CN117303341A - Preparation method of ferric manganese phosphate precursor - Google Patents
Preparation method of ferric manganese phosphate precursor Download PDFInfo
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- 239000002243 precursor Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 title description 8
- AWKHTBXFNVGFRX-UHFFFAOYSA-K iron(2+);manganese(2+);phosphate Chemical compound [Mn+2].[Fe+2].[O-]P([O-])([O-])=O AWKHTBXFNVGFRX-UHFFFAOYSA-K 0.000 claims abstract description 43
- 239000011572 manganese Substances 0.000 claims abstract description 41
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- 238000003756 stirring Methods 0.000 claims description 25
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 12
- 238000000967 suction filtration Methods 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 4
- 238000005580 one pot reaction Methods 0.000 claims description 2
- 230000001502 supplementing effect Effects 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 abstract description 3
- 239000002245 particle Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 239000007774 positive electrode material Substances 0.000 description 9
- 229910019142 PO4 Inorganic materials 0.000 description 6
- 239000010452 phosphate Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910000616 Ferromanganese Inorganic materials 0.000 description 5
- 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 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000008103 glucose Substances 0.000 description 5
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- 238000001238 wet grinding Methods 0.000 description 5
- 238000000975 co-precipitation Methods 0.000 description 4
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000004682 monohydrates Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 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
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- -1 phosphorus ions Chemical class 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- 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
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- 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
- C01P2006/80—Compositional purity
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Composite Materials (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of a manganese iron phosphate precursor, which is characterized in that a nano-scale (Mn x Fe （1‑x） ) 2 O 3 And H 3 PO 4 Reacting to directly obtain a manganese iron phosphate precursor; wherein x is more than or equal to 0.4 and less than or equal to 0.8. The preparation method of the invention has no wastewater, is green and environment-friendly, and the prepared manganese iron phosphate precursor has good purity and accurate proportion, and avoids Mn 2+ Is not easy to oxidize into Mn 3+ Is difficult.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a preparation method of a ferric manganese phosphate precursor.
Background
Iron-manganese phosphate precursors are commonly used precursor materials for preparing iron-manganese phosphate, which have a variety of applications, including as battery materials, catalysts, or components of electrochemical sensors. At present, the manganese iron phosphate precursor has too few species and is prepared in a 2-valent salt systemMainly, e.g. NH 4 (MnFe)PO 4 And (MnFe) HPO 4 . The common preparation method of the ferromanganese phosphate comprises the steps of converting a ferromanganese phosphate precursor into ferromanganese phosphate by adopting a coprecipitation-oxidation method, wherein manganese, iron and phosphorus ions in the precursor are coprecipitated in a solution to form a precipitate in the reaction process, then the precipitate and the solution are separated, and the precipitate is washed and then subjected to heat treatment under proper oxygen or oxidation atmosphere to be converted into ferromanganese phosphate. The process for preparing iron manganese phosphate coprecipitation-oxidation has several drawbacks and limitations, including (1) difficulty in completely removing all impurities during the coprecipitation and washing steps, which may lead to a decrease in purity of the final product; (2) In the oxidation step, mn 2+ Is not easy to oxidize into Mn 3+ Also, the purity of the final product is reduced; (3) The ferromanganese phosphate crystal structure prepared by the coprecipitation method has defects, so that the sintering difficulty is increased, and the optimal capacity level is difficult to reach; (4) The coprecipitation method for preparing the manganese iron phosphate is difficult to ensure that the ratio Me/P of transition metal and phosphate radical is in a proper range; (5) Waste liquid is generated in the coprecipitation method process, and may contain harmful waste, and environmental and safety problems exist in the waste liquid.
Disclosure of Invention
Based on the problems existing in the background technology, the invention provides a preparation method of the manganese iron phosphate precursor, which is free of waste water, green and environment-friendly, and the prepared manganese iron phosphate precursor has good purity and accurate proportion, and avoids Mn 2+ Is not easy to oxidize into Mn 3+ Is difficult.
The invention is implemented by the following technical scheme:
a method for preparing a manganese iron phosphate precursor by a one-step method for preparing a nano-scale (Mn x Fe （1-x） ) 2 O 3 And H 3 PO 4 Reacting to directly obtain a manganese iron phosphate precursor;
wherein x is more than or equal to 0.4 and less than or equal to 0.8.
Further, (Mn) x Fe （1-x） ) 2 O 3 The purity of (2) is more than or equal to 99.0 percent; d50 is less than or equal to 50nm.
Further toGround, H 3 PO 4 Is industrial phosphoric acid with purity not less than 85%.
Further, (Mn) x Fe （1-x） ) 2 O 3 And H 3 PO 4 The molar ratio of the dosage is 1: (1-1.2).
Further, the one-step reaction is specifically operated as: will (Mn) x Fe （1-x） ) 2 O 3 Adding into pure water, and dropwise adding H under stirring 3 PO 4 And (3) keeping stirring on, setting the reaction temperature to be 80-100 ℃, enabling the system to be always in reflux heating, along with the reaction, raising the viscosity of the system, supplementing pure water to keep the viscosity of the system, stopping the reaction for 8-12 hours, carrying out suction filtration on the reacted materials, washing the materials with pure water for 3-5 times, and drying in a blast oven to obtain the manganese iron phosphate precursor.
Further, the stirring rate is 200-500rpm.
Further, H 3 PO 4 The drop rate of (2) is 25-100% of the total feed amount/h.
Further, the reaction process maintains the viscosity of the system below 5000cps.
The manganese iron phosphate precursor is prepared by the preparation method of the manganese iron phosphate precursor, and has a structural formula of Mn y Fe （1-y） PO 4 Wherein y is more than or equal to 0.4 and less than or equal to 0.8.
The lithium iron manganese phosphate anode material is obtained by mixing and sintering the lithium source with the manganese iron phosphate precursor material.
The invention has the beneficial effects that:
1. the preparation method of the invention adopts a one-step method to make the nanometer (Mn x Fe （1-x） ) 2 O 3 And H 3 PO 4 And the reaction is carried out to directly obtain the manganese iron phosphate precursor, no redundant impurities are generated in the reaction process, and the prepared manganese iron phosphate precursor product has good purity and accurate proportioning. The manganese iron phosphate precursors prepared by the method are all nanoscale particles, can be used for preparing nano manganese iron phosphate lithium, and can effectively improve the electrochemical performance of manganese iron phosphate lithium.
2. The preparation method has the advantages that no waste water is generated in the reaction process, and the method is environment-friendly; the preparation method has simple process and low comprehensive cost, and is suitable for large-scale production.
3. The preparation method directly selects the nano (Mn x Fe （1-x） ) 2 O 3 And H 3 PO 4 Reaction, mn is avoided 2+ Is not easy to oxidize into Mn 3+ Is difficult.
Drawings
The accompanying drawings are included to provide a further explanation of the invention and are incorporated in and constitute a part of this specification, illustrate the invention and together with the embodiments of the invention, serve to explain the invention. In the drawings:
FIG. 1 is an XRD pattern of a manganese iron phosphate precursor prepared in example 1 of the present invention;
FIG. 2 is an XRD pattern of a precursor of manganese iron phosphate prepared in example 2 of the present invention;
FIG. 3 is an XRD pattern of a precursor of manganese iron phosphate prepared in comparative example 1 of the present invention;
fig. 4 is an XRD pattern of the iron-manganese phosphate precursor prepared in comparative example 2 of the present invention.
Detailed Description
The technical scheme of the present invention will be further described in detail with reference to the following specific examples, but the scope of the present invention is not limited to the following examples.
In the examples and comparative examples of the present application, the nano-scale (Mn x Fe （1-x） ) 2 O 3 The material was purchased from first-come nanometer.
Example 1
Preparation of ferric manganese phosphate precursor
The particles having a median particle diameter D50 of 40nm (Mn 0.5 Fe 0.5 ） 2 O 3 (purity 99.1%,6.25 mol) 1.00kg, 5L of pure water was added, and 0.863kg of 85% technical phosphoric acid (7.490 mol, excess 20%) was added dropwise at 25% total charge/h under stirring at 200 r/min; stirring is kept on, the reaction temperature is 80 ℃, and the reaction is always in reflux heating; as the reaction proceeds, the viscosity of the system increases, and pure water is properly replenishedTo reduce the viscosity, maintain the viscosity of the system below 5000cps (4800 cps measured, test conditions (the same applies below) rotor viscometer 3# rotor, 6 rpm); simultaneously, the color of the mixture is gradually changed from reddish brown to blackish green; stopping the reaction after reacting for 10 hours, and carrying out suction filtration on the reacted materials; washing with pure water for 3-5 times, and drying in a blast oven to obtain the manganese iron phosphate precursor.
Example 2
Preparation of ferric manganese phosphate precursor
The particles having a median particle diameter D50 of 30nm (Mn 0.7 Fe 0.3 ） 2 O 3 (purity 99.3%,6.27 mol) 1.00kg, 5L of pure water was added, and 0.831kg of 85% technical phosphoric acid (7.208 mol, 15% excess) was added dropwise at a total feed rate of 50%/h under stirring at a rotational speed of 350 r/min; stirring is kept on, the reaction temperature is 80 ℃, and the reaction is always in reflux heating; as the reaction proceeds, the viscosity of the system increases, and pure water is properly replenished to reduce the viscosity, keeping the viscosity of the system below 5000cps (actually measured 3700 cps); simultaneously, the color of the mixture is gradually changed from reddish brown to blackish green; after reacting for 12 hours, stopping the reaction, and carrying out suction filtration on the reacted materials; washing with pure water for 3-5 times, and drying in a blast oven to obtain the manganese iron phosphate precursor.
Example 3
Preparation of ferric manganese phosphate precursor
The particles having a median particle diameter D50 of 50nm (Mn 0.6 Fe 0.4 ） 2 O 3 (purity 99.0%,6.24 mol) 1.00kg, 5L of pure water was added, and 0.863kg of 85% technical phosphoric acid (7.488 mol, excess 20%) was added dropwise at a total dosage of 50%/h under stirring at a rotational speed of 350 r/min; stirring is kept on, the reaction temperature is 80 ℃, and the reaction is always in reflux heating; as the reaction proceeds, the viscosity of the system increases, and pure water is properly added to reduce the viscosity, keeping the viscosity of the system below 5000cps (3200 cps in actual measurement); simultaneously, the color of the mixture is gradually changed from reddish brown to blackish green; after reacting for 12 hours, stopping the reaction, and carrying out suction filtration on the reacted materials; washing with pure water for 3-5 times, and drying in a blast oven to obtain the manganese iron phosphate precursor.
Example 4
Preparation of ferric manganese phosphate precursor
The particles having a median particle diameter D50 of 25nm (Mn 0.8 Fe 0.2 ） 2 O 3 (purity 99.2%,6.27 mol) 1.00kg, 5L of pure water was added, and 0.795kg of 85% technical phosphoric acid (7.897 mol, 10% excess) was added dropwise at a total dosage of 75%/h under stirring at a rotational speed of 300 r/min; stirring is kept on, the reaction temperature is 80 ℃, and the reaction is always in reflux heating; as the reaction proceeds, the viscosity of the system increases, and pure water is properly replenished to reduce the viscosity, keeping the viscosity of the system below 5000cps (measured 4100 cps); simultaneously, the color of the mixture is gradually changed from reddish brown to blackish green; after reacting for 12 hours, stopping the reaction, and carrying out suction filtration on the reacted materials; washing with pure water for 3-5 times, and drying in a blast oven to obtain the manganese iron phosphate precursor.
Example 5
Preparation of ferric manganese phosphate precursor
The particles having a median particle diameter D50 of 20nm (Mn 0.5 Fe 0.5 ） 2 O 3 (purity 99.3%,6.25 mol) 1.00kg, 5L pure water was added, and 0.829kg of 85% technical phosphoric acid (7.188 mol, 15% excess) was added dropwise at 50% total charge/h under stirring at 200 r/min; stirring is kept on, the reaction temperature is 80 ℃, and the reaction is always in reflux heating; as the reaction proceeds, the viscosity of the system increases, and pure water is properly replenished to reduce the viscosity, keeping the viscosity of the system below 5000cps (measured 3900 cps); simultaneously, the color of the mixture is gradually changed from reddish brown to blackish green; stopping the reaction after reacting for 10 hours, and carrying out suction filtration on the reacted materials; washing with pure water for 3-5 times, and drying in a blast oven to obtain the manganese iron phosphate precursor.
Comparative example 1
The median particle diameter D50 was 3um (Mn 0.5 Fe 0.5 ） 2 O 3 (purity 99.0%,6.25 mol) 1.00kg, 5L pure water was added, and 0.863kg of 85% technical phosphoric acid (7.490 mol, excess 20%) was added dropwise at 25% total charge/h under stirring at 200 r/min; stirring is kept on, the reaction temperature is 80 ℃, and the reaction is always in reflux heating; as the reaction proceeds, the viscosity of the system increases, and pure water is properly supplementedWater to reduce the viscosity, keeping the viscosity of the system below 5000cps (4400 cps measured); at the same time the reddish brown color of the mixture is slightly lighter; stopping the reaction after reacting for 10 hours, and carrying out suction filtration on the reacted materials; washing with pure water for 3-5 times, and drying in a forced air oven to obtain the product 1.
Comparative example 2
The median particle diameter D50 was 3um (Mn 0.7 Fe 0.3 ） 2 O 3 (purity 99.5%,6.27 mol) 1.00kg, 5L pure water was added, and 0.831kg of 85% technical phosphoric acid (7.208 mol, 15% excess) was added dropwise at 50% total charge/h under stirring at 350 r/min; stirring is kept on, the reaction temperature is 80 ℃, and the reaction is always in reflux heating; as the reaction proceeds, the viscosity of the system increases, and pure water is properly replenished to reduce the viscosity, keeping the viscosity of the system below 5000cps (measured 3900 cps); the color of the mixture is changed from reddish brown to reddish gray; after reacting for 12 hours, stopping the reaction, and carrying out suction filtration on the reacted materials; washing with pure water for 3-5 times, and drying in a forced air oven to obtain the product 2.
Comparative example 3
Selecting a material having a median particle diameter D50 of 500nm (Mn 0.6 Fe 0.4 ） 2 O 3 (purity 99.0%,6.24 mol) 1.00kg, 5L of pure water was added, and 0.863kg of 85% technical phosphoric acid (7.488 mol, excess 20%) was added dropwise at a total dosage of 50%/h under stirring at a rotational speed of 350 r/min; stirring is kept on, the reaction temperature is 80 ℃, and the reaction is always in reflux heating; as the reaction proceeds, the viscosity of the system increases, and pure water is properly replenished to reduce the viscosity, keeping the viscosity of the system below 5000cps (3500 cps in actual measurement); the color of the mixture is changed from reddish brown to reddish gray; after reacting for 12 hours, stopping the reaction, and carrying out suction filtration on the reacted materials; washing with pure water for 3-5 times, and drying in a forced air oven to obtain the product 3.
Comparative example 4
The median particle diameter D50 was selected to be 2um (Mn 0.8 Fe 0.2 ） 2 O 3 (purity 99.2%,6.27 mol) 1.00kg, 5L of pure water was added, and 0.795kg of 85% technical phosphoric acid (7.897 mol, 10% excess) was added dropwise at a total dosage of 75%/h under stirring at a rotational speed of 300 r/min; holding stirringStirring and starting, wherein the reaction temperature is 80 ℃ and the mixture is always in reflux heating; as the reaction proceeds, the viscosity of the system increases, and pure water is properly replenished to reduce the viscosity, keeping the viscosity of the system below 5000cps (3800 cps in actual measurement); the color of the mixture is changed from reddish brown to reddish gray; after reacting for 12 hours, stopping the reaction, and carrying out suction filtration on the reacted materials; washing with pure water for 3-5 times, and drying in a forced air oven to obtain the product 4.
Comparative example 5
The particles having a median particle diameter D50 of 200nm (Mn 0.5 Fe 0.5 ） 2 O 3 (purity 99.3%,6.25 mol) 1.00kg, 5L pure water was added, and 0.829kg of 85% technical phosphoric acid (7.188 mol, 15% excess) was added dropwise at 50% total charge/h under stirring at 200 r/min; stirring is kept on, the reaction temperature is 80 ℃, and the reaction is always in reflux heating; as the reaction proceeds, the viscosity of the system increases, and pure water is properly replenished to reduce the viscosity, keeping the viscosity of the system below 5000cps (4200 cps, found); the color of the mixture is changed from reddish brown to reddish gray; stopping the reaction after 10 hours, and carrying out suction filtration on the reacted materials; washing with pure water for 3-5 times, and drying in a forced air oven to obtain the product 5.
Test example 1
The products of examples 1-5 and comparative examples 1-5 were subjected to main element content, XRD and particle size measurement, wherein the main element content was measured by ICP-OES, the particle size was measured by a laser particle sizer, and the purity of the products was calculated by a peak area method based on XRD results of the products, and the XRD patterns of examples 1-2 and comparative examples 1-2 are shown in FIGS. 1-4.
TABLE 1
In table 1, (mn+fe)/P molar ratio= (Mn element percentage/Mn element relative atomic mass+fe element percentage/Fe element relative atomic mass)/(P element percentage/P element relative atomic mass).
As can be seen from the results of Table 1, the manganese iron phosphate precursor in examples 1 to 5 is Mn monohydrate y Fe （1-y） PO 4 The molar ratio of (Mn+Fe)/P is basically maintained at about 0.98, and the median particle diameter of the powder is below 0.51 nm; in comparative examples 1 to 5, however, the main component of the obtained product was still (Mn 0.5 Fe 0.5 ） 2 O 3 Comprises a small part of Mn y Fe （1-y） PO 4 The molar ratio of (Mn+Fe)/P is 1.7 or more. It can also be seen from FIGS. 1-4 that the manganese iron phosphate precursor of examples 1 and 2 is Mn monohydrate y Fe （1-y） PO 4 The main components of comparative examples 1 and 2 are (Mn 0.7 Fe 0.3 ） 2 O 3 Comprises a small amount of Mn y Fe （1-y） PO 4 。
Test example 2
Battery testing
(1) 500g of the manganese iron phosphate precursor in example 1 was mixed with 112.6g of battery grade lithium carbonate powder (molar ratio of Li: M: P=1.02: 0.98: 1), 50g of glucose, 5L of water was added, wet milling was performed, and powder was sprayed again, and sintered at 700℃for 8 hours in a nitrogen atmosphere, to obtain a positive electrode material A.
(2) 500g of the manganese iron phosphate precursor in example 2 was mixed with 116.9g of battery grade lithium carbonate powder (molar ratio of Li: M: P=1.05: 0.97: 1), 50g of glucose, 5L of water was added, wet milling was performed, the powder was spray-dried, and the mixture was sintered at 680℃for 6 hours in a nitrogen atmosphere, to obtain a positive electrode material B.
(3) 500g of the manganese iron phosphate precursor in example 3 was mixed with 114.7g of battery grade lithium carbonate powder (molar ratio of Li: M: P=1.03: 0.98: 1), 50g of glucose, 5L of water was added, wet milling was performed, and powder was sprayed, and sintered at 700℃for 8 hours in a nitrogen atmosphere, to obtain a positive electrode material C.
(4) 500g of the manganese iron phosphate precursor in example 4 was mixed with 114.7g of battery grade lithium carbonate powder (molar ratio of Li: M: P=1.03: 0.97: 1), 50g of glucose, 5L of water was added, wet milling was performed, and powder was sprayed, and sintered at 700℃for 8 hours in a nitrogen atmosphere, to obtain a positive electrode material D.
(5) 500g of the manganese iron phosphate precursor in example 5 was mixed with 115.9g of battery grade lithium carbonate powder (molar ratio of Li: M: P=1.04: 0.97: 1), 50g of glucose, 5L of water was added, wet milling was performed, and powder was sprayed, and sintered at 700℃for 8 hours in a nitrogen atmosphere, to obtain a positive electrode material E.
The positive electrode material A prepared by the method is used as a positive electrode active material, the positive electrode active material SP (superconducting carbon black) is homogenized by PVDF (polyvinylidene fluoride) according to the mass ratio of 90:5:5, and the positive electrode active material A is coated on aluminum foil with the thickness of 20 mu m to prepare the positive electrode sheet with the surface density of 8mg/cm 2 Then drying, rolling, die cutting and punching to form a positive pole piece A; and assembling the positive electrode plate A, the diaphragm and the lithium sheet into a button cell in a glove box for testing. The button cell was subjected to charge and discharge tests in a voltage range of 2.0 to 4.3V, and the results were shown in table 2.
TABLE 2
The products of comparative examples 1 to 5 were not qualified in element ratio and could not be used as precursors for lithium iron manganese phosphate production, i.e., could not be prepared into electrode materials.
The preparation method of the invention directly adopts the nanometer-scale (Mn x Fe （1-x） ) 2 O 3 And H 3 PO 4 The prepared manganese iron phosphate precursor product has good purity and accurate proportion, and the prepared manganese iron phosphate precursor product has good electrochemical performance and high capacity when being applied to manganese iron phosphate anode materials.
Finally, it should be noted that: the above examples merely illustrate several embodiments of the present invention and are not intended to limit the invention, and any modifications, equivalent substitutions, improvements, etc. made by those skilled in the art without departing from the spirit of the present invention are intended to be included in the scope of the present invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (9)
1. A method for preparing a manganese iron phosphate precursor, characterized in that a nano-scale (Mn x Fe （1-x） ) 2 O 3 And H 3 PO 4 Reacting to directly obtain a manganese iron phosphate precursor;
wherein x is more than or equal to 0.4 and less than or equal to 0.8.
2. The method according to claim 1, wherein (Mn x Fe （1-x） ) 2 O 3 The purity of (2) is more than or equal to 99.0 percent; d50 is less than or equal to 50nm.
3. The method of claim 1, wherein H 3 PO 4 Is industrial phosphoric acid with purity not less than 85%.
4. The method according to claim 1, wherein (Mn x Fe （1-x） ) 2 O 3 And H 3 PO 4 The molar ratio of the dosage is 1: (1-1.2).
5. The method of claim 1, wherein the one-step reaction is specifically performed as: will (Mn) x Fe （1-x） ) 2 O 3 Adding into pure water, and dropwise adding H under stirring 3 PO 4 And (3) keeping stirring on, setting the reaction temperature to be 80-100 ℃, enabling the system to be always in reflux heating, along with the reaction, raising the viscosity of the system, supplementing pure water to keep the viscosity of the system, stopping the reaction for 8-12 hours, carrying out suction filtration on the reacted materials, washing the materials with pure water for 3-5 times, and drying in a blast oven to obtain the manganese iron phosphate precursor.
6. The method according to claim 5, wherein the stirring rate is 200 to 500rpm.
7. The process according to claim 5, wherein H 3 PO 4 The drop rate of (2) is 25-100%/h of the total feed amount.
8. The process of claim 5 wherein the reaction maintains a viscosity of the system below 5000cps.
9. The manganese iron phosphate precursor is characterized in that the manganese iron phosphate precursor is prepared by the preparation method according to any one of claims 1-8, and has a structural formula Mn y Fe （1-y） PO 4 Wherein y is more than or equal to 0.4 and less than or equal to 0.8.
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| CN115535992A (en) * | 2022-12-01 | 2022-12-30 | 深圳中芯能科技有限公司 | Ferromanganese phosphate precursor, lithium iron manganese phosphate anode material and preparation method |
| CN116826040A (en) * | 2022-11-11 | 2023-09-29 | 中科致良新能源材料(浙江)有限公司 | Manganese iron phosphate with nano-porous structure and preparation method and application thereof |
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| CN116826040A (en) * | 2022-11-11 | 2023-09-29 | 中科致良新能源材料(浙江)有限公司 | Manganese iron phosphate with nano-porous structure and preparation method and application thereof |
| CN115535992A (en) * | 2022-12-01 | 2022-12-30 | 深圳中芯能科技有限公司 | Ferromanganese phosphate precursor, lithium iron manganese phosphate anode material and preparation method |
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