to produce ferromanganese phosphate, but the ferromanganese phosphate obtained was small in tap density and uneven in particle size distribution in the presence of a particularly large specific surface area under the conditions of changing the solid content or pH. And under the condition that the pH value is controlled to be 3-5 and the solid content is 10-100 g/L, the intermittent method is adopted to produce the manganese iron phosphate (comparative examples 4-1 and 4-2), so that the problems of poor repeatability and poor stability exist.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. A method for continuously producing ferromanganese phosphate, which is characterized by comprising the following steps:
step S1, dissolving a manganese source and an iron source in deionized water, adding an antioxidant, and filtering to obtain a solution A; dissolving a phosphorus source in deionized water, and filtering to obtain a solution B; preparing a pH regulator solution C;
s2, adding water into a reaction kettle, adjusting the pH value to 3-5, continuously flowing solution A, solution B, solution C and deionized water in a parallel flow manner under a non-oxidizing atmosphere, stirring, and keeping the pH value of a system in the reaction kettle to 3-5 and the solid content to 10-100 g/L; along with the progress of the reaction, the reaction slurry flows out through an overflow port at the upper part of the reaction kettle;
and S3, aging and solid-liquid separation are carried out on overflow slurry, and drying and calcining are carried out on a solid phase to obtain the ferromanganese phosphate.
2. The method of claim 1, wherein the iron source is at least one of titanium dioxide byproduct ferrous sulfate, technical grade ferrous sulfate, ferrous nitrate, ferrous chloride, ferrous oxalate, ferrous acetate; the manganese source is at least one of manganese sulfate, manganese nitrate, manganese chloride, manganese oxalate and manganese acetate; the phosphorus source is at least one of phosphoric acid, diammonium hydrogen phosphate, ammonium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate and sodium phosphate; the antioxidant is at least one of ascorbic acid, hydrazine hydrate, sodium sulfite and sodium nitrite.
3. The method according to claim 2, wherein the total molar concentration of manganese and iron in the solution a is 0.2-2.0 mol/L, and the molar ratio of manganese to iron is 1-2: 1, a step of; in the solution A, the addition amount of the antioxidant is 0.5-1.5 g/L.
4. The method according to claim 2, wherein the molar concentration of the solution B is 0.2 to 2.0mol/L.
5. The method according to claim 1, wherein the pH regulator is at least one of ammonia water and sodium hydroxide, and the molar concentration of the solution C is 5-10mol/L.
6. The method according to claim 1, wherein the acid for adjusting the pH value of the water in the reaction vessel in step S2 is one or more of phosphoric acid, sulfuric acid, hydrochloric acid, oxalic acid, and acetic acid.
7. The method according to claim 1, wherein in the step S2, the stirring speed is controlled to be 200-1200 rmp; the temperature of the system is controlled to be 40-60 ℃; the feeding flow rate of the solution A is controlled to be 50-500ml/min; solution B was determined from the flow rate of solution A and the molar ratio of (Mn+Fe)/P was 0.95-1.05.
8. The method of claim 1, wherein the non-oxidizing atmosphere is a nitrogen atmosphere and the nitrogen flow is 0.1-50ml/min.
9. The method of claim 1, wherein the aging temperature is 60-80 ℃ and the aging time is 4-6 hours; the drying temperature is 100-150 ℃; the calcination temperature is 300-600 ℃.
10. Lithium iron phosphate, characterized in that it is prepared by the process according to any one of claims 1 to 9.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117263154A (en) * | 2023-10-13 | 2023-12-22 | 金驰能源材料有限公司 | Ferric phosphate and continuous production method and application thereof |
| CN117566716A (en) * | 2023-11-23 | 2024-02-20 | 新洋丰农业科技股份有限公司 | Preparation method of low-impurity high-performance ferric manganese phosphate and ferric manganese lithium phosphate |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102092798A (en) * | 2010-12-01 | 2011-06-15 | 兰州金川新材料科技股份有限公司 | Method for continuously synthesizing precursor of lithium ion battery positive material |
| CN108306003A (en) * | 2018-01-29 | 2018-07-20 | 蒋央芳 | A kind of preparation method of iron manganese phosphate |
| CN111908442A (en) * | 2020-08-07 | 2020-11-10 | 上海华谊（集团）公司 | Ferromanganese phosphate, lithium iron manganese phosphate and preparation method thereof |
| CN114057177A (en) * | 2021-11-23 | 2022-02-18 | 湖北融通高科先进材料有限公司 | Ferrous manganese phosphate and preparation method and application thereof |
| CN115231541A (en) * | 2022-06-27 | 2022-10-25 | 广东邦普循环科技有限公司 | Preparation method and application of lithium iron manganese phosphate |
| CN115321507A (en) * | 2022-08-25 | 2022-11-11 | 广东邦普循环科技有限公司 | Method for preparing ferromanganese phosphate by coprecipitation and application thereof |
| CN115709979A (en) * | 2022-12-07 | 2023-02-24 | 埃索凯循环能源科技(广西)有限公司 | Method for preparing battery-grade manganese iron phosphate by taking high-iron manganese ore as raw material |
| US20230060433A1 (en) * | 2022-05-25 | 2023-03-02 | Hubei Rt Advanced Materials Co., Ltd. | Preparation method of high-safety high-capacity lithium manganese iron phosphate |
-
2023
- 2023-03-09 CN CN202310222914.1A patent/CN116062726A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102092798A (en) * | 2010-12-01 | 2011-06-15 | 兰州金川新材料科技股份有限公司 | Method for continuously synthesizing precursor of lithium ion battery positive material |
| CN108306003A (en) * | 2018-01-29 | 2018-07-20 | 蒋央芳 | A kind of preparation method of iron manganese phosphate |
| CN111908442A (en) * | 2020-08-07 | 2020-11-10 | 上海华谊（集团）公司 | Ferromanganese phosphate, lithium iron manganese phosphate and preparation method thereof |
| CN114057177A (en) * | 2021-11-23 | 2022-02-18 | 湖北融通高科先进材料有限公司 | Ferrous manganese phosphate and preparation method and application thereof |
| US20230060433A1 (en) * | 2022-05-25 | 2023-03-02 | Hubei Rt Advanced Materials Co., Ltd. | Preparation method of high-safety high-capacity lithium manganese iron phosphate |
| CN115231541A (en) * | 2022-06-27 | 2022-10-25 | 广东邦普循环科技有限公司 | Preparation method and application of lithium iron manganese phosphate |
| CN115321507A (en) * | 2022-08-25 | 2022-11-11 | 广东邦普循环科技有限公司 | Method for preparing ferromanganese phosphate by coprecipitation and application thereof |
| CN115709979A (en) * | 2022-12-07 | 2023-02-24 | 埃索凯循环能源科技(广西)有限公司 | Method for preparing battery-grade manganese iron phosphate by taking high-iron manganese ore as raw material |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117263154A (en) * | 2023-10-13 | 2023-12-22 | 金驰能源材料有限公司 | Ferric phosphate and continuous production method and application thereof |
| CN117263154B (en) * | 2023-10-13 | 2024-04-19 | 金驰能源材料有限公司 | Ferric phosphate and continuous production method and application thereof |
| CN117566716A (en) * | 2023-11-23 | 2024-02-20 | 新洋丰农业科技股份有限公司 | Preparation method of low-impurity high-performance ferric manganese phosphate and ferric manganese lithium phosphate |
| CN117566716B (en) * | 2023-11-23 | 2024-05-17 | 新洋丰农业科技股份有限公司 | Preparation method of low-impurity high-performance ferric manganese phosphate and ferric manganese lithium phosphate |
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