CN104103831A - Method for preparing multi-doped lithium iron phosphate through converter sludge - Google Patents
Method for preparing multi-doped lithium iron phosphate through converter sludge Download PDFInfo
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- CN104103831A CN104103831A CN201410350243.8A CN201410350243A CN104103831A CN 104103831 A CN104103831 A CN 104103831A CN 201410350243 A CN201410350243 A CN 201410350243A CN 104103831 A CN104103831 A CN 104103831A
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- Prior art keywords
- doped lithium
- converter mud
- ferrous phosphate
- prepare
- component doped
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- 238000000034 method Methods 0.000 title 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 title abstract description 7
- 239000010802 sludge Substances 0.000 title abstract description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000002994 raw material Substances 0.000 claims abstract description 28
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000498 ball milling Methods 0.000 claims abstract description 22
- 239000002245 particle Substances 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 12
- 229910052742 iron Inorganic materials 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 238000000227 grinding Methods 0.000 claims abstract description 11
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 9
- 239000010452 phosphate Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 7
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 7
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 7
- 239000007800 oxidant agent Substances 0.000 claims abstract description 7
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 5
- 239000002270 dispersing agent Substances 0.000 claims abstract description 5
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 40
- 229910052744 lithium Inorganic materials 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 34
- 229940116007 ferrous phosphate Drugs 0.000 claims description 30
- 229910000155 iron(II) phosphate Inorganic materials 0.000 claims description 30
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 claims description 30
- IPBYARKNCJJHKZ-UHFFFAOYSA-L [Fe+2].O.[PH2](=O)[O-].[PH2](=O)[O-] Chemical compound [Fe+2].O.[PH2](=O)[O-].[PH2](=O)[O-] IPBYARKNCJJHKZ-UHFFFAOYSA-L 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 14
- 238000000967 suction filtration Methods 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000706 filtrate Substances 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 239000013049 sediment Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000004677 Nylon Substances 0.000 claims description 8
- 229920001778 nylon Polymers 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 7
- 239000013589 supplement Substances 0.000 claims description 7
- 238000004458 analytical method Methods 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 238000002441 X-ray diffraction Methods 0.000 claims description 5
- 239000000470 constituent Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 230000008020 evaporation Effects 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000002386 leaching Methods 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- KVCWSJZUKMSPLM-UHFFFAOYSA-N O.O[PH2]=O Chemical compound O.O[PH2]=O KVCWSJZUKMSPLM-UHFFFAOYSA-N 0.000 claims description 4
- 235000013312 flour Nutrition 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 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 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- 238000013459 approach Methods 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- -1 polypropylene Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 238000004364 calculation method Methods 0.000 claims description 2
- 239000004567 concrete Substances 0.000 claims description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 230000004044 response Effects 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- RQKNQWUJROKKEQ-UHFFFAOYSA-K iron(3+);phosphate;hydrate Chemical compound [OH-].[Fe+3].OP([O-])([O-])=O RQKNQWUJROKKEQ-UHFFFAOYSA-K 0.000 abstract 2
- 238000001308 synthesis method Methods 0.000 abstract 1
- 239000005955 Ferric phosphate Substances 0.000 description 18
- 229940032958 ferric phosphate Drugs 0.000 description 18
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 18
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 18
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 15
- 229910052493 LiFePO4 Inorganic materials 0.000 description 12
- 229910052782 aluminium Inorganic materials 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 229910052749 magnesium Inorganic materials 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- 229910052725 zinc Inorganic materials 0.000 description 7
- 229910010710 LiFePO Inorganic materials 0.000 description 6
- 229910052791 calcium Inorganic materials 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 6
- 229910052748 manganese Inorganic materials 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 230000036571 hydration Effects 0.000 description 5
- 238000006703 hydration reaction Methods 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 239000004411 aluminium Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 229910021653 sulphate ion Inorganic materials 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 210000003298 dental enamel Anatomy 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- RFGNMWINQUUNKG-UHFFFAOYSA-N iron phosphoric acid Chemical compound [Fe].OP(O)(O)=O RFGNMWINQUUNKG-UHFFFAOYSA-N 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 238000009628 steelmaking Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 230000017105 transposition Effects 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229960004793 sucrose Drugs 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- 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
-
- 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 method for preparing multi-doped lithium iron phosphate through converter sludge. The method comprises the steps as follows: (1) baking and grinding the converter sludge to obtain a fine reaction raw material; (2) performing acidolysis treatment on the reaction raw material obtained in Step (1) with a sulfuric acid solution, after acidolysis, adding an oxidizing agent in the solution, then adding a phosphate radial solution, continuously stirring the solution after the set PH value is reached through reactions, and washing precipitated particles to obtain an amorphous iron phosphate hydrate product; (3) drying the iron phosphate hydrate obtained in Step (2), adding lithium salt and a dispersing agent, performing ball milling on the mixture in a ball mill, and adding a carbon source after drying to obtain the carbon-coated multi-doped lithium iron phosphate. The method has the benefits that the converter sludge is used for providing an iron source and various doping element sources, so that the synthesis cost of the lithium iron phosphate is reduced, the limitation that all raw materials come from chemical reagents in a traditional synthesis method is broken through, and meanwhile, a feasible way is provided for the high-added-value utilization of the converter sludge.
Description
Technical field
The present invention relates to anode material for lithium-ion batteries preparation field, relate in particular to a kind of method of utilizing converter mud to prepare multi-component doped lithium ferrous phosphate.
Background technology
Converter mud is the pitchy particle that the dust that overflows with furnace gas in convertor steelmaking process obtains through wet dedusting, because its unique physicochemical properties make its application in steel plant limited, although for example can solve large problem of utilizing of revolving furnace mud as iron-bearing material production sintering deposit, but sludge moisture content is high, fine size, too large with the granularmetric composition great disparity of other raw materials for sintering, cause the segregation of raw materials for sintering composition and the deterioration of sintering deposit gas permeability, affect the product quality of sintering deposit, and contain P as pneumatic steelmaking flux etc. because of it, harmful elements such as S and its consumption is restricted etc.And in converter mud, contain a large amount of valuable metal elements, as iron, magnesium, manganese, zinc etc., reported at present and utilized mud to prepare highly purified chemical product mainly for a great number of elements Fe in revolving furnace mud, and other useful metallic elements are out in the cold, cause the waste of resource.
LiFePO4 is because having environmental friendliness, safe, the good first-selection that becomes anode material for lithium-ion batteries of cycle performance.And its intrinsic low electronic conductivity and ionic conductivity make it need in actual applications to adopt a series of measures to improve, general method is to utilize carbon to be coated and metal ion mixing.That in the preparation process of doped lithium ferric phosphate, generally takes at present three adds the LiFePO4 of the synthetic pure phase with suitable doping ratio of a small amount of chemical reagent in main material, significantly improves its ionic conductivity.
Flourish along with national ev industry, will constantly increase the demand of LiFePO4, carry out the synthetic cost of material that makes of LiFePO4 merely higher with pure chemistry reagent, cause battery product price to be difficult to decline.The synthetic method of therefore seeking the LiFePO4 of low cost, high-quality has important practical significance.And converter mud is the discarded object in convertor steelmaking process, along with a large amount of converter mud of the annual generation of increase of iron and steel output, wherein contain a large amount of ferro elements and the transition metal of lot of trace, these metallic element majorities are the doped chemicals in LiFePO4 that are entrained in of having reported.Therefore, seek source of iron and the doped chemical source of suitable preparation path using the ferro element in converter mud and multiple transition metal as doped lithium ferric phosphate, thereby breakthrough LiFePO4 synthesis material only derives from the limitation of chemical reagent, significantly reduce the preparation cost of LiFePO4.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of method of utilizing converter mud to prepare multi-component doped lithium ferrous phosphate is provided, reduce the synthetic cost of the coated multi-component doped lithium ferrous phosphate of carbon, for the high value added utilization of converter mud provides feasible path.
The present invention is achieved through the following technical solutions: a kind of method of utilizing converter mud to prepare multi-component doped lithium ferrous phosphate, comprises following methods step: the preliminary treatment of S1. converter mud: converter mud obtains tiny reaction raw materials through baking and grinding; S2. hypophosphite monohydrate is iron standby: utilize sulfuric acid solution to carry out acidolysis processing above-mentioned steps S1 gained reaction raw materials, after acidolysis, in solution, add oxidant and phosphate radical solution, rear the continuing of pH value that question response reaches setting stirs, and obtains unformed hypophosphite monohydrate iron product through washing precipitation particle; S3. the coated multi-component doped lithium ferrous phosphate of carbon is synthetic: unformed above-mentioned steps gained hypophosphite monohydrate iron is dried, add lithium salts and dispersant, ball milling post-drying in ball mill, dries in afterproduct and add carbon source, obtains the coated multi-component doped lithium ferrous phosphate of carbon.
Preferably, in described step S1, baking temperature is 80～100 DEG C, and material tiling thickness is 10～50mm, and baking time is 3～5 hours, takes pendulum-type flour mill or ball mill to carry out grinding to dry converter mud.
Preferably, described step S2 acidolysis utilizes X-fluorescence diffraction approach and X-ray diffraction method respectively reaction raw materials to be carried out to constituent analysis and material phase analysis before processing.
Preferably, step S2 hypophosphite monohydrate is iron for comprising following concrete steps: (1) accurately takes reaction raw materials, determine constituent content and the physical form of converter mud by X-fluorescence and X ray, calculate the amount of required sulfuric acid with this, the sulfuric acid solution of configuration 1～3mol/L, wherein sulfuric acid content is calculated value 100～103%; Treat that bath temperature is elevated to 70～90 DEG C reaction raw materials is put into sulfuric acid solution, in acidolysis process, supplement the moisture of evaporation to keep liquid level constant, reaction continues 0.5～2h, after pH is stable, supplement deionized water, guarantee that the sulfate that acidolysis generates all dissolves, and prevents that sulphate crystal from separating out; (2) suction filtration, washing leaching cake 2～3 times, suction filtration to filtrate is not suspended thing; (3) in the time that being down to 60～70 DEG C, water-bath temperature adds while stirring oxidant and phosphate radical solution in filtrate, add alkalescence to regulate reagent to regulate pH value to 2～5, in the water-bath of 60～70 DEG C, stir 0.5～1h, then carry out suction filtration with quick filter paper, the baking oven that after washing gained sediment 3～4 times, sediment is placed in to 80～120 DEG C is dried.
Preferably, the H that described oxidant is 30%
2o
2, dense HNO
3, HClO
4in one or several mixture.
Preferably, described phosphate radical solution is selected from the K in SPA, soluble phosphate
3pO
4, Na
3pO
4, (NH
4)
3pO
4in one or several mixture.
Preferably, the alkalescence using regulates the dense NH that reagent is 30%
3h
2the mixed solution of one or several in O or dense NaOH, dense KOH solution.
Preferably, the synthesis step of the coated multi-component doped lithium ferrous phosphate of carbon is as follows:
(1) above-mentioned steps is obtained to unformed hypophosphite monohydrate iron dries at 80～120 DEG C, utilize the constitution water number of TG-DTA analytical calculation hypophosphite monohydrate iron, according to chemical equation with addition of lithium salts, the nylon tank of the agate ball that is equipped with different-grain diameter will be placed in addition of good reaction raw materials, taking ethanol, methyl alcohol or isopropyl alcohol as dispersant, in planetary ball mill, after ball milling a few hours, take out and dry;
(2) by dry material with addition of carbon source, after mixing, put into crucible, be placed in reacting furnace and carry out synthetic reaction, 5～10 DEG C/min of reacting furnace heating rate, synthesis reaction temperature is controlled in 680～750 DEG C and is incubated 8～10 hours under a certain fixed temperature, obtains the coated multi-component doped lithium ferrous phosphate of needed carbon.
Preferably, lithium salts is selected from as LiOHH
2o, Li
2cO
3, CH
3one in COOLi.
Preferably, described carbon source is selected from the one in polypropylene, sucrose or glucose.
Beneficial effect of the present invention is, utilize converter mud to provide source of iron and multiple doped chemical source to reach the object that reduces the synthetic cost of LiFePO4, break through traditional synthetic method Raw all from the limitation of chemical reagent, simultaneously for the high value added utilization of converter mud provides feasible approach.
Brief description of the drawings
Fig. 1 is the selected converter mud XRD analysis result of the present invention;
Fig. 2 is the interpretation of result of multi-element doping hypophosphite monohydrate iron, (a) TG-DTA of hypophosphite monohydrate iron analyzes, (b) the XRD collection of illustrative plates of the unformed ferric phosphate of hydration, dehydration amorphous state ferric phosphate, dehydration crystallne phosphoric acid iron, (c) the unformed ferric phosphate SEM figure of hydration, (d) the SEM figure of dehydration crystallne phosphoric acid iron;
Fig. 3 is multi-element doping LiFePO
4the physical property of/C characterizes, (a) multi-element doping LiFePO
4the XRD figure of/C, (b) multi-element doping LiFePO
4the SEM figure of/C;
Fig. 4 is the charging and discharging curve of three kinds of synthetic carbon-coated LiFePO 4 for lithium ion batteries of formula,
Fig. 5 accounts for lithium position according to aluminium to prepare the C-V curve that LiFePO4 and pure reagent are prepared LiFePO4.
Embodiment
Below, by specific embodiment, technical scheme of the present invention is elaborated by reference to the accompanying drawings.
The selected converter mud of the present invention becomes to be analyzed as follows:
The main chemical compositions (wt%) of table 1 revolving furnace mud raw ore
Consult Fig. 1 simultaneously, from X-fluorescence and the XRD analysis result of converter mud, major metal element in converter mud is iron, form with FeO exists, next is calcium and magnesium, form with carbonate exists, and is that silicon exists with the form of silicate again, is finally that micro-transition metal exists with the form of composite oxides.
The transfers such as needed Fe element and multiple valuable metal element M g, Mn, Zn, Al can be entered in filtrate by sulfuric acid solution, a large amount of calcium forms calcium sulfate and is filtered and removes, and the dissolubility of hydrated calcium sulfate in acid solution is along with the acidity of solution and the variation of temperature and change, and selects suitable sulphuric acid and suitable acidolysis temperature to guarantee that excessive calcium constituent exists and is removed with calcium sulfate at this.
Embodiment 1
S1. the preliminary treatment of converter mud
Obtain dry and the tiny uniform reaction raw materials of particle by converter mud being toasted with grinding step, baking temperature is 80 DEG C, material tiling thickness is 10mm, baking time is 4 hours, take pendulum-type flour mill to carry out grinding to dry converter mud, finally obtain the reaction raw materials that particle is tiny;
S2. multi-element doping hypophosphite monohydrate iron is synthetic
(1) accurately take S1 step gained reaction raw materials 50g, add the sulfuric acid solution of 254ml, 3mol/L, treat that bath temperature is elevated to 80 DEG C 50g revolving furnace mud is put into sulfuric acid solution, in acidolysis process, supplement the moisture of evaporation, keep liquid level constant, supplementary deionized water after acidolysis completes, makes liquid level reach 400ml, guarantee that the sulfate that acidolysis generates all dissolves, and prevents that sulphate crystal from separating out;
(2) above-mentioned solution is carried out to suction filtration, washing leaching cake 2～3 times, suction filtration to filtrate is not suspended thing;
(3) in the time that water-bath temperature is down to 70 DEG C, be 30% hydrogen peroxide, the SPA of 36ml to adding while stirring 33ml concentration in filtrate, stop adding concentrated ammonia liquor by 30% concentrated ammonia liquor regulator solution pH value to 3.5, in the water-bath of 70 DEG C, stir half an hour, then carry out suction filtration with quick filter paper, the baking oven that after washing gained sediment 3～4 times, sediment is placed in to 80～120 DEG C is dried.
Above-mentioned reaction equation is:
FeSO
4+H
2O
2+H
3PO
4+2NH
3·H
2O＝＝FePO
4·1.5H
2O↓+(NH
4)2SO
4+2H
2O+1/2O
2↑
Or be:
6FeSO
4+6H
3PO
4+NaClO
3+12NaOH＝＝6FePO
4·2H
2O↓+6Na
2SO
4+NaCl+3H
2O
Consult accompanying drawing 2, the interpretation of result of multi-element doping hypophosphite monohydrate iron, can find out from the TG-DTA spectrogram of gained ferric phosphate, lose the process of Free water at 80～150 DEG C for hypophosphite monohydrate iron, 150～370 DEG C is the process that gained hypophosphite monohydrate iron loses constitution water, and the molecular formula that can obtain as calculated hypophosphite monohydrate iron is FePO
41.5H
2o, near the exothermic peak 545 DEG C is ferric phosphate crystallization process, near the exothermic peak 630 DEG C is the crystal transfer process of ferric phosphate.From the XRD spectra of ferric phosphate, consistent with TG-DTA analysis result, 545 DEG C of calcinings are amorphous substance, at 680 DEG C, calcining obtains the ferric phosphate of crystalline state, and occur without any impurity peaks, associative list 2 data can learn, multiple element doping enters in the structure cell of ferric phosphate instead of forms impurity phase.Amorphous state hypophosphite monohydrate iron particle prepared by SEM figure demonstration homogeneous precipitation method is tiny evenly, regular, even through the crystallne phosphoric acid iron pattern after calcining.
Table 2 is chemical component tables of the multi-element doping ferric phosphate prepared of revolving furnace mud raw ore and homogeneous precipitation method, as can be seen from the table, multiple valuable element in revolving furnace mud is successfully retained in presoma ferric phosphate, the rate of recovery of Fe, Al, Zn, Mn, Mg reaches respectively 90.82wt.%, 95wt.%, 64wt.%, 24wt.%, 4wt.% as calculated, and atomic ratio: ∑ (FeCaMgZnAl): P:O ≈ 1:1:4, i.e. the molecular formula FePO of ferric phosphate
4.
The chemical composition contrast of table 2 converter mud raw ore and synthetic ferric phosphate
S3. the coated multi-component doped lithium ferrous phosphate of carbon is synthetic
Allocate synthetic hydration multi-element doping ferric phosphate into lithium source and carbon source, reaction equation is as follows:
(1) prepare burden according to equation (a), take FePO
41.5H
2o.8g, take LiOHH according to the ratio of lithium excessive 2%
2o1.925g, puts into both in the nylon tank that is equipped with different-grain diameter agate ball, carries out ball milling mix taking absolute ethyl alcohol as decentralized medium, and level control is at nylon tank volume below 2/3.Ball milling parameter is: rotating, 0.5h transposition once, Ball-milling Time 4.0h, rotating speed is 350r/min.After taking-up, sample is placed in to glass container, considers safety factor, in baking oven, be first dried to without obvious ethanol liquid with 60 DEG C, and then with 110 DEG C of baking 2.0h.Last same ball milling and drying work repeats once, to obtain LiFePO
4presoma.
(2) LiFePO mixing according to every 10g ball milling
4presoma is allocated 2.8g polypropylene powder into, and in agate mortar, simple ground and mixed, then proceeds in enamel crucible manual jolt ramming.Be placed in tubular type constant temperature oven, rise to 700 DEG C of insulation 8.0h with the heating rate of 8 DEG C/min, be cooled to 80 DEG C of following samples that take out with stove, make LiFePO
4/ C.
As can be seen from Table 2, in polynary hydration ferric phosphate, mainly contain Ca, Mg, Zn, Al, Mn equal size doped chemical not etc., the elements such as the research conclusion according to most researchers: Ca, Mg, Zn, Mn occupy the ionic conductivity that Fe (M2) position is more conducive to improve positive electrode, and Al element occupies the more excellent existence dispute of Li position M1 or Fe (M2) position.And utilize converter mud to contain multiple doped chemical in preparing multi-component doped lithium ferrous phosphate at this, the residing environment difference of aluminium atom, therefore, in the process of preparing multi-component doped lithium ferrous phosphate, by aluminium element according to Li doped (M1) position and doped F e (M2) the synthetic multi-component doped lithium ferrous phosphate of preparing burden, and with pure reagent FeSO
4the carbon-coated LiFePO 4 for lithium ion batteries of taking identical homogeneous precipitation method to prepare contrasts.
(1) occupying Fe (M2) according to all doped chemicals prepares burden:
N (∑ (FeCaMgZnAlMn) PO
41.5H
2o): n (LiOHH
2o)=1:1.02 takes material;
(2) occupy Li (M1) according to Al element, the elements such as Ca, Mg, Zn, Mn occupy Fe (M2) and prepare burden: n ((Al) PO41.5H of ∑ (FeCaMgZnMn)
2o): n (LiOHH
2o)=1:1.016 takes material;
(3) take and utilize pure reagent FeSO
4the hypophosphite monohydrate iron synthesizing iron lithium phosphate of taking identical homogeneous precipitation method to prepare, contrasts: n (FePO
41.5H
2o): n (LiOHH
2o)=1:1.02 prepares burden.
After above three kinds of materials have taken, pass through ball milling, join carbon source, high temperature solid state reaction synthesizing iron lithium phosphate, and synthetic sample is carried out to XRD, sem analysis.
Consulting Fig. 3 is multi-element doping LiFePO
4the physical property of/C characterizes, and can find out prepared LiFePO from Fig. 3 (a)
4/ C perfect crystalline, does not have obvious impurity peaks to occur, illustrates that multiple doped chemical in the polynary hydration ferric phosphate of presoma adulterates and enter LiFePO as Ca, Mg, Mn, Zn, Al etc. in pyrocarbon thermal reduction process
4in/C structure cell and non-formation impurity phase.Fig. 3 (b) shows prepared multi-element doping LiFePO
4/ C form rule and even particle size distribution, show with homogeneous precipitation method prepare multi-element doping hypophosphite monohydrate iron, two step ball milling one step pyrocarbon thermal reductions are conducive to prepare the multi-element doping LiFePO that particle diameter is even, pattern is regular
4/ C.
Consulting Fig. 4 and Fig. 5 is multi-element doping LiFePO
4the electrochemical properties test result of/C, it shown in Fig. 4, is the charging and discharging curve of three kinds of distribution synthesizing iron lithium phosphates, account for as seen from the figure the poor minimum of charging/discharging voltage platform of the synthetic carbon-coated LiFePO 4 for lithium ion batteries in lithium position according to aluminium, the polarization minimum that shows this material, can draw identical conclusion in conjunction with C-V curve.Under low current density, utilizing the charge/discharge capacity of LiFePO4 prepared by pure reagent the highest, may be that aluminium accounts for lithium position and reduced the content of reversible lithium and caused volume lowering.But the reaction invertibity of learning multi-component doped lithium ferrous phosphate from C-V figure is more excellent, demonstrates more excellent performance at high rate charge-discharge.
Embodiment 2
S1. the preliminary treatment of converter mud
Obtain dry and the tiny uniform reaction raw materials of particle by converter mud being toasted with grinding step, baking temperature is 100 DEG C, and material tiling thickness is 50mm, and baking time is 3 hours, take ball mill to carry out grinding to dry converter mud, obtain the tiny reaction raw materials of particle;
S2. multi-element doping hypophosphite monohydrate iron is synthetic
(1) accurately take S1 step gained reaction raw materials 50g, add the sulfuric acid solution of 360ml, 2mol/L, treat that bath temperature is elevated to 70 DEG C 50g reaction raw materials is put into sulfuric acid solution, in acidolysis process, supplement the moisture of evaporation, keep liquid level constant, supplementary deionized water after acidolysis completes, makes liquid level reach 380ml, guarantee that the sulfate that acidolysis generates all dissolves, and prevents that sulphate crystal from separating out;
(2) above-mentioned solution is carried out to suction filtration, washing leaching cake 2～3 times, suction filtration to filtrate is not suspended thing;
(3) in the time that being down to 60 DEG C, water-bath temperature adds while stirring the dense HNO of 40ml in filtrate
3, 32ml Na
3pO
4, stop adding conditioning agent by concentrated NaOH solution regulator solution pH value to 5, in the water-bath of 65 DEG C, stir 0.8h, then carry out suction filtration with quick filter paper, the baking oven that after washing gained sediment 3～4 times, sediment is placed in to 100～110 DEG C is dried.
S3. the coated multi-component doped lithium ferrous phosphate of carbon is synthetic
(1) prepare burden according to equation, take hypophosphite monohydrate iron, take Li according to the ratio of lithium excessive 2%
2cO
3, both are put into the nylon tank that is equipped with different-grain diameter agate ball, to carry out ball milling taking methyl alcohol as decentralized medium and mix, level control is at nylon tank volume below 2/3.Ball milling parameter is: rotating, 0.5h transposition once, Ball-milling Time 4.0h, rotating speed is 350r/min.After taking-up, sample is placed in to glass container, considers safety factor, in baking oven, be first dried to without obvious methanol liquid with 60 DEG C, and then with 110 DEG C of baking 2.0h.Last same ball milling and drying work repeats once, to obtain LiFePO
4presoma.
(2) LiFePO that ball milling mixes
4in presoma, allocate cane sugar powder into, in agate mortar, simple ground and mixed, then proceeds in enamel crucible manual jolt ramming.Be placed in tubular type constant temperature oven, rise to 680 DEG C of insulation 10h with the heating rate of 5 DEG C/min, be cooled to 80 DEG C of following samples that take out with stove, make LiFePO
4/ C.
Embodiment 3
Obtain dry and the tiny uniform reaction raw materials of particle by converter mud being toasted with grinding step, baking temperature is 90 DEG C, material tiling thickness is 30mm, baking time is 5 hours, take pendulum-type flour mill to carry out grinding to dry converter mud, finally obtain the reaction raw materials that particle is tiny;
S2. multi-element doping hypophosphite monohydrate iron is synthetic
(1) accurately take S1 step gained reaction raw materials 50g, add the sulfuric acid solution of 750ml, 1mol/L, treat that bath temperature is elevated to 90 DEG C 50g reaction raw materials is put into sulfuric acid solution, in acidolysis process, supplement the moisture of evaporation, keep liquid level constant, supplementary deionized water after acidolysis completes, makes liquid level reach 780ml, guarantee that the sulfate that acidolysis generates all dissolves, and prevents that sulphate crystal from separating out;
(2) above-mentioned solution is carried out to suction filtration, washing leaching cake 2～3 times, suction filtration to filtrate is not suspended thing;
(3) in the time that being down to 70 DEG C, water-bath temperature adds while stirring 45mlHClO in filtrate
4, 35ml K
3pO
4, stop adding conditioning agent by dense KOH solution regulator solution pH value to 2, in the water-bath of 60 DEG C, stir 1h, then carry out suction filtration with quick filter paper, the baking oven that after washing gained sediment 3～4 times, sediment is placed in to 80～90 DEG C is dried.
S3. the coated multi-component doped lithium ferrous phosphate of carbon is synthetic
(1) prepare burden according to equation, take hypophosphite monohydrate iron, take CH according to the ratio of lithium excessive 2%
3cOOLi, puts into both in the nylon tank that is equipped with different-grain diameter agate ball, carries out ball milling mix taking isopropyl alcohol as decentralized medium, and level control is at nylon tank volume below 2/3.Ball milling parameter is: rotating, 0.5h transposition once, Ball-milling Time 4.0h, rotating speed is 350r/min.After taking-up, sample is placed in to glass container, considers safety factor, in baking oven, be first dried to without obvious isopropanol liquid with 60 DEG C, and then with 120 DEG C of baking 2.0h.Last same ball milling and drying work repeats once, to obtain LiFePO
4presoma.
(2) LiFePO that ball milling mixes
4in presoma, allocate powdered glucose into, in agate mortar, simple ground and mixed, then proceeds in enamel crucible manual jolt ramming.Be placed in tubular type constant temperature oven, rise to 750 DEG C of insulation 8h with the heating rate of 10 DEG C/min, be cooled to 80 DEG C of following samples that take out with stove, make LiFePO
4/ C.
The above; it is only preferably embodiment of the present invention; but protection scope of the present invention is not limited to this; any be familiar with those skilled in the art the present invention disclose technical scope in; be equal to replacement or changed according to technical scheme of the present invention and inventive concept thereof, within all should being encompassed in protection scope of the present invention.
Claims (10)
1. utilize converter mud to prepare a method for multi-component doped lithium ferrous phosphate, it is characterized in that, comprise following methods step: the preliminary treatment of S1. converter mud: converter mud obtains tiny reaction raw materials through baking and grinding; S2. hypophosphite monohydrate is iron standby: utilize sulfuric acid solution to carry out acidolysis processing above-mentioned steps S1 gained reaction raw materials, after acidolysis, in solution, add oxidant and phosphate radical solution, rear the continuing of pH value that question response reaches setting stirs, and obtains unformed hypophosphite monohydrate iron product through washing precipitation particle; S3. the coated multi-component doped lithium ferrous phosphate of carbon is synthetic: unformed above-mentioned steps gained hypophosphite monohydrate iron is dried, add lithium salts and dispersant, ball milling post-drying in ball mill, dries in afterproduct and add carbon source, obtains the coated multi-component doped lithium ferrous phosphate of carbon.
2. the method for utilizing converter mud to prepare multi-component doped lithium ferrous phosphate according to claim 1, it is characterized in that, in described step S1, baking temperature is 80 ~ 100 DEG C, material tiling thickness is 10 ~ 50 mm, baking time is 3 ~ 5 hours, takes pendulum-type flour mill or ball mill to carry out grinding to dry converter mud.
3. the method for utilizing converter mud to prepare multi-component doped lithium ferrous phosphate according to claim 1, is characterized in that, described step S2 acidolysis utilizes X-fluorescence diffraction approach and X-ray diffraction method respectively reaction raw materials to be carried out to constituent analysis and material phase analysis before processing.
4. prepare the method for multi-component doped lithium ferrous phosphate according to the converter mud that utilizes described in claim 1 or 3, it is characterized in that, step S2 hypophosphite monohydrate is iron for comprising following concrete steps: (1) accurately takes reaction raw materials, determine constituent content and the physical form of converter mud by X-fluorescence and X ray, calculate the amount of required sulfuric acid with this, the sulfuric acid solution of configuration 1 ~ 3mol/L, wherein sulfuric acid content is calculated value 100 ~ 103%; Treat that bath temperature is elevated to 70 ~ 90 DEG C reaction raw materials is put into sulfuric acid solution, supplement the moisture of evaporation to keep liquid level constant in acidolysis process, reaction continues 0.5 ~ 2h, after pH is stable, supplements deionized water; (2) suction filtration, washing leaching cake 2 ~ 3 times; (3) in the time that being down to 60 ~ 70 DEG C, water-bath temperature adds while stirring oxidant and phosphate radical solution in filtrate, with alkaline conditioner adjusting pH value to 2 ~ 5, in the water-bath of 60 ~ 70 DEG C, stir 0.5 ~ 1h, rear suction filtration fast, the baking oven that after washing gained sediment 3 ~ 4 times, sediment is placed in to 80 ~ 120 DEG C is dried.
5. prepare the method for multi-component doped lithium ferrous phosphate according to the converter mud that utilizes described in claim 1 or 4, it is characterized in that the H that described oxidant is 30%
2o
2, dense HNO
3, HClO
4in one or several mixture.
6. prepare the method for multi-component doped lithium ferrous phosphate according to the converter mud that utilizes described in claim 1 or 4, it is characterized in that, described phosphate radical solution is selected from the K in SPA, soluble phosphate
3pO
4, Na
3pO
4, (NH
4)
3pO
4in one or several mixture.
7. the method for utilizing converter mud to prepare multi-component doped lithium ferrous phosphate according to claim 4, is characterized in that, the alkalescence using regulates the dense NH that reagent is 30%
3h
2the mixed solution of one or several in O or dense NaOH, dense KOH solution.
8. the method for utilizing converter mud to prepare multi-component doped lithium ferrous phosphate according to claim 1, is characterized in that, the synthesis step of the coated multi-component doped lithium ferrous phosphate of carbon is as follows:
(1) above-mentioned steps is obtained to unformed hypophosphite monohydrate iron dries at 80 ~ 120 DEG C, utilize the constitution water number of TG-DTA analytical calculation hypophosphite monohydrate iron, according to chemical equation with addition of lithium salts, to be placed in nylon tank with addition of good reaction raw materials, taking ethanol, methyl alcohol or isopropyl alcohol as dispersant, in planetary ball mill, after ball milling a few hours, take out and dry;
(2) by dry material with addition of carbon source, after mixing, put into crucible, be placed in reacting furnace and react, reacting furnace heating rate is 5 ~ 10 DEG C/min, reaction temperature is controlled in 680 ~ 750 DEG C and is incubated 8 ~ 10 hours under a certain fixed temperature, obtains the coated multi-component doped lithium ferrous phosphate of carbon.
9. prepare the method for multi-component doped lithium ferrous phosphate according to the converter mud that utilizes described in claim 1 or 9, it is characterized in that, lithium salts is selected from as LiOHH
2o, Li
2cO
3, CH
3one in COOLi.
10. prepare the method for multi-component doped lithium ferrous phosphate according to the converter mud that utilizes described in claim 1 or 9, it is characterized in that, described carbon source is selected from the one in polypropylene, sucrose or glucose.
?
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