CN114105118A - Preparation method of carbon-coated lithium iron manganese phosphate and lithium ion battery - Google Patents
Preparation method of carbon-coated lithium iron manganese phosphate and lithium ion battery Download PDFInfo
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- CN114105118A CN114105118A CN202111412239.6A CN202111412239A CN114105118A CN 114105118 A CN114105118 A CN 114105118A CN 202111412239 A CN202111412239 A CN 202111412239A CN 114105118 A CN114105118 A CN 114105118A
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- Prior art keywords
- lithium
- manganese
- phosphate
- carbon
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- 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 title claims abstract description 67
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 54
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000706 filtrate Substances 0.000 claims abstract description 71
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 53
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000002699 waste material Substances 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 45
- 239000011572 manganese Substances 0.000 claims abstract description 42
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 37
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims abstract description 33
- 239000007787 solid Substances 0.000 claims abstract description 33
- 239000002243 precursor Substances 0.000 claims abstract description 31
- 239000002351 wastewater Substances 0.000 claims abstract description 31
- 239000002002 slurry Substances 0.000 claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 claims abstract description 28
- 230000002378 acidificating effect Effects 0.000 claims abstract description 26
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002270 dispersing agent Substances 0.000 claims abstract description 23
- 238000002791 soaking Methods 0.000 claims abstract description 22
- 229910052742 iron Inorganic materials 0.000 claims abstract description 21
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 21
- 238000012360 testing method Methods 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 15
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 10
- 239000011574 phosphorus Substances 0.000 claims abstract description 10
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 4
- 230000001502 supplementing effect Effects 0.000 claims abstract description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 27
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 27
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 claims description 24
- 238000009616 inductively coupled plasma Methods 0.000 claims description 19
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 11
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 11
- 239000011702 manganese sulphate Substances 0.000 claims description 11
- 235000007079 manganese sulphate Nutrition 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
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 238000001694 spray drying Methods 0.000 claims description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 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 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-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
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229940006186 sodium polystyrene sulfonate Drugs 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 238000005660 chlorination reaction Methods 0.000 abstract description 20
- 239000000463 material Substances 0.000 abstract description 9
- 238000004064 recycling Methods 0.000 abstract description 7
- 235000010215 titanium dioxide Nutrition 0.000 description 23
- 238000000498 ball milling Methods 0.000 description 13
- 229910019142 PO4 Inorganic materials 0.000 description 10
- 229940099596 manganese sulfate Drugs 0.000 description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 238000001354 calcination Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- 239000010926 waste battery Substances 0.000 description 2
- 229910011870 LiFe0.9Mn0.1PO4 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- -1 hydrogen ions Chemical class 0.000 description 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 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000003900 soil pollution Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- 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
- C01P2006/10—Solid density
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
Abstract
The invention relates to the technical field of battery materials, in particular to a preparation method of carbon-coated lithium iron manganese phosphate and a lithium ion battery. The preparation method of the carbon-coated lithium iron manganese phosphate comprises the following steps: soaking waste solid lithium iron phosphate separated from a lithium ion battery by using acidic wastewater in a chlorination-process titanium dioxide production process, and performing solid-liquid separation after soaking to obtain a filtrate; carrying out ICP test on the filtrate; supplementing an iron source and/or a manganese source, a lithium source and a phosphorus source, and reacting to obtain a lithium manganese iron phosphate precursor; and uniformly mixing the lithium manganese iron phosphate precursor, a carbon source, water and a dispersing agent to obtain lithium manganese iron phosphate slurry, and sequentially grinding, drying and roasting the lithium manganese iron phosphate slurry to obtain the carbon-coated lithium manganese iron phosphate. The method provided by the invention not only effectively solves the problems of recycling of acidic wastewater and waste solid lithium iron phosphate separated from a lithium ion battery in the production process of titanium dioxide by a chlorination method, but also greatly reduces the production cost of carbon-coated lithium manganese iron phosphate.
Description
Technical Field
The invention relates to the technical field of battery materials, in particular to a preparation method of carbon-coated lithium iron manganese phosphate and a lithium ion battery.
Background
At present, lithium ion secondary batteries using lithium iron phosphate as a positive electrode material gradually become a better choice for electrochemical energy storage due to good safety performance, good high-temperature performance and low cost, occupy most market shares, and have a certain proportion in the power battery market. After the lithium ion battery is cycled for hundreds of times, the internal structure of the battery deforms or collapses, so that the diffusion of lithium ions is inhibited, and the electrode material is inactivated, thereby causing the battery to be scrapped. With the use of a large number of lithium ion batteries, the number of scrapped lithium ion batteries is increasing due to long-time charge-discharge cycles, and a large number of waste lithium ion batteries which cannot meet corresponding energy storage requirements are generated. The active substance in the anode material of the waste battery basically reserves the components and the structure of the active substance before failure. If the waste batteries are directly treated like other wastes, serious environmental pollution is likely to be caused, and the hidden danger of fire caused by short circuit of the batteries also exists. Therefore, it becomes necessary to recycle the lithium battery waste in order to recycle the materials, save the cost, and protect the environment. However, the existing method for recycling the lithium ion battery waste has the defects of complex process, low recycling rate, incomplete recycling and easy generation of secondary pollution.
Titanium dioxide is an important white pigment and is widely applied to the fields of coatings, printing ink and the like. The prior art methods for preparing titanium dioxide can be divided into sulfuric acid methods and chlorination methods. The technological process of producing titanium white powder by chlorination process includes mainly three steps of preparing titanium tetrachloride, oxidizing titanium tetrachloride and surface treatment of titanium dioxide. A large amount of waste acid solution containing hydrogen ions and ferrous ions is generated in the production process of titanium dioxide by a chlorination method. If the treatment is not proper, the problems of resource waste, water body and soil pollution and other environmental pollution are caused.
In view of the above, the present invention is proposed.
Disclosure of Invention
The invention aims to provide a preparation method of carbon-coated lithium iron manganese phosphate, which solves the problem of comprehensive utilization of acidic wastewater in the production process of titanium dioxide by a chlorination method and waste solid lithium iron phosphate in a lithium ion battery.
The second purpose of the invention is to provide a lithium ion battery, which comprises carbon-coated lithium ferric manganese phosphate prepared by taking acid wastewater in the production process of titanium dioxide and waste solid lithium iron phosphate in the lithium ion battery as raw materials, and greatly reduces the production cost of the lithium ion battery.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the invention provides a preparation method of carbon-coated lithium iron manganese phosphate, which comprises the following steps:
(A) soaking waste solid lithium iron phosphate separated from a lithium ion battery by using acidic wastewater in a chlorination-process titanium dioxide production process, and performing solid-liquid separation after soaking to obtain a filtrate;
(B) carrying out ICP (inductively coupled plasma) test on the filtrate to obtain the contents of Li element, Fe element, Mn element and P element in the filtrate;
(C) supplementing an iron source and/or a manganese source according to the mole number x + y of Fe and Mn in the filtrate as 1, wherein: x is 0.6-0.9, and y is 0.1-0.4; according to the molar ratio of Li element to the sum of Fe and Mn elements in the filtrate of 1-1.05: 1 adding a lithium source; according to the molar ratio of P element to the sum of Fe and Mn element in the filtrate of 1: 1 adding a phosphorus source; adjusting the pH value of the filtrate to 8-11, and reacting to obtain a lithium manganese iron phosphate precursor;
(D) and uniformly mixing the lithium manganese iron phosphate precursor, a carbon source, water and a dispersing agent to obtain lithium manganese iron phosphate slurry, and sequentially grinding, drying and roasting the lithium manganese iron phosphate slurry to obtain the carbon-coated lithium manganese iron phosphate.
The invention also provides a lithium ion battery which comprises the carbon-coated lithium iron manganese phosphate prepared by the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention provides a preparation method of carbon-coated lithium iron manganese phosphate, which takes acidic wastewater generated in the production process of titanium dioxide by a chlorination method and waste solid lithium iron phosphate separated from a lithium ion battery as raw materials, effectively solves the problems of recycling the acidic wastewater generated in the production process of the titanium dioxide by the chlorination method and the waste solid lithium iron phosphate in the lithium ion battery, reduces the discharge amount of industrial wastewater and waste residues, and reduces the treatment cost of the waste liquid and the waste residues. The acid wastewater in the production process of titanium dioxide by the chlorination method and the waste solid lithium iron phosphate separated from the lithium ion battery are wide in source and low in price, and the whole preparation method has the advantages of high recovery rate of waste materials, simpler steps, convenience in operation, difficulty in generating secondary pollution and environmental friendliness.
(2) The invention soaks the acid waste water in the production process of titanium dioxide by chlorination method into the waste solid lithium iron phosphate separated from the lithium ion battery, and the obtained filtrate has Li with a certain concentration+、PO4 3-、Fe2+And Mn2+The use of raw materials such as lithium source, phosphorus source, iron source, manganese source and the like can be reduced under the condition of producing the same lithium ferric manganese phosphate. The same effect as that of preparing the lithium manganese iron phosphate by adopting a pure lithium source, an iron source, phosphoric acid and a manganese source can be achieved by controlling the ratio of the four elements, so that the resource loss and the addition of auxiliary materials are reduced, and the production cost is greatly reduced.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 shows Li obtained in example 1 of the present invention1.04Fe0.9Mn0.1PO4SEM image of 10.00kx for/C.
FIG. 2 shows Li obtained in example 1 of the present invention1.04Fe0.9Mn0.1PO4SEM image of 30.00kx for/C.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following detailed description, but those skilled in the art will understand that the following described examples are some, not all, of the examples of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The preparation method of the carbon-coated lithium iron manganese phosphate and the lithium ion battery of the embodiment of the invention are specifically described below.
Some embodiments of the present invention provide a method for preparing carbon-coated lithium iron manganese phosphate, comprising the steps of:
(A) soaking waste solid lithium iron phosphate separated from a lithium ion battery by using acidic wastewater in a chlorination-process titanium dioxide production process, and performing solid-liquid separation after soaking to obtain a filtrate;
(B) carrying out ICP (inductively coupled plasma) test on the filtrate to obtain the contents of Li element, Fe element, Mn element and P element in the filtrate;
(C) supplementing an iron source and/or a manganese source according to the mole number x + y of Fe and Mn in the filtrate as 1, wherein: x is 0.6-0.9, and y is 0.1-0.4; according to the molar ratio of Li element to the sum of Fe and Mn elements in the filtrate of 1-1.05: 1 adding a lithium source; according to the molar ratio of P element to the sum of Fe and Mn element in the filtrate of 1: 1 adding a phosphorus source; adjusting the pH value of the filtrate to 8-11, and reacting to obtain a lithium manganese iron phosphate precursor;
(D) and uniformly mixing the lithium manganese iron phosphate precursor, a carbon source, water and a dispersing agent to obtain lithium manganese iron phosphate slurry, and sequentially grinding, drying and roasting the lithium manganese iron phosphate slurry to obtain the carbon-coated lithium manganese iron phosphate.
The invention takes the acidic wastewater in the production process of titanium dioxide by chlorination process and the waste solid lithium iron phosphate separated from the lithium ion battery as raw materials, and adopts the method that the acidic wastewater directly soaks the waste solid lithium iron phosphate, thereby not only solving the problems of recycling and treating the acidic wastewater and the waste solid lithium iron phosphate in the lithium ion battery in the production process of titanium dioxide by chlorination process, but also reducing the discharge amount of industrial wastewater and waste residues; and the recovery rate of the waste materials is high, the addition of auxiliary materials such as pure lithium sources, iron sources, phosphorus sources, manganese sources and the like in the preparation process is reduced, and the production cost of the carbon-coated lithium manganese iron phosphate is greatly reduced.
In order to ensure the accuracy of the test, ICP is adopted to test the filtrate, and other test methods can be adopted in the process of obtaining the content of Li element, Fe element, Mn element and P element.
In some embodiments of the present invention, the molar ratio of the Fe element to the Mn element is 0.6 to 0.9: 0.1 to 0.4.
In some specific embodiments of the present invention, the molar ratio of the Li element, the Fe element, the Mn element, and the P element is 1.04: 0.9: 0.1: 1, different molar ratios have different influences on the material, and the performance of the material can be further improved by adopting a proper ratio.
In some embodiments of the invention, in the step (a), the mass ratio of the acidic wastewater to the waste solid lithium iron phosphate is 5-50: 1; typically, but not limitatively, for example, the mass ratio of the acidic wastewater to the waste solid lithium iron phosphate is 5: 1. 10: 1. 20: 1. 30: 1. 40: 1 or 50: 1.
in some embodiments of the invention, in the step (A), the soaking time is 2-6 hours, and the soaking temperature is 30-80 ℃; typically, but not by way of limitation, for example, the soaking time is 2h, 3h, 4h, 5h, or 6 h; the soaking temperature is 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃ or 80 ℃; preferably, the soaking time is 4-5 h, and the soaking temperature is 50-70 ℃.
In some embodiments of the invention, in the step (a), the acidic wastewater in the production process of titanium dioxide by chlorination method is obtained by dissolving waste solids collected by a cyclone dust collector with an acidic solution at the lower end of a chlorination furnace, and mainly contains elements of Fe, Mn and Cl; the pH value of the acidic wastewater is 0.1-2; typically, but not by way of limitation, the pH of the acidic wastewater is, for example, 0.1, 0.5, 1, 1.5, or 2.
In some embodiments of the present invention, step (C) further includes washing the obtained lithium manganese iron phosphate precursor with water.
In some embodiments of the invention, in step (C), the iron source comprises one or more of ferric nitrate, ferric chloride and ferric sulfate; preferably, the iron source comprises ferric chloride.
In some embodiments of the invention, in step (C), the source of manganese comprises one or more of manganese nitrate, manganese acetate and manganese sulfate; preferably, the source of manganese comprises manganese sulfate.
In some embodiments of the invention, in step (C), the lithium source comprises one or more of lithium carbonate, lithium hydroxide, lithium acetate, and lithium oxalate; preferably, the lithium source comprises lithium carbonate.
In some embodiments of the invention, in step (C), the source of phosphorus comprises one or more of ammonium monohydrogen phosphate, ammonium dihydrogen phosphate, and ammonium phosphate; preferably, the source of phosphorus comprises ammonium hydrogen phosphate.
In some embodiments of the present invention, in the step (C), the reaction temperature is 80-100 ℃, and the reaction time is 3-5 h; typically, but not by way of limitation, the temperature of the reaction is, for example, 80 ℃, 90 ℃ or 100 ℃; the reaction time is 3h, 4h or 5 h; preferably, the reaction temperature is 90 ℃ and the reaction time is 5 h.
In some embodiments of the invention, in the step (C), the adjusting the pH of the filtrate to 8 to 11 specifically comprises adding an alkali to the filtrate until the pH of the filtrate is 8 to 11; preferably, the pH value of the filtrate is adjusted to 9-10.
In some embodiments of the invention, in step (C), the base comprises sodium carbonate.
In some embodiments of the invention, in step (D), the carbon source comprises one or more of glucose, sucrose, citric acid, graphene, and carbon nanotubes; preferably, the carbon source comprises citric acid.
In some embodiments of the present invention, in the step (D), the mass ratio of the carbon source to the lithium manganese iron phosphate precursor is 1: 10-20; typically, but not limitatively, for example, the mass ratio of the carbon source to the lithium manganese iron phosphate precursor is 1: 10. 1: 13. 1: 14. 1: 15. 1: 16. 1: 17. 1: 18. 1: 19 or 1: 20; preferably, the mass ratio of the carbon source to the lithium ferric manganese phosphate precursor is 1: 20.
in some embodiments of the invention, in step (D), the dispersant comprises one or more of propylene glycol, ethanol, polyethylene oxide, polyvinyl alcohol, sodium polystyrene sulfonate, cetyltrimethylammonium chloride, and octadecyltrimethylammonium chloride polyethylene glycol; preferably, the dispersant comprises propylene glycol.
In some embodiments of the invention, in the step (D), the dispersant accounts for 0.1-5% of the mass of the lithium manganese iron phosphate slurry; typically, but not by way of limitation, for example, the dispersant comprises 0.1%, 1%, 2%, 3%, 4%, or 5% by mass of the lithium manganese iron phosphate slurry; preferably, the dispersant accounts for 1-2% of the mass of the lithium ferric manganese phosphate slurry.
In some embodiments of the present invention, in the step (D), the particle size of the milled lithium manganese iron phosphate slurry is 0.1 to 1 μm; typically, but not by way of limitation, the particle size of the milled lithium ferric manganese phosphate slurry is 0.1 μm, 0.3 μm, 0.5 μm, 0.7 μm, 0.9 μm, or 1 μm, for example.
In some embodiments of the present invention, in the step (D), the lithium ferric manganese phosphate precursor, the carbon source, water and the dispersant are mixed uniformly, which comprises the following steps: uniformly mixing a lithium ferric manganese phosphate precursor and a carbon source to obtain a mixture; and grinding the mixture uniformly, adding water and a dispersing agent, and mixing uniformly to obtain lithium manganese iron phosphate slurry.
In some embodiments of the present invention, in the step (D), the lithium ferric manganese phosphate precursor, the carbon source, water and the dispersant are mixed uniformly, which includes the following steps: putting the lithium ferric manganese phosphate precursor and a carbon source into a vacuum stirrer according to a mass ratio, and performing dry mixing and stirring until the mixture is uniform to obtain a mixture; and grinding the mixture uniformly, adding deionized water, adding a dispersing agent, and carrying out ball milling for 10-15 h under the condition of 600-800 r/min to obtain lithium manganese iron phosphate slurry.
In some embodiments of the present invention, the drying in step (D) comprises subjecting the milled lithium manganese iron phosphate slurry to high-speed spray drying at 220 to 280 ℃.
In some embodiments of the invention, in step (D), the firing comprises the steps of: heating the dried lithium ferric manganese phosphate slurry to 700-800 ℃ under the inert gas atmosphere, and keeping the temperature for 8-10 h; preferably, the inert gas comprises one or more of nitrogen, argon and helium; in a specific embodiment of the invention, the calcination comprises calcination at 720 ℃ for 10h under argon atmosphere.
Some embodiments of the present invention provide a lithium ion battery, including the carbon-coated lithium iron manganese phosphate prepared by the above method for preparing carbon-coated lithium iron manganese phosphate.
The lithium ion battery provided by the invention comprises the carbon-coated lithium ferric manganese phosphate prepared by the method, and the waste material is used as the raw material, so that the production cost of the lithium ion battery is greatly reduced.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
Weighing 100g of waste solid lithium iron phosphate separated from a lithium ion battery, placing the waste solid lithium iron phosphate in 500g of acidic wastewater with the pH value of 0.3 in the production process of titanium dioxide by a chlorination method, soaking for 4 hours at 70 ℃, and filtering to obtain filtrate; carrying out ICP (inductively coupled plasma) test on the filtrate to obtain the contents of Li element, Fe element, Mn element and P element in the filtrate; according to the element mole ratio of nLi: nFe: nMn: nP ═ 1.04: 0.9: 0.1: 1, adding lithium carbonate, manganese sulfate and ammonium hydrogen phosphate into the filtrate; adjusting the pH value of the filtrate to 9.2 by using sodium carbonate, placing the filtrate in a water bath kettle at the temperature of 90 ℃, stirring and reacting for 5 hours, and performing suction filtration, washing and drying to obtain the lithium ferric manganese phosphate precursor.
Mixing a lithium ferric manganese phosphate precursor and citric acid according to a mass ratio of 20: 1, placing the mixture in a vacuum stirrer to be dry-mixed and stirred uniformly; adding 1% of propylene glycol dispersant and 400mL of water, ball-milling for 10h under the condition of 700r/min, and then carrying out high-speed spray drying on slurry obtained by ball-milling at 240 ℃; after drying, calcining for 10h in the atmosphere of argon at 720 ℃ to obtain Li1.04Fe0.9Mn0.1PO4/C。
As shown in FIG. 1, Li prepared in this example1.04Fe0.9Mn0.1PO4SEM image of 10.00kx for/C.
As shown in FIG. 2, Li prepared in this example1.04Fe0.9Mn0.1PO4SEM image of 30.00kx for/C.
Example 2
Weighing 100g of waste solid lithium iron phosphate separated from a lithium ion battery, placing the waste solid lithium iron phosphate in 500g of acidic wastewater with the pH value of 0.27 in the production process of titanium dioxide by a chlorination method, soaking for 4 hours at the temperature of 60 ℃, and filtering to obtain filtrate; carrying out ICP (inductively coupled plasma) test on the filtrate to obtain the contents of Li element, Fe element, Mn element and P element in the filtrate; according to the element mole ratio of nLi: nFe: nMn: nP ═ 1.04: 0.8: 0.2: 1, adding lithium carbonate, manganese sulfate and ammonium hydrogen phosphate into the filtrate; adjusting the pH value of the filtrate to 9.0 by using sodium carbonate, placing the filtrate in a water bath kettle at the temperature of 90 ℃, stirring and reacting for 5 hours, and performing suction filtration, washing and drying to obtain the lithium ferric manganese phosphate precursor.
Mixing a lithium ferric manganese phosphate precursor and citric acid according to a mass ratio of 20: 1, placing the mixture in a vacuum stirrer to be dry-mixed and stirred uniformly; adding 1% of propylene glycol dispersant and 400mL of water, ball-milling for 10h under the condition of 700r/min, and then carrying out high-speed spray drying on slurry obtained by ball-milling at 240 ℃; after drying, calcining for 10h in the atmosphere of argon at 720 ℃ to obtain Li1.04Fe0.8Mn0.2PO4/C。
Example 3
Weighing 100g of waste solid lithium iron phosphate separated from a lithium ion battery, placing the waste solid lithium iron phosphate in 500g of acidic wastewater with the pH value of 0.21 in the production process of titanium dioxide by a chlorination method, soaking for 4 hours at the temperature of 50 ℃, and filtering to obtain filtrate; carrying out ICP (inductively coupled plasma) test on the filtrate to obtain the contents of Li element, Fe element, Mn element and P element in the filtrate; according to the element mole ratio of nLi: nFe: nMn: nP ═ 1.04: 0.7: 0.3: 1, adding lithium carbonate, manganese sulfate and ammonium hydrogen phosphate into the filtrate; adjusting the pH value of the filtrate to 9.0 by using sodium carbonate, placing the filtrate in a water bath kettle at the temperature of 90 ℃, stirring and reacting for 5 hours, and performing suction filtration, washing and drying to obtain the lithium ferric manganese phosphate precursor.
Mixing a lithium ferric manganese phosphate precursor and citric acid according to a mass ratio of 20: 1, placing the mixture in a vacuum stirrer to be dry-mixed and stirred uniformly; adding 1% of propylene glycol dispersant and 400mL of water, ball-milling for 10h under the condition of 700r/min, and then carrying out high-speed spray drying on slurry obtained by ball-milling at 240 ℃; after drying, calcining for 10h in the atmosphere of argon at 720 ℃ to obtain Li1.04Fe0.7Mn0.3PO4/C。
Example 4
Weighing 100g of waste solid lithium iron phosphate separated from a lithium ion battery, placing the waste solid lithium iron phosphate in 1000g of acidic wastewater with the pH value of 0.1 in the production process of titanium dioxide by a chlorination method, soaking the waste solid lithium iron phosphate in the acidic wastewater at the temperature of 30 ℃ for 2 hours, and filtering the waste solid lithium iron phosphate to obtain filtrate; carrying out ICP (inductively coupled plasma) test on the filtrate to obtain the contents of Li element, Fe element, Mn element and P element in the filtrate; according to the element mole ratio of nLi: nFe: nMn: nP ═ 1.04: 0.6: 0.4: 1, adding lithium carbonate, manganese sulfate and ammonium hydrogen phosphate into the filtrate; adjusting the pH value of the filtrate to 8 by using sodium carbonate, placing the filtrate in a water bath kettle at 100 ℃, stirring and reacting for 3 hours, and performing suction filtration, washing and drying to obtain the lithium manganese iron phosphate precursor.
Mixing a lithium ferric manganese phosphate precursor and citric acid according to a mass ratio of 10: 1, placing the mixture in a vacuum stirrer to be dry-mixed and stirred uniformly; adding 5% of propylene glycol dispersant and 400mL of water, ball-milling for 10h under the condition of 700r/min, and then carrying out high-speed spray drying on slurry obtained by ball-milling at 220 ℃; after drying, calcining for 10h in an argon atmosphere at 700 ℃ to obtain Li1.04Fe0.6Mn0.4PO4/C。
Example 5
Weighing 50g of waste solid lithium iron phosphate separated from the lithium ion battery, placing the waste solid lithium iron phosphate in 2500g of acidic wastewater with the pH value of 2 in the production process of titanium dioxide by using a chlorination method, soaking the wastewater for 6 hours at the temperature of 80 ℃, and filtering the wastewater to obtain filtrate; carrying out ICP (inductively coupled plasma) test on the filtrate to obtain the contents of Li element, Fe element, Mn element and P element in the filtrate; according to the element mole ratio of nLi: nFe: nMn: nP ═ 1: 0.9: 0.1: 1, adding lithium carbonate, manganese sulfate and ammonium hydrogen phosphate into the filtrate; adjusting the pH value of the filtrate to 11 by using sodium carbonate, placing the filtrate in a water bath kettle at the temperature of 80 ℃, stirring and reacting for 5 hours, and then carrying out suction filtration, washing and drying to obtain the lithium manganese iron phosphate precursor.
Mixing a lithium ferric manganese phosphate precursor and citric acid according to a mass ratio of 20: 1, placing the mixture in a vacuum stirrer to be dry-mixed and stirred uniformly; adding 0.1% of propylene glycol dispersant and 400mL of water, ball-milling for 10h under the condition of 700r/min, and then carrying out high-speed spray drying on slurry obtained by ball-milling at 280 ℃; after drying, calcining for 8h in the argon atmosphere at 800 ℃ to obtain LiFe0.9Mn0.1PO4/C。
Example 6
Weighing 100g of waste solid lithium iron phosphate separated from a lithium ion battery, placing the waste solid lithium iron phosphate in 3000g of acidic wastewater with the pH value of 1 in the production process of titanium dioxide by a chlorination method, soaking for 4 hours at the temperature of 40 ℃, and filtering to obtain filtrate; carrying out ICP (inductively coupled plasma) test on the filtrate to obtain the contents of Li element, Fe element, Mn element and P element in the filtrate; according to the element mole ratio of nLi: nFe: nMn: nP ═ 1.05: 0.9: 0.1: 1, adding lithium carbonate, manganese sulfate and ammonium hydrogen phosphate into the filtrate; adjusting the pH value of the filtrate to 10 by using sodium carbonate, placing the filtrate in a water bath kettle at the temperature of 90 ℃, stirring and reacting for 4 hours, and then carrying out suction filtration, washing and drying to obtain the lithium manganese iron phosphate precursor.
Mixing a lithium ferric manganese phosphate precursor and citric acid according to a mass ratio of 20: 1, placing the mixture in a vacuum stirrer to be dry-mixed and stirred uniformly; adding 3% of propylene glycol dispersant and 400mL of water, ball-milling for 10h under the condition of 700r/min, and then carrying out high-speed spray drying on slurry obtained by ball-milling at 260 ℃; after drying, calcining for 9h in argon atmosphere at 750 ℃ to obtain Li1.05Fe0.9Mn0.1PO4/C。
Comparative example 1
This comparative example refers to the preparation of example 1, differing only in that the molar ratio of the elements nLi: nFe: nMn: nP ═ 1.0: 0.3: 0.7: 1, adding lithium carbonate, manganese sulfate and ammonium hydrogen phosphate into the filtrate.
Comparative example 2
This comparative example refers to the preparation of example 1, differing only in that the molar ratio of the elements nLi: nFe: nMn: nP ═ 1.0: 0.1: 0.9: 1, adding lithium carbonate, manganese sulfate and ammonium hydrogen phosphate into the filtrate.
Test examples
The carbon-coated lithium manganese iron phosphate prepared in examples 1 to 6 and comparative examples 1 to 2 was subjected to physicochemical index and electrochemical property tests, and the results are shown in table 1.
The compaction density test method comprises the following steps: the measurement was carried out according to the measurement method specified in appendix L of GB/T2433and 2009.
Conductivity test method: the measurement was carried out according to the measurement method specified in appendix G of GB/T30835-2014.
Electrochemical test method: the preparation of the anode material comprises the following steps of coating carbon-coated iron manganese phosphate powder: super P: PVDF 96: 2: 2, mixing slurry according to the proportion; and coating, punching and drying the mixed slurry, wherein the negative electrode material is a metal lithium sheet. The cell was sealed and left to stand for 10 hours before testing. And (3) testing the button type half cell by a CT2001A cell testing system at 25 ℃, wherein the testing voltage range is 2V-4.4V, the 1C circulating multiplying power test is carried out, and the 0.1C first reversible specific capacity test is carried out.
TABLE 1
As can be seen from table 1, the carbon-coated lithium manganese iron phosphate prepared according to the embodiments of the present invention has good electrical properties. As can be seen from comparison of examples 1-6 with comparative examples 1-2, the performance of the material can be further improved by adopting a proper ratio.
In conclusion, the preparation method of the carbon-coated lithium iron manganese phosphate not only effectively solves the problems of recycling of acidic wastewater generated in the production process of titanium dioxide by a chlorination method and waste solid lithium iron phosphate in a lithium ion battery, but also reduces the use of raw materials such as a lithium source, a phosphorus source, an iron source, a manganese source and the like, reduces the loss of resources and the addition of auxiliary materials, greatly reduces the production cost, and the prepared carbon-coated lithium iron manganese phosphate has excellent electrochemical performance.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made without departing from the spirit and principle of the present invention shall be included in the protection of the present invention.
Claims (10)
1. A preparation method of carbon-coated lithium iron manganese phosphate is characterized by comprising the following steps:
(A) soaking waste solid lithium iron phosphate separated from a lithium ion battery by using acidic wastewater in a chlorination-process titanium dioxide production process, and performing solid-liquid separation after soaking to obtain a filtrate;
(B) performing ICP (inductively coupled plasma) test on the filtrate to obtain the contents of Li element, Fe element, Mn element and P element in the filtrate;
(C) supplementing an iron source and/or a manganese source according to the mole number x + y of Fe and Mn in the filtrate as 1, wherein: x is 0.6-0.9, and y is 0.1-0.4; according to the molar ratio of Li element to the sum of Fe and Mn elements in the filtrate of 1-1.05: 1 adding a lithium source; according to the molar ratio of the P element to the sum of Fe and Mn elements in the filtrate of 1: 1 adding a phosphorus source; adjusting the pH value of the filtrate to 8-11, and reacting to obtain a lithium manganese iron phosphate precursor;
(D) and uniformly mixing the lithium manganese iron phosphate precursor, a carbon source, water and a dispersing agent to obtain lithium manganese iron phosphate slurry, and sequentially grinding, drying and roasting the lithium manganese iron phosphate slurry to obtain the carbon-coated lithium manganese iron phosphate.
2. The method for preparing carbon-coated lithium iron manganese phosphate according to claim 1, wherein in the step (A), the mass ratio of the acidic wastewater to the waste solid lithium iron phosphate is 5-50: 1;
preferably, the soaking time is 2-6 h, and the soaking temperature is 30-80 ℃;
preferably, the pH value of the acidic wastewater is 0.1-2.
3. The method for preparing carbon-coated lithium iron manganese phosphate according to claim 1, wherein in step (C), the iron source comprises one or more of ferric nitrate, ferric chloride and ferric sulfate;
preferably, the manganese source comprises one or more of manganese nitrate, manganese acetate and manganese sulphate;
preferably, the lithium source comprises one or more of lithium carbonate, lithium hydroxide, lithium acetate and lithium oxalate;
preferably, the source of phosphorus comprises one or more of ammonium monohydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate.
4. The method for preparing carbon-coated lithium iron manganese phosphate according to claim 1, wherein in the step (C), the reaction temperature is 80-110 ℃, and the reaction time is 3-5 h;
preferably, the adjusting the pH value of the filtrate to 8-11 specifically comprises adding alkali to the filtrate until the pH value of the filtrate is 8-11;
preferably, the pH value of the filtrate is adjusted to 9-10;
preferably, the base comprises sodium carbonate.
5. The method for preparing carbon-coated lithium iron manganese phosphate according to claim 1, wherein in step (D), the carbon source comprises one or more of glucose, sucrose, citric acid, graphene and carbon nanotubes;
preferably, the mass ratio of the carbon source to the lithium ferric manganese phosphate precursor is 1: 10 to 20.
6. The method for preparing carbon-coated lithium iron manganese phosphate according to claim 1, wherein in step (D), the dispersant comprises one or more of propylene glycol, ethanol, polyethylene oxide, polyvinyl alcohol, sodium polystyrene sulfonate, cetyltrimethylammonium chloride and octadecyltrimethylammonium chloride polyethylene glycol;
preferably, the dispersant accounts for 0.1-5% of the mass of the lithium ferric manganese phosphate slurry.
7. The method for preparing carbon-coated lithium iron manganese phosphate according to claim 1, wherein in the step (D), the particle size of the milled lithium iron manganese phosphate slurry is 0.1-1 μm.
8. The method for preparing carbon-coated lithium iron manganese phosphate according to claim 1, wherein in the step (D), the lithium iron manganese phosphate precursor, the carbon source, water and the dispersing agent are mixed uniformly, and the method comprises the following steps:
uniformly mixing the lithium ferric manganese phosphate precursor and the carbon source to obtain a mixture;
and grinding the mixture uniformly, adding water and a dispersing agent, and mixing uniformly to obtain lithium manganese iron phosphate slurry.
9. The method for preparing carbon-coated lithium iron manganese phosphate according to claim 1, wherein in the step (D), the drying comprises performing high-speed spray drying on the ground lithium iron manganese phosphate slurry at 220-280 ℃;
the roasting comprises the following steps: and under the atmosphere of inert gas, heating the dried lithium ferric manganese phosphate slurry to 700-800 ℃, and keeping the temperature for 8-10 hours.
10. A lithium ion battery comprising the carbon-coated lithium iron manganese phosphate prepared by the method for preparing carbon-coated lithium iron manganese phosphate according to any one of claims 1 to 9.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114620703A (en) * | 2022-03-31 | 2022-06-14 | 重庆长安新能源汽车科技有限公司 | Carbon-coated lithium manganese iron phosphate composite material and preparation method thereof |
| CN114899371A (en) * | 2022-04-29 | 2022-08-12 | 佛山市德方纳米科技有限公司 | Low-water-content cathode material, preparation method thereof and lithium ion battery |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105470510A (en) * | 2016-01-11 | 2016-04-06 | 山东玉皇新能源科技有限公司 | Modified lithium iron manganese phosphate positive electrode material and preparation method therefor |
| CN106997975A (en) * | 2017-06-06 | 2017-08-01 | 安徽安凯汽车股份有限公司 | A kind of method of waste lithium iron phosphate battery and lithium manganate battery regeneration |
| CN111333048A (en) * | 2020-03-10 | 2020-06-26 | 桑顿新能源科技(长沙)有限公司 | Method for preparing lithium manganese iron phosphate by using waste lithium iron phosphate and lithium manganate materials |
| WO2020134773A1 (en) * | 2018-12-29 | 2020-07-02 | 宁德时代新能源科技股份有限公司 | Method for recovering and preparing lithium iron phosphate cathode material |
| CN112520777A (en) * | 2020-12-03 | 2021-03-19 | 山东鲁北企业集团总公司 | Process for preparing calcium chloride by using byproduct hydrochloric acid slag water of titanium white |
-
2021
- 2021-11-25 CN CN202111412239.6A patent/CN114105118A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105470510A (en) * | 2016-01-11 | 2016-04-06 | 山东玉皇新能源科技有限公司 | Modified lithium iron manganese phosphate positive electrode material and preparation method therefor |
| CN106997975A (en) * | 2017-06-06 | 2017-08-01 | 安徽安凯汽车股份有限公司 | A kind of method of waste lithium iron phosphate battery and lithium manganate battery regeneration |
| WO2020134773A1 (en) * | 2018-12-29 | 2020-07-02 | 宁德时代新能源科技股份有限公司 | Method for recovering and preparing lithium iron phosphate cathode material |
| CN111333048A (en) * | 2020-03-10 | 2020-06-26 | 桑顿新能源科技(长沙)有限公司 | Method for preparing lithium manganese iron phosphate by using waste lithium iron phosphate and lithium manganate materials |
| CN112520777A (en) * | 2020-12-03 | 2021-03-19 | 山东鲁北企业集团总公司 | Process for preparing calcium chloride by using byproduct hydrochloric acid slag water of titanium white |
Non-Patent Citations (1)
| Title |
|---|
| 肖成伟: "《电动汽车工程手册 第4卷 动力蓄电池》", vol. 1, 机械工业出版社, pages: 73 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114620703A (en) * | 2022-03-31 | 2022-06-14 | 重庆长安新能源汽车科技有限公司 | Carbon-coated lithium manganese iron phosphate composite material and preparation method thereof |
| CN114899371A (en) * | 2022-04-29 | 2022-08-12 | 佛山市德方纳米科技有限公司 | Low-water-content cathode material, preparation method thereof and lithium ion battery |
| CN114899371B (en) * | 2022-04-29 | 2024-03-19 | 深圳市德方纳米科技股份有限公司 | Low-water-content positive electrode material, preparation method thereof and lithium ion battery |
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