CN117361475A - Preparation method of precursor ferromanganese phosphate of lithium ion battery anode material - Google Patents
Preparation method of precursor ferromanganese phosphate of lithium ion battery anode material Download PDFInfo
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- CN117361475A CN117361475A CN202311272132.5A CN202311272132A CN117361475A CN 117361475 A CN117361475 A CN 117361475A CN 202311272132 A CN202311272132 A CN 202311272132A CN 117361475 A CN117361475 A CN 117361475A
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- lithium ion
- ion battery
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- 239000002243 precursor Substances 0.000 title claims abstract description 47
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 29
- 239000010405 anode material Substances 0.000 title claims abstract description 16
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 229910000616 Ferromanganese Inorganic materials 0.000 title claims description 8
- 229910019142 PO4 Inorganic materials 0.000 title claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims description 8
- 239000010452 phosphate Substances 0.000 title claims description 8
- 239000000243 solution Substances 0.000 claims abstract description 95
- 239000011572 manganese Substances 0.000 claims abstract description 76
- 239000002253 acid Substances 0.000 claims abstract description 41
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 30
- 238000001914 filtration Methods 0.000 claims abstract description 26
- 238000005406 washing Methods 0.000 claims abstract description 26
- 239000007774 positive electrode material Substances 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 15
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 claims abstract description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 14
- 239000007800 oxidant agent Substances 0.000 claims abstract description 13
- 239000000725 suspension Substances 0.000 claims abstract description 13
- 230000001590 oxidative effect Effects 0.000 claims abstract description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000002696 manganese Chemical class 0.000 claims abstract description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 11
- 239000011574 phosphorus Substances 0.000 claims abstract description 11
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 229910052742 iron Inorganic materials 0.000 claims abstract description 9
- 239000007790 solid phase Substances 0.000 claims abstract description 9
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000012266 salt solution Substances 0.000 claims abstract description 4
- 230000032683 aging Effects 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 36
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 18
- 235000017550 sodium carbonate Nutrition 0.000 claims description 14
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 11
- 239000011790 ferrous sulphate Substances 0.000 claims description 11
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 11
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 11
- 229940099596 manganese sulfate Drugs 0.000 claims description 11
- 235000007079 manganese sulphate Nutrition 0.000 claims description 11
- 239000011702 manganese sulphate Substances 0.000 claims description 11
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 229960002089 ferrous chloride Drugs 0.000 claims description 4
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 4
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 4
- 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 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 3
- -1 permanganate Chemical compound 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- 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
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 239000012065 filter cake Substances 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 2
- 229940062993 ferrous oxalate Drugs 0.000 claims 1
- 229960001781 ferrous sulfate Drugs 0.000 claims 1
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 66
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 6
- 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 6
- 229910052748 manganese Inorganic materials 0.000 abstract description 4
- 239000012429 reaction media Substances 0.000 abstract description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 abstract description 3
- 239000011593 sulfur Substances 0.000 abstract description 3
- 238000011112 process operation Methods 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract description 2
- 239000007787 solid Substances 0.000 description 20
- 239000012286 potassium permanganate Substances 0.000 description 11
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 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 5
- 238000012360 testing method Methods 0.000 description 4
- 229910016953 Fe0.5Mn0.5PO4 Inorganic materials 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 1
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- SBWRUMICILYTAT-UHFFFAOYSA-K lithium;cobalt(2+);phosphate Chemical compound [Li+].[Co+2].[O-]P([O-])([O-])=O SBWRUMICILYTAT-UHFFFAOYSA-K 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000003017 phosphorus Chemical class 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of a precursor ferric manganese phosphate of a positive electrode material of a lithium ion battery, which comprises the following steps: uniformly mixing carbonate solution and ferric salt and manganese salt solution, filtering and washing to obtain solid phase Fe x Mn (1‑x) CO 3 The method comprises the steps of carrying out a first treatment on the surface of the Forming Fe by using phosphorus-containing acid solution to solid phase x Mn (1‑x) PO 4 An acid solution; adding an acid solution and an oxidant solution into a hydrothermal reaction kettle in parallel, and heating and ageing to obtain Fe x Mn (1‑x) PO 4 Filtering, washing and drying the precursor suspension to obtain a precursor Fe of the lithium ion battery anode material x Mn (1‑x) PO 4 ·H 2 O, wherein 0 < x < 1. The manganese iron phosphate prepared by the two-step method of the invention greatly reduces the weight in the finished productMetal impurities and sulfur content; the temperature of the reaction medium is 75-105 ℃, the production cost is low, the reaction medium is safe and the process operation is simple; meanwhile, the sodium carbonate and the phosphorus source are excessive, so that the recovery rate of the iron and manganese metal reaches more than 99.5%, and the iron and manganese resources are fully utilized; in addition, the iron-manganese ratio can be adjusted, and the required precursor can be obtained by adjusting the iron-manganese ratio.
Description
Technical Field
The invention relates to a preparation method of a precursor ferric manganese phosphate of a positive electrode material of a lithium ion battery, belonging to the field of battery materials.
Background
The new energy automobile has a limited space, so that the energy density of the storage battery is high, and the more the electric quantity discharged by the battery in unit volume and unit weight is, the longer the mileage of one-time charging is. However, the voltage of the lithium iron phosphate battery is only 3.2V, and the theoretical energy density is only 165Wh/kg, which seriously affects the endurance mileage of an automobile carrying the lithium iron phosphate battery. For this reason, many power cells are turned to lithium nickel cobalt manganese or lithium nickel cobalt aluminate cells with higher energy densities, but these cells have serious safety problems that limit their use. The safety of lithium iron phosphate materials benefits from their stable structure. For this reason, researchers have developed phosphate system battery materials such as lithium manganese phosphate, lithium cobalt phosphate, lithium iron manganese phosphate and the like on the basis of lithium iron phosphate. Lithium iron manganese phosphate battery materials are currently being widely focused and studied. It has a similar structure to that of lithium iron phosphate, similar specific capacity, but higher discharge voltage (3.9-4.1V), which means that the energy density is improved by 20-28% on the basis of lithium iron phosphate. The lithium iron manganese phosphate is hopeful to replace the lithium iron phosphate to become a new power and energy storage lithium battery first choice positive electrode material.
However, the existing synthesis methods of lithium iron manganese phosphate are all hydrothermal synthesis by a one-step method, and have large burden on equipment and potential danger. Or the precursor of the ferromanganese phosphate is synthesized by adopting a high-hazard oxidant, for example: ozone or nitric acid, these oxidants can escape gases that are more harmful to the human body during synthesis. Or some processes and formulations that require reaction in an organic solvent to produce stable iron or lithium manganese phosphate.
Disclosure of Invention
The invention aims to: the invention aims to provide a simple preparation method of battery-grade manganese iron phosphate, which is synthesized by a two-step method, has no additional pollution to an oxidant and is suitable for industrial production.
The technical scheme is as follows: the preparation method of the precursor ferric manganese phosphate of the positive electrode material of the lithium ion battery comprises the following steps:
step (1): uniformly mixing carbonate solution and ferric salt and manganese salt solution, filtering and washing to obtain solid phase Fe x Mn (1-x) CO 3 ；
Step (2): forming Fe by using a phosphoric acid solution to the solid phase x Mn (1-x) PO 4 An acid solution;
step (3): the acid solution and the oxidant solution are added into a hydrothermal reaction kettle in parallel to be heated and aged to obtain Fe x Mn (1-x) PO 4 Filtering, washing and drying the precursor suspension to obtain a precursor Fe of the lithium ion battery anode material x Mn (1-x) PO 4 ·H 2 O, wherein 0 < x < 1.
Further, the carbonate in the step (1) is one of soluble carbonates such as sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate and the like, preferably sodium carbonate; the concentration is 0.05 to 5mol/L, preferably 2mol/L.
Further, the ferric salt is one of soluble iron such as ferrous chloride, ferrous sulfate, ferric nitrate, ferric chloride, etc., preferably ferrous sulfate.
Further, the manganese salt is one of soluble manganese salts such as manganese sulfate and manganese nitrate, and preferably manganese sulfate; the concentration is 0.05 to 5mol/L, preferably 2mol/L.
Further, in the step (1), the molar ratio of the carbonate to the iron salt manganese salt is 0.8 to 5, preferably 1.1.
Further, the molar ratio of the ferric salt to the manganese salt in the ferric salt manganese salt solution is 2:8-9:1, preferably 3:7.
Further, in the step (2), the solid phase material Fe x Mn (1-x) CO 3 Formation of Fe with phosphorus-containing acid solution x Mn (1-x) PO 4 The molar ratio of the ferro-manganese metal to the phosphorus in the acid solution is 0.9-5, preferably 1.7.
Further, the pH of the phosphoric acid-containing solution is preferably from 0 to 6 and is preferably 1.1.
Further, the phosphoric acid solution is a solution obtained by mixing one or more of phosphoric acid, ammonium phosphate, sodium phosphate and other phosphorus salts with one or more of sulfuric acid, nitric acid, hydrochloric acid, acetic acid, oxalic acid and other acids, and is preferably pure phosphoric acid.
Further, the concentration of phosphorus in the phosphorus-containing acid solution is 0.1 to 4.5mol/L, preferably 1.7.
Further, the pH of the phosphoric acid-containing solution is 0 to 6, preferably 1.1.
Further, in the step (3), the oxidant is one or more of nitric acid, nitrate, hydrogen peroxide, permanganate, sodium peroxide, sodium persulfate, hypochlorite and ozone, preferably potassium permanganate; the concentration is 0.001 to 5mol/L, preferably 0.1 to 0.4mol/L.
Further, fe x Mn (1-x) PO 4 The molar ratio of the amount of metal in the acid solution to the amount of oxidant is 0.1 to 10, preferably 0.25.
Further, in the step (3), the Fe x Mn (1-x) PO 4 The co-current flow rate ratio of the acid solution to the oxidant solution is 0.1-10, preferably 1; the aging temperature of heating is 75-105 ℃, preferably 92 ℃; fe (Fe) x Mn (1-x) PO 4 The drying temperature of the filter cake is 40-400 ℃, preferably 105 ℃.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable advantages: 1. the manganese iron phosphate prepared by the two-step method greatly reduces the contents of heavy metal impurities and sulfur in the finished product; 2. the temperature of the reaction medium is 75-105 ℃, the production cost is low, the reaction medium is safe and the process operation is simple; 3. the sodium carbonate and the phosphorus source are excessive, so that the recovery rate of the iron and manganese metal reaches more than 99.5%, and the iron and manganese resources are fully utilized; 4. the ratio of iron to manganese can be adjusted, and the required precursor can be obtained by adjusting the ratio of iron to manganese.
Drawings
FIG. 1 is an XRD pattern of iron manganese phosphate prepared in example 1 of the present invention;
FIG. 2 is a SEM image of low magnification of ferromanganese phosphate prepared in example 1 of the present invention;
FIG. 3 is a SEM image of the high magnification of ferromanganese phosphate prepared in example 1 of the present invention;
FIG. 4 is a flow chart of the preparation of ferromanganese phosphate according to the present invention.
Detailed Description
The technical scheme of the invention is further described below with reference to the accompanying drawings.
Example 1
Mixing 2.2L of 2mol/L sodium carbonate solution with 2L of 0.6mol/L ferrous sulfate and 1.4mol/L manganese sulfate solution uniformly, filtering and washing to obtain Fe 0.3 Mn 0.7 CO 3 A solid; dissolving the solid with 4L of 1.7mol/L phosphoric acid solution to form Fe 0.3 Mn 0.7 PO 4 An acid solution; fe is added to 0.3 Mn 0.7 PO 4 The acid solution and 5L of 0.2mol/L potassium permanganate solution are added into a hydrothermal reaction kettle in parallel, and are heated to 92 ℃ and aged for 2 hours to obtain Fe 0.3 Mn 0.7 PO 4 Filtering, washing and drying the precursor suspension at 105 ℃ to obtain a precursor Fe of the lithium ion battery anode material 0.3 Mn 0.7 PO 4 ·H 2 O. See fig. 4.
Example 2
Mixing 2.2L of 2mol/L sodium carbonate solution with 2L of 0.8mol/L ferrous sulfate and 1.2mol/L manganese sulfate solution uniformly, filtering and washing to obtain Fe 0.4 Mn 0.6 CO 3 A solid; dissolving the solid with 4L of 1.7mol/L phosphoric acid solution to form Fe 0.4 Mn 0.6 PO 4 An acid solution; fe is added to 0.4 Mn 0.6 PO 4 The acid solution and 5L,0.2mol/L potassium permanganate solution are added into a hydrothermal reaction kettle in parallel, heated to 92 ℃ and aged for 2 hours to obtain Fe 0.4 Mn 0.6 PO 4 Filtering, washing and drying the precursor suspension at 105 ℃ to obtain a precursor Fe of the lithium ion battery anode material 0.4 Mn 0.6 PO 4 ·H 2 O. See fig. 4.
Example 3
Mixing 2.2L of 2mol/L sodium carbonate solution with 2L of 1mol/L ferrous sulfate and 1mol/L manganese sulfate solution uniformly, filtering,Washing to obtain Fe 0.5 Mn 0.5 CO 3 A solid; dissolving the solid with 4L of 1.7mol/L phosphoric acid solution to form Fe 0.5 Mn 0.5 PO 4 An acid solution; fe is added to 0.5 Mn 0.5 PO 4 The acid solution and 5L of 0.2mol/L potassium permanganate solution are added into a hydrothermal reaction kettle in parallel, and are heated to 92 ℃ and aged for 2 hours to obtain Fe 0.5 Mn 0.5 PO 4 Filtering, washing and drying the precursor suspension at 105 ℃ to obtain a precursor Fe of the lithium ion battery anode material 0.5 Mn 0.5 PO 4 ·H 2 O. See fig. 4.
Example 4
Mixing 2.2L of 2mol/L sodium carbonate solution with 2L of 1.2mol/L ferrous sulfate and 0.8mol/L manganese sulfate solution uniformly, filtering and washing to obtain Fe 0.6 Mn 0.4 CO 3 A solid; dissolving the solid with 4L of 1.7mol/L phosphoric acid solution to form Fe 0.6 Mn 0.4 PO 4 An acid solution; fe is added to 0.6 Mn 0.4 PO 4 The acid solution and 5L of 0.2mol/L potassium permanganate solution are added into a hydrothermal reaction kettle in parallel, and are heated to 92 ℃ and aged for 2 hours to obtain Fe 0.6 Mn 0.4 PO 4 Filtering, washing and drying the precursor suspension at 105 ℃ to obtain a precursor Fe of the lithium ion battery anode material 0.6 Mn 0.4 PO 4 ·H 2 O. See fig. 4.
Example 5
Mixing 2.2L of 2mol/L sodium carbonate solution with 2L of 1.4mol/L ferrous sulfate and 0.6mol/L manganese sulfate solution uniformly, filtering and washing to obtain Fe 0.7 Mn 0.3 CO 3 A solid; dissolving the solid with 4L of 1.7mol/L phosphoric acid solution to form Fe 0.7 Mn 0.3 PO 4 An acid solution; fe is added to 0.7 Mn 0.3 PO 4 The acid solution and 5L of 0.2mol/L potassium permanganate solution are added into a hydrothermal reaction kettle in parallel, and are heated to 92 ℃ and aged for 2 hours to obtain Fe 0.7 Mn 0.3 PO 4 Filtering, washing and drying the precursor suspension at 105 ℃ to obtain a precursor Fe of the lithium ion battery anode material 0.7 Mn 0.3 PO 4 ·H 2 O. SeeFig. 4.
Example 6
Mixing 2.2L of 2mol/L sodium carbonate solution with 2L of 0.6mol/L ferrous sulfate and 1.4mol/L manganese sulfate solution uniformly, filtering and washing to obtain Fe 0.3 Mn 0.7 CO 3 A solid; dissolving the solid with 4L of 1.7mol/L phosphoric acid solution to form Fe 0.3 Mn 0.7 PO 4 An acid solution; fe is added to 0.3 Mn 0.7 PO 4 The acid solution and 2.5L of 0.4mol/L potassium permanganate solution are added into a hydrothermal reaction kettle in parallel, heated to 92 ℃ and aged for 2 hours to obtain Fe 0.3 Mn 0.7 PO 4 Filtering, washing and drying the precursor suspension at 105 ℃ to obtain a precursor Fe of the lithium ion battery anode material 8 0.3 Mn 0.7 PO 4 ·H 2 O. See fig. 4.
Example 7
Mixing 2.2L of 2mol/L sodium carbonate solution with 2L of 0.6mol/L ferrous chloride and 1.4mol/L manganese sulfate solution uniformly, filtering and washing to obtain Fe 0.3 Mn 0.7 CO 3 A solid; dissolving the solid with 4L of 1.7mol/L phosphoric acid solution to form Fe 0.3 Mn 0.7 PO 4 An acid solution; fe is added to 0.3 Mn 0.7 PO 4 The acid solution and 5L of 0.2mol/L potassium permanganate solution are added into a hydrothermal reaction kettle in parallel, and are heated to 92 ℃ and aged for 2 hours to obtain Fe 0.3 Mn 0.7 PO 4 Filtering, washing and drying the precursor suspension at 105 ℃ to obtain a precursor Fe of the lithium ion battery anode material 0.3 Mn 0.7 PO 4 ·H 2 O. See fig. 4.
Example 8
Mixing 2.2L of 2mol/L sodium carbonate solution with 2L of 0.6mol/L ferrous sulfate and 1.4mol/L manganese nitrate solution uniformly, filtering and washing to obtain Fe 0.3 Mn 0.7 CO 3 A solid; dissolving the solid with 4L of 1.7mol/L phosphoric acid solution to form Fe 0.3 Mn 0.7 PO 4 An acid solution; fe is added to 0.3 Mn 0.7 PO 4 The acid solution and 5L of 0.2mol/L potassium permanganate solution are added into a hydrothermal reaction kettle in parallel, and are heated to 92 ℃ and aged for 2 hours to obtain Fe 0.3 Mn 0.7 PO 4 Filtering, washing and drying the precursor suspension at 105 ℃ to obtain a precursor Fe of the lithium ion battery anode material 0.3 Mn 0.7 PO 4 ·H 2 O. See fig. 4.
Example 9
Mixing 2.2L of 2mol/L sodium carbonate solution with 2L of 0.6mol/L ferrous chloride and 1.4mol/L manganese nitrate solution uniformly, filtering and washing to obtain Fe 0.4 Mn 0.6 CO 3 A solid; dissolving the solid with 4L of 1.7mol/L phosphoric acid solution to form Fe 0.4 Mn 0.6 PO 4 An acid solution; fe is added to 0.4 Mn 0.6 PO 4 The acid solution and 5L of 0.2mol/L potassium permanganate solution are added into a hydrothermal reaction kettle in parallel, and are heated to 92 ℃ and aged for 2 hours to obtain Fe 0.4 Mn 0.6 PO 4 Filtering, washing and drying the precursor suspension at 105 ℃ to obtain a precursor Fe of the lithium ion battery anode material 0.4 Mn 0.6 PO 4 ·H 2 O. See fig. 4.
Example 10
Mixing 2.2L of 2mol/L sodium carbonate solution with 2L of 0.6mol/L ferrous sulfate and 1.4mol/L manganese sulfate solution uniformly, filtering and washing to obtain Fe 0.3 Mn 0.7 CO 3 A solid; dissolving the solid with 4L of 1.3mol/L phosphoric acid solution to form Fe 0.3 Mn 0.7 PO 4 An acid solution; fe is added to 0.3 Mn 0.7 PO 4 The acid solution and 5L of 0.2mol/L potassium permanganate solution are added into a hydrothermal reaction kettle in parallel, and are heated to 92 ℃ and aged for 2 hours to obtain Fe 0.3 Mn 0.7 PO 4 Filtering, washing and drying the precursor suspension at 105 ℃ to obtain a precursor Fe of the lithium ion battery anode material 0.3 Mn 0.7 PO 4 ·H 2 O. See fig. 4.
Test case
Physicochemical analysis was performed on the manganese iron phosphate prepared in example 1-example 10, and specific components are shown in table 1.
Table 1
As can be seen from Table 1, the prepared manganese iron phosphate greatly reduces the contents of heavy metal impurities and sulfur in the finished product, and the iron-manganese ratio is controllable.
Manufacturing of lithium ion battery
1) Preparing a positive electrode plate:
preparing a positive electrode material: the lithium iron manganese phosphate precursor prepared in the embodiment and lithium carbonate are mixed according to Li: mixing the P and the glucose in a molar ratio of 1:1, adding the glucose with the weight percent of 6 percent into the mixed raw material, sanding to the granularity of 100-200 nm, then spray drying, calcining the dried material for 10 hours at the temperature of 750 ℃, and naturally cooling to obtain the anode material. The positive electrode material prepared by the method is used as a positive electrode active material, and the positive electrode active material is prepared by the following steps: SP (superconducting carbon black): PVDF (polyvinylidene fluoride) at a mass ratio of 84:8:8, coating on aluminum foil with the thickness of 20 mu m, drying, rolling, die cutting and punching to obtain the positive electrode plate. A lithium sheet was used as a negative electrode, and a PE separator was used, and 80. Mu.mL of an electrolyte was added dropwise. The electrochemical performance test is carried out on the prepared batteries respectively, and specifically comprises the following steps: performing 1C cycle performance test at 25 ℃; testing the prepared button cell by using a blue electric tester; placing the prepared button cell in an incubator at 25 ℃ for charge and discharge test, wherein the voltage range is 2.0-4.35V, and the charge and discharge of 0.1C are activated for one circle, and then charging and discharging are carried out at constant current and constant voltage of 0.1C; constant current charge and discharge was performed with a current of 0.5C. The test results are shown in Table 2.
Table 2
As can be seen from table 2, the electrical properties are better, the compaction is excellent, and the voltage plateau is stable.
Claims (10)
1. The preparation method of the precursor ferromanganese phosphate of the positive electrode material of the lithium ion battery is characterized by comprising the following steps:
step (1): uniformly mixing carbonate solution and ferric salt and manganese salt solution, filtering and washing to obtain solid phase Fe x Mn (1-x) CO 3 ；
Step (2): forming Fe by using a phosphoric acid solution to the solid phase x Mn (1-x) PO 4 An acid solution;
step (3): the acid solution and the oxidant solution are added into a hydrothermal reaction kettle in parallel to be heated and aged to obtain Fe x Mn (1-x) PO 4 Filtering, washing and drying the precursor suspension to obtain a precursor Fe of the lithium ion battery anode material x Mn (1-x) PO 4 ·H 2 O, wherein 0 < x < 1.
2. The method for preparing the precursor ferric manganese phosphate of the positive electrode material of the lithium ion battery according to claim 1, wherein the carbonate is one of sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate and ammonium bicarbonate, and the concentration of the carbonate is 0.05-5 mol/L.
3. The method for preparing the precursor ferric manganese phosphate of the positive electrode material of the lithium ion battery according to claim 1, wherein the ferric salt is soluble ferric salt, and the soluble ferric salt is selected from one of ferrous chloride, ferrous sulfate and ferrous oxalate.
4. The method for preparing the precursor ferric manganese phosphate of the positive electrode material of the lithium ion battery according to claim 1, wherein the manganese salt is soluble manganese salt, and the concentration of the soluble manganese salt is 0.05-5 mol/L selected from manganese sulfate and manganese nitrate.
5. The method for preparing the precursor ferric manganese phosphate of the positive electrode material of the lithium ion battery according to claim 1, wherein the molar ratio of carbonate to ferric salt and manganese salt is 0.8-5, and the molar ratio of ferric salt to manganese salt is 2:8-9:1.
6. The method for preparing the precursor ferric manganese phosphate of the positive electrode material of the lithium ion battery according to claim 1, wherein the solid phase substance Fe x Mn (1-x) CO 3 Formation of Fe with phosphorus-containing acid solution x Mn (1-x) PO 4 The molar ratio of metal to phosphorus is 0.9-5 when the acid solution is used.
7. The method for preparing the precursor ferric manganese phosphate of the positive electrode material of the lithium ion battery according to claim 1, wherein the solid phase substance Fe x Mn (1-x) CO 3 Formation of Fe with phosphorus-containing acid solution x Mn (1-x) PO 4 When the acid solution is the solution obtained by mixing one or more of phosphoric acid, ammonium phosphate and sodium phosphate with one or more of sulfuric acid, nitric acid, hydrochloric acid, acetic acid and oxalic acid, the concentration of the phosphorus in the acid solution is 0.1-4.5 mol/L, and the pH value of the acid solution is 0-6.
8. The preparation method of the precursor ferric manganese phosphate of the positive electrode material of the lithium ion battery, according to claim 1, wherein the oxidant is one or a combination of more of nitric acid, nitrate, hydrogen peroxide, permanganate, sodium peroxide, persulfate, hypochlorite and ozone, and the concentration of the oxidant is 0.001-5 mol/L.
9. The method for preparing the precursor ferric manganese phosphate of the positive electrode material of the lithium ion battery according to claim 1, wherein the precursor ferric manganese phosphate is Fe x Mn (1-x) PO 4 The molar ratio of the metal amount in the acid solution to the oxidant amount is 0.1-10.
10. The method for preparing the precursor ferric manganese phosphate of the positive electrode material of the lithium ion battery according to claim 1, wherein the precursor ferric manganese phosphate is Fe x Mn (1-x) PO 4 The ratio of the parallel flow rate of the acid solution to the oxidant solution is 0.01 to 10, the heating aging temperature is 75 to 105 ℃, and Fe x Mn (1-x) PO 4 The drying temperature of the filter cake is 55-280 ℃.
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