CN116374984A - Preparation of lithium iron manganese phosphate precursor and method for preparing lithium iron manganese phosphate by using same - Google Patents
Preparation of lithium iron manganese phosphate precursor and method for preparing lithium iron manganese phosphate by using same Download PDFInfo
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- manganese phosphate
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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 63
- 239000002243 precursor Substances 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000011572 manganese Substances 0.000 claims abstract description 26
- 239000011259 mixed solution Substances 0.000 claims abstract description 25
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 21
- 229910052742 iron Inorganic materials 0.000 claims abstract description 19
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 19
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 18
- CADNYOZXMIKYPR-UHFFFAOYSA-B ferric pyrophosphate Chemical compound [Fe+3].[Fe+3].[Fe+3].[Fe+3].[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O CADNYOZXMIKYPR-UHFFFAOYSA-B 0.000 claims abstract description 18
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 17
- 235000007144 ferric diphosphate Nutrition 0.000 claims abstract description 15
- 239000011706 ferric diphosphate Substances 0.000 claims abstract description 15
- 229940036404 ferric pyrophosphate Drugs 0.000 claims abstract description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 14
- 239000011574 phosphorus Substances 0.000 claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 9
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 9
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 8
- 238000005507 spraying Methods 0.000 claims description 8
- 238000001694 spray drying Methods 0.000 claims description 7
- 239000012065 filter cake Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000012670 alkaline solution Substances 0.000 claims description 4
- 239000011268 mixed slurry Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 239000010405 anode material Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 16
- 229910000616 Ferromanganese Inorganic materials 0.000 abstract description 7
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 abstract description 7
- 229910019142 PO4 Inorganic materials 0.000 abstract description 5
- 239000010452 phosphate Substances 0.000 abstract description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 5
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract description 5
- 238000009826 distribution Methods 0.000 abstract description 4
- 239000007791 liquid phase Substances 0.000 abstract description 4
- 238000009827 uniform distribution Methods 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract 1
- 239000003638 chemical reducing agent Substances 0.000 abstract 1
- 230000007935 neutral effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 8
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000013507 mapping Methods 0.000 description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 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 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 239000005955 Ferric phosphate Substances 0.000 description 2
- 230000005536 Jahn Teller effect Effects 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000004964 aerogel Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 229940032958 ferric phosphate Drugs 0.000 description 2
- 230000037427 ion transport Effects 0.000 description 2
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- 239000006012 monoammonium phosphate Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 239000004966 Carbon aerogel Substances 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 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 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- JLUGKDWGQPNDGX-UHFFFAOYSA-L azanium;manganese(2+);phosphate Chemical compound [NH4+].[Mn+2].[O-]P([O-])([O-])=O JLUGKDWGQPNDGX-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 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 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 239000012688 phosphorus precursor Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- 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
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- 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
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- 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
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- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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Abstract
The invention provides a preparation of a precursor of lithium iron manganese phosphate and a method for preparing lithium iron manganese phosphate by using the precursor, wherein iron pyrophosphate is used as an iron source for preparing lithium iron manganese phosphate by a liquid phase method, the pH value is adjusted to dissolve the iron pyrophosphate, and then the iron source is uniformly mixed with a soluble manganese source, a soluble phosphorus source and an organic reducing agent, and the pH value of a mixed solution is controlled to clarify the mixed solution; and (3) rapidly controlling the pH value of the mixed solution to be nearly neutral by using strong alkali such as hydrazine hydrate or ethylenediamine and the like to coprecipitate to form a lithium manganese iron phosphate precursor. Finally, the precursor, a lithium source, a water-soluble carbon source and the like are mixed and calcined at high temperature to prepare the lithium iron manganese phosphate material. The method breaks through the conventional operation of taking ferric pyrophosphate as an iron source of a solid-phase method, solves the problem of uneven distribution of ferromanganese in the preparation of the lithium ferromanganese phosphate, and has the advantages of uniform distribution of ferromanganese in the prepared lithium ferromanganese phosphate and better electrical property.
Description
Technical Field
The invention belongs to the field of lithium ion batteries and the field of energy materials, and particularly relates to preparation of a lithium iron manganese phosphate precursor and a method for preparing lithium iron manganese phosphate by using the same.
Background
Among phosphate materials, liFePO is the most widely studied at present 4 The synthesis is relatively simple, and the large-scale production is realized. However, liFePO 4 The material has lower lithium-removing potential platform (about 3.4V), so that the energy density of the whole battery is reduced, and the development of the battery on an electric automobile is limited. And LiMnPO 4 The operating voltage for Li is 4.1V, if LiMnPO 4 Can obtain LiFePO 4 The equivalent specific capacity means that it is equivalent to LiFePO 4 The energy density will be 35% higher than compared. Meanwhile, the raw material cost is low, and the material is environment-friendly and is LiMnPO 4 Is provided. However, liMnPO 4 Is very low, almost as an insulator, only LiFePO 4 One thousandth of (a); meanwhile, jahn-Teller effect exists in the oxidation-reduction reaction process, so that the material has poor rate capability and low specific discharge capacity. LiMnPO for increasing olivine structure 4 Mainly by accelerating both electron and ion transport. The ion transport can be improved by reducing the particle size and ensuring a uniform size distribution, and the electron transport can be improved by carbon coating and doping. As can be seen from the current state of research, liMn x Fe (1-x) PO 4 The positive electrode material contains high energy density and can compensate LiFePO 4 The cathode material is deficient in this respect while improving LiMnPO 4 The problem of low multiplying power and discharge specific capacity of the positive electrode material is solved, and the possibility that the phosphoric acid positive electrode material becomes a power lithium ion battery material is improved.
At present, a single high-temperature solid phase method is used for preparing a lithium iron manganese phosphate material, and Fe and Mn are difficult to uniformly distribute in a main structure of the material when a precursor is prepared, so that Mn is caused 3+ The Jahn-Teller effect is severe, affecting the cycle and rate performance of the battery. Aiming at the point, CN106887586B provides a carbon aerogel network manganese iron phosphate lithium battery electrode material and a preparation method thereof to solve the problem of uneven iron and manganese distribution, wherein the segmentation effect of the aerogel is utilized to react to obtain manganese iron phosphate lithium with uniform particles, but the compaction density of manganese iron phosphate lithium is reduced by adding low-density aerogel in the method. For example, CN106340620a provides a method for preparing a lithium iron manganese phosphate/carbon composite positive electrode material for a lithium battery, which uses ammonium oxalate as a precipitator to obtain a precursor of ferric manganese oxalate, and synthesizes the precursor with a lithium source, a phosphorus source and a carbon source to obtain lithium iron manganese phosphate.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of a lithium iron manganese phosphate anode material of a lithium battery and a precursor thereof, which comprises the following specific technical scheme:
the first aspect of the invention provides a preparation method of lithium iron manganese phosphate, which comprises the following steps:
(1) Mixing ferric pyrophosphate with pure water to dissolve ferric pyrophosphate to obtain a mixed solution A, and continuously stirring;
(2) Sequentially adding a manganese source and a phosphorus source into the mixed solution A, and fully mixing to obtain a mixed solution B;
(3) Mixing alkaline solution and pure water to prepare fixed solution C, then rapidly spraying the fixed solution C into continuously stirred mixed solution B, and stopping spraying until the pH value of the mixed solution B is stabilized at 6-6.5;
(4) Filtering the mixed slurry obtained in the step (3) to obtain a filter cake, repeatedly washing the filter cake with pure water, and then drying in vacuum to obtain the lithium iron manganese phosphate precursor.
And (3) adjusting the pH value of the mixed solution A to be less than or equal to 0.8 after the ferric pyrophosphate in the step (1) is dissolved, wherein the pH value in the step (3) is 6.5-7.0.
The manganese source in the step (2) is one or more of water-soluble or acid-soluble manganese sources, and the phosphorus source is one or more of water-soluble or acid-soluble phosphorus sources.
More specifically, the manganese source is one or more of manganous chloride, manganous sulfate, manganous carbonate and manganous nitrate;
the phosphorus source is one or more of phosphoric acid, monoammonium phosphate and ammonium phosphate.
The manganese source and the phosphorus source in the (1) are respectively based on Mn and PO 4 3- The calculated molar ratio is 1.0 (1.0-1.1); the sum of the concentration of the iron source and the manganese source in the mixed solution B is calculated according to Fe + Mn is 0.5-2 mol/L.
The alkaline solution in the step (3) is one or a mixture of two of a hydrazine hydrate solution and an ethylenediamine solution, and the total weight ratio of the hydrazine hydrate, the ethylenediamine or the hydrazine hydrate and the ethylenediamine in the fixed solution C in the step (3) is 1-20wt%.
The addition time of the fixing solution C in the step (3) is 20-40s.
The washing end condition in the step (4) is that the conductivity of the finally washed filtrate is less than or equal to 0.5mS/cm.
In a second aspect, the invention provides a method of lithium iron manganese phosphate comprising the steps of:
(1) Mixing a lithium iron manganese phosphate precursor, a lithium source, a carbon source and pure water, and then sanding to obtain slurry;
(2) Spray drying the sanded slurry obtained in the step (1) to obtain powder;
(3) And finally calcining, crushing and sieving the powder obtained in the step (2) under the protection of inert gas to obtain the lithium iron manganese phosphate.
The sanding process controls the D50 of the slurry to be less than or equal to 250nm.
The lithium source is one or more of lithium carbonate, lithium hydroxide and lithium nitrate.
The carbon source is one or more of starch, sucrose, glucose, polyethylene glycol and citric acid.
The lithium source and the lithium iron manganese phosphate precursor are respectively prepared according to Li and Fe + The mole ratio of Mn is (1.0-1.05) 1, and the carbon source accounts for 5-10wt% of the total amount of the lithium source, the lithium iron manganese phosphate precursor and the carbon source.
Ferric pyrophosphate is slightly soluble in water and is generally used as an iron source in preparing lithium ferromanganese phosphate by a solid phase method and cannot be used as an iron source by a liquid phase method, but the use of ferric pyrophosphate as an iron source by a solid phase method for preparing lithium ferromanganese phosphate is prone to the problem of uneven ferromanganese distribution. The method for preparing the lithium iron manganese phosphate by taking the ferric pyrophosphate as the liquid-phase method iron source has the following beneficial effects compared with the prior art:
according to the invention, ferric pyrophosphate is used as an iron source for preparing lithium manganese iron phosphate by a liquid phase method, the pH value is adjusted to dissolve the ferric phosphate, and then the ferric phosphate is uniformly mixed with a soluble manganese source and a soluble phosphorus source, and the pH value of the mixed solution is controlled to clarify the mixed solution; and then preparing a uniform mixture of iron, manganese and phosphorus precursor iron phosphate and manganese ammonium phosphate by a coprecipitation method under a proper pH value, and finally preparing lithium iron manganese phosphate by using the precursor.
Drawings
Fig. 1 is a TEM image of a lithium iron manganese phosphate precursor prepared in example 1.
FIG. 2 is a TEM-Mapping diagram of a lithium iron manganese phosphate precursor prepared in example 1.
Fig. 3 is a TEM image of the lithium iron manganese phosphate precursor prepared in comparative example 1.
FIG. 4 is a TEM-Mapping diagram of the lithium iron manganese phosphate precursor prepared in comparative example 1.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications could be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present invention.
Example 1
1. Preparation of lithium iron manganese phosphate precursor
(1) Mixing 2.79g of ferric pyrophosphate with 37.5g of pure water, regulating the pH value to 0.5 to obtain a mixed solution A, and keeping stirring;
(2) Adding 3.40g of manganese sulfate and 2.72g of ammonium dihydrogen phosphate into the mixed solution A in sequence, and fully mixing to obtain a mixed solution B;
(3) Preparing a fixed solution C with hydrazine hydrate accounting for 5wt%, then rapidly spraying the fixed solution C into a continuously stirred mixed solution B, stopping when the pH value of the mixed solution B is stabilized at 6, and continuously stirring for a period of time after spraying is finished to obtain mixed slurry, wherein the whole spraying time is 40 s;
(4) Filtering the mixed slurry obtained in the step (3) to obtain a filter cake, repeatedly washing the filter cake with pure water until the conductivity in the filtrate obtained in the last washing is less than or equal to 0.5mS/cm, and drying in vacuum to obtain a precursor.
FIG. 1 is a TEM image of a lithium iron manganese phosphate precursor prepared in this example, and the primary particle size of the precursor synthesized in this example is about 30-80 nm. Fig. 2 is a TEM-Mapping diagram of a lithium iron manganese phosphate precursor prepared in this example, and it can be seen from the diagram that the oxygen, phosphorus, manganese and iron elements in the precursor material synthesized in this example all show a uniform distribution.
2. Preparation of lithium iron manganese phosphate
1) Mixing the lithium iron manganese phosphate precursor obtained in step 1 with 1.46g of lithium carbonate, 0.73g of glucose and 23.57g of pure water, then sanding, wherein D50 of the sanded slurry is less than or equal to 250nm, spray drying the sanded slurry, wherein the air inlet temperature is 150 ℃, the air outlet temperature is 75 ℃, and obtaining powder after spray drying.
2) Calcining the powder dried in the step 1) for 8 hours at 600 ℃ under the protection of nitrogen, and crushing and sieving to obtain the lithium iron manganese phosphate material.
Example 2
The method and procedure are the same as in example 1, except that the pH value is adjusted to 0.8 during the preparation of the lithium iron manganese phosphate precursor.
Example 3
The method and procedure are the same as in example 1, except that the pH value is adjusted to 1.0 during the preparation of the lithium iron manganese phosphate precursor.
Example 4
The method and the steps are the same as in example 1, and spraying is stopped after the pH value of the mixed solution B is stabilized at 6.5 only in the preparation process of the lithium manganese iron phosphate precursor.
Example 5
The method and steps are the same as in example 1, and the fixed solution C with the hydrazine hydrate accounting for 20 weight percent is prepared only in the preparation process of the lithium manganese iron phosphate precursor.
Example 6
The procedure and procedure were as in example 1 except that the amount of ferric pyrophosphate added was 2.10g, the amount of manganese sulfate added was 3.96, and the amount of monoammonium phosphate added was 3.17.
Comparative example 1
(1) 2.79g of ferric pyrophosphate, 1.72g of manganomanganic oxide, 2.59g of ammonium dihydrogen phosphate and 18.25g of pure water are mixed and then are sanded, D50 of the sanded slurry is less than or equal to 250nm, spray drying is carried out on the sanded slurry, the air inlet temperature is 150 ℃, the air outlet temperature is 75 ℃, and the lithium manganese iron phosphate precursor is obtained after the spray drying is finished.
FIG. 3 is a TEM image of a lithium iron manganese phosphate precursor prepared in this comparative example, and the primary particle size of the precursor synthesized in this comparative example is about 50 to 150nm.
Fig. 4 is a TEM-Mapping graph of the lithium iron manganese phosphate precursor prepared in this comparative example, from which it can be seen that the oxygen, phosphorus, manganese and iron elements in the precursor material synthesized in this comparative example are unevenly distributed.
(2) The lithium iron manganese phosphate precursor prepared in the example, 1.46g of lithium carbonate, 0.74g of glucose and 23.91g of pure water are mixed and then are subjected to sand grinding, D50 of the slurry after sand grinding is less than or equal to 250nm, the slurry after sand grinding is subjected to spray drying to obtain powder, and the powder is calcined for 10 hours at 650 ℃ under the protection of nitrogen, and is crushed and sieved to obtain the lithium iron manganese phosphate material.
Test results
According to the embodiment of the invention, ferric pyrophosphate is used as an iron source, a coprecipitation method is adopted to synthesize a lithium iron phosphate precursor, manganese and iron in the synthesized precursor are uniformly distributed, a lithium source and a carbon source are added into the precursor to finally synthesize a lithium iron phosphate material, the lithium iron phosphate material is synthesized by adopting a solid phase method through ferric pyrophosphate in comparative example 1, and then the prepared lithium iron phosphate material is respectively tested, and the test results show that the discharge capacity and the multiplying power performance of the lithium iron phosphate prepared by the method are improved.
Claims (10)
1. The preparation method of the lithium iron manganese phosphate precursor is characterized by comprising the following steps of:
(1) Mixing ferric pyrophosphate with pure water to dissolve ferric pyrophosphate to obtain a mixed solution A, and continuously stirring;
(2) Sequentially adding a manganese source and a phosphorus source into the mixed solution A, and fully mixing to obtain a mixed solution B;
(3) Mixing an alkaline solution and pure water to prepare a fixed solution C, then rapidly spraying the fixed solution C into a continuously stirred mixed solution B, and stopping spraying until the pH value of the mixed solution B is stabilized at 6-6.5;
(4) Filtering the mixed slurry obtained in the step (3) to obtain a filter cake, repeatedly washing the filter cake with pure water, and then drying in vacuum to obtain the lithium iron manganese phosphate precursor.
2. The method for preparing a lithium iron manganese phosphate precursor according to claim 1, wherein the pH value of the mixed solution a is adjusted to be less than or equal to 0.8 after the iron pyrophosphate is dissolved in the step (1), and the pH value is 6.5 to 7.0 in the step (3).
3. The method for preparing a lithium iron manganese phosphate precursor according to claim 1, wherein the manganese source in the step (2) is one or more of water-soluble or acid-soluble manganese sources, and the phosphorus source is one or more of water-soluble or acid-soluble phosphorus sources.
4. The method for preparing a lithium iron manganese phosphate precursor according to claim 1, wherein the manganese source and the phosphorus source in (1) are respectively selected from the group consisting of Mn and PO 4 3- The molar ratio is 1.0 (1.0-1.1); and the sum of the concentration of the iron source and the concentration of the manganese source in the mixed solution B is 0.5-2 mol/L according to Fe+Mn.
5. The preparation method of the lithium iron manganese phosphate precursor according to claim 1, wherein the alkaline solution in the step (3) is one or a mixture of two of a hydrazine hydrate solution and an ethylenediamine solution, and the ratio of the hydrazine hydrate, ethylenediamine or the sum of the addition amounts of the hydrazine hydrate and the ethylenediamine in the fixed solution C in the step (3) is 0-20wt%.
6. The method for preparing a lithium iron manganese phosphate precursor according to claim 1, wherein the addition time of the fixing solution C in the step (3) is 20 to 40s.
7. The method for preparing a lithium iron manganese phosphate precursor according to claim 1, wherein the washing end condition in the step (4) is that the conductivity of the finally washed filtrate is less than or equal to 0.5mS/cm.
8. A method for preparing lithium iron manganese phosphate by using the lithium iron manganese phosphate precursor prepared by the method according to any one of claims 1 to 7, comprising the following steps:
(1) Mixing a lithium iron manganese phosphate precursor, a lithium source, a carbon source and pure water, and then sanding to obtain slurry;
(2) Spray drying the sanded slurry obtained in the step (1) to obtain powder;
(3) And finally calcining, crushing and sieving the powder obtained in the step (2) under the protection of inert gas to obtain the lithium iron manganese phosphate.
9. The preparation method of the lithium iron manganese phosphate according to claim 8, wherein the molar ratio of the lithium source to the lithium iron manganese phosphate precursor is (1.0-1.05) 1, calculated as Li and Fe+Mn, respectively, and the carbon source accounts for 5-10wt% of the total amount of the lithium source, the lithium iron manganese phosphate precursor and the carbon source.
10. A lithium iron manganese phosphate prepared by the method according to any one of claims 8 to 9, which is characterized by being applied to the field of lithium battery anode materials.
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