CN115506006A - Preparation method of battery-grade single-crystal iron phosphate - Google Patents
Preparation method of battery-grade single-crystal iron phosphate Download PDFInfo
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- CN115506006A CN115506006A CN202211012399.6A CN202211012399A CN115506006A CN 115506006 A CN115506006 A CN 115506006A CN 202211012399 A CN202211012399 A CN 202211012399A CN 115506006 A CN115506006 A CN 115506006A
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- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 title claims abstract description 45
- 229910000398 iron phosphate Inorganic materials 0.000 title claims abstract description 39
- 239000013078 crystal Substances 0.000 title claims abstract description 18
- 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 66
- 229910052742 iron Inorganic materials 0.000 claims abstract description 33
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 30
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims abstract description 29
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 20
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 239000012065 filter cake Substances 0.000 claims abstract description 10
- 238000005245 sintering Methods 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 230000032683 aging Effects 0.000 claims abstract description 5
- 239000002131 composite material Substances 0.000 claims abstract description 3
- 229960004063 propylene glycol Drugs 0.000 claims description 15
- 239000002893 slag Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 235000013772 propylene glycol Nutrition 0.000 claims description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 abstract description 13
- 238000005056 compaction Methods 0.000 abstract description 8
- 239000005955 Ferric phosphate Substances 0.000 abstract description 6
- 229940032958 ferric phosphate Drugs 0.000 abstract description 6
- 239000012535 impurity Substances 0.000 abstract description 6
- 229910000399 iron(III) phosphate Inorganic materials 0.000 abstract description 6
- 238000004090 dissolution Methods 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 2
- 239000012716 precipitator Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 21
- 239000000463 material Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- AFSWOABZOLEQMR-UHFFFAOYSA-J iron(4+);hydroxide;phosphate Chemical compound [OH-].[Fe+4].[O-]P([O-])([O-])=O AFSWOABZOLEQMR-UHFFFAOYSA-J 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 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
- 239000006227 byproduct Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- -1 iron-phosphorus-iron-lithium Chemical compound 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/14—Phosphates
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
- C30B29/66—Crystals of complex geometrical shape, e.g. tubes, cylinders
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of battery-grade single-crystal iron phosphate, which comprises the following steps: s1, adding an iron source into a phosphoric acid solution for full dissolution to obtain an iron-phosphorus solution; s2, adding hydrogen peroxide and 1,2-propylene glycol into the iron-phosphorus liquid, stirring and reacting for 10-30min at normal temperature, heating and stirring and reacting for 3-6h at 70-100 ℃, standing, aging and filtering after the reaction is finished, washing and drying the obtained filter cake, and sintering at high temperature to obtain the iron-phosphorus composite filter cake. The reaction process of the invention does not need to adjust the pH value and add a precipitator, the interference of impurity ions is avoided while the process steps are simplified, the prepared ferric phosphate is in an octahedral single crystal shape without impurity phase, the purity is high, the granularity is small, the high compaction density is realized, and the method can be used for preparing Gao Yashi lithium iron phosphate.
Description
Technical Field
The invention relates to the technical field of lithium ion battery materials, in particular to a preparation method of battery-grade single crystal iron phosphate.
Background
With the rapid development of global economy, the existing human resources are increasingly deficient, and the development of new energy becomes the guide of the existing society. Lithium iron phosphate (LiFePO) 4 ) As a novel lithium ion battery cathode material, the lithium ion battery cathode material has excellent cycle stability and high temperature resistance, is popular in the new energy market, but has poor low-temperature performance and energy density compared with a ternary battery. The compacted density of the lithium iron phosphate material is influenced by sintering temperature, grinding particle size and a precursor, wherein the sintering temperature and the grinding particle size have limited space for improving the compacted density, and the precursor is improvedThe compaction density of the lithium iron phosphate material is improved, so that the compaction of the lithium iron phosphate material is the most effective and effective method.
The ferric phosphate is one of important materials for industrially producing the lithium iron phosphate, in a plurality of ferric phosphate synthesis methods, the cost required by the ferric phosphate synthesized by taking ferrous sulfate which is a byproduct of titanium white slag as a raw material is low, but the step of extracting the ferrous sulfate in the synthesis process is complex, and a large amount of pure water is required for washing out the over-standard sulfate radical (SO) in the subsequent preparation 4 2- ) The water resource is wasted, and the production cost is increased. In addition, the ferric phosphate produced by the process has many impurities and low compaction density, so that the subsequent production of the lithium iron phosphate has poor electrochemical performance.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a preparation method of battery-grade single-crystal iron phosphate.
The invention provides a preparation method of battery grade single crystal iron phosphate, which comprises the following steps:
s1, adding an iron source into a phosphoric acid solution for full dissolution to obtain an iron-phosphorus solution;
s2, adding hydrogen peroxide and 1,2-propylene glycol into the iron-phosphorus liquid, stirring and reacting for 10-30min at normal temperature, heating and stirring and reacting for 3-6h at 70-100 ℃, standing, aging and filtering after the reaction is finished, washing and drying the obtained filter cake, and sintering at high temperature to obtain the iron-phosphorus composite filter cake.
In S2, the obtained filter cake is hydrated hydroxyl iron phosphate, and the reaction mechanism of the reaction for obtaining the hydrated hydroxyl iron phosphate is as follows: 10Fe 2+ +5H 2 O 2 +8HPO 4 2- ——2Fe 5 (PO 4 ) 4 (OH) 3 ·2H 2 O+4H + 。
Preferably, the iron source is industrial waste containing elementary iron, and is preferably at least one of iron sheet, scrap iron and iron slag.
Preferably, the carbon content in the iron sheet, the iron scrap and the iron slag is less than or equal to 3 percent.
Preferably, the mass fraction of the phosphoric acid solution is 30 to 60wt%.
Preferably, the mass ratio of the iron source to the phosphoric acid solution is 1: (3-6).
Preferably, the ratio of the iron source to the hydrogen peroxide is 1g: (1-2) mL, wherein the mass fraction of the hydrogen peroxide is 20-30wt%.
Preferably, the mass ratio of the iron source to 1,2-propanediol is 1: (0.05-0.1).
In S1, complete dissolution means no obvious bubbles are generated; preferably, the dissolving temperature in S1 is 50-70 ℃ and the time is 20-30h.
In the S1, after the iron source is added into the phosphoric acid solution and fully dissolved, the conventional filtration and impurity removal steps can be further included, and the filtrate is collected after filtration, namely the iron-phosphorus solution.
Preferably, in S2, the stirring speed is 200-500rpm.
Preferably, in S2, the standing and aging time is 10-30min.
Preferably, in S2, the temperature of high-temperature sintering is 600-800 ℃ and the time is 5-10h.
The battery grade single crystal iron phosphate is prepared by the preparation method.
The invention has the following beneficial effects:
according to the preparation method of the iron phosphate, industrial waste iron scrap pieces, scrap iron and iron slag can be used as raw materials, and the conditions such as concentration proportion, temperature, stirring speed, reaction time and the like of the raw materials are controlled, so that the high-purity iron phosphate can be prepared without adjusting pH and other precipitants in the process of preparing the iron phosphate; meanwhile, the phosphoric acid generated by the reaction can be recycled to continuously dissolve iron, so that closed circulation and zero wastewater discharge are realized, the process flow is simplified, and the production cost, the impurity removal cost and the wastewater treatment cost are reduced. According to the method, 1,2 propylene glycol is used as a surfactant, the prepared iron phosphate is octahedral and single-crystal in shape, high in purity and suitable for preparing high-compaction-density lithium iron phosphate.
Drawings
Fig. 1 is an SEM image of iron phosphate prepared in example 1 of the present invention.
Fig. 2 is an SEM image of the iron phosphate prepared in comparative example 1 of the present invention.
Fig. 3 is an SEM image of the iron phosphate prepared in comparative example 2 of the present invention.
Fig. 4 is an SEM image of the iron phosphate prepared in comparative example 3 of the present invention.
Fig. 5 is an SEM image of iron phosphate prepared in comparative example 4 of the present invention.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
In the following examples and comparative examples, the carbon content of the scrap iron pieces used was 2wt%.
Example 1
S1, adding 60g of waste iron sheets into 293.1g of phosphoric acid solution with the mass fraction of 60wt%, standing and dissolving for 24 hours under the heating of a water bath at 60 ℃, then filtering, and collecting filtrate to obtain iron-phosphorus liquid;
s2, adding 4.93g of 1,2 propylene glycol and 80mL of hydrogen peroxide with the mass fraction of 30wt% into the iron-phosphorus solution, stirring and reacting at the normal temperature at the rotating speed of 300rpm for 10min, then heating to 80 ℃, preserving the temperature at the rotating speed of 300rpm, stirring and reacting for 4h, standing for 10min, filtering, washing the obtained filter cake with deionized water for 3 times, then drying at 100 ℃ for 12h, and then sintering at 600 ℃ for 5h to obtain the battery-grade monocrystalline iron phosphate.
Example 2
Example 2 differs from example 1 only in that: the phosphoric acid solution had a mass concentration of 52wt%.
Example 3
Example 2 differs from example 1 only in that: the phosphoric acid solution had a mass concentration of 42wt%.
Example 4
S1, adding 60g of waste iron sheets into 349.2g of 35wt% phosphoric acid solution, standing and dissolving for 30 hours under heating of a water bath at 50 ℃, filtering, and collecting filtrate to obtain iron-phosphorus liquid;
s2, adding 6g of 1,2 propylene glycol and 120mL of hydrogen peroxide with the mass fraction of 30wt% into the iron-phosphorus solution, stirring and reacting at the normal temperature at the rotating speed of 200rpm for 20min, then heating to 70 ℃, keeping the temperature at the rotating speed of 200rpm, stirring and reacting for 6h, standing for 20min, filtering, washing the obtained filter cake with deionized water for 3 times, drying at the temperature of 100 ℃ for 12h, and sintering at the temperature of 700 ℃ for 8h to obtain the battery-grade monocrystalline iron phosphate.
Example 5
S1, adding 60g of waste iron pieces into 232.2g of phosphoric acid solution with the mass fraction of 42wt%, standing and dissolving for 20 hours under the heating of a water bath at 70 ℃, then filtering, and collecting filtrate to obtain iron-phosphorus liquid;
s2, adding 3g of 1,2 propylene glycol and 60mL of hydrogen peroxide with the mass fraction of 30wt% into the iron-phosphorus solution, stirring and reacting for 30min at the normal temperature at the rotating speed of 500rpm, then heating to 95 ℃, keeping the temperature and stirring and reacting for 4h at the rotating speed of 200rpm, standing for 10min, filtering, washing the obtained filter cake for 3 times with deionized water, then drying for 12h at 100 ℃, and then sintering for 5h at 800 ℃ to obtain the battery-grade monocrystalline iron phosphate.
Comparative example 1
Comparative example 1 differs from example 1 only in that: polyethylene glycol was used instead of 1,2 propylene glycol.
Comparative example 2
Comparative example 2 differs from example 1 only in that: sodium metaaluminate is used instead of 1,2 propylene glycol.
Comparative example 3
Comparative example 3 differs from example 1 only in that: sodium dodecylbenzene sulfonate was used in place of 1,2 propylene glycol.
Comparative example 4
Comparative example 1 differs from example 1 only in that: no 1,2 propylene glycol was added.
Test examples
SEM images of the iron phosphate prepared in example 1 and comparative examples 1 to 3 are shown in fig. 1 to 4. It can be seen that the morphology of FIG. 1 is that of octahedral large single crystal, which is due to the participation of the surfactant 1,2-propanediol, fe 3+ The hexa-coordinate geometric (i.e. octahedral) configuration of the coordination ions of 1,2-propylene glycol can be functionalized to form hydrated hydroxyl iron phosphate single crystal octahedrons, and anhydrous single crystal octahedron iron phosphate is formed through high-temperature dehydration, and the grain diameter is 1-3 mu m. Comparative examples 1 to 3 using other surfactants, comparative example 4 using no surfactant, the iron phosphate formed was in the form of fine flakes having a lamella thickness of 20 to 40nm, wherein comparative examples 1 to 3 were compared with comparative example 4The final shape of the ferric phosphate is improved.
The iron phosphate of examples 1 to 3 and comparative examples 1 to 4 was used to prepare iron-phosphorus-iron-lithium according to a conventional method, comprising the steps of:
s01: mixing iron phosphate, lithium carbonate and glucose according to a molar ratio of 1:1.02:0.2, preparing materials, premixing for 12 hours, and performing sand grinding treatment and spraying to obtain a dried material;
s02: and under the protection of nitrogen, placing the dried material in an atmosphere furnace, and preserving heat for 10 hours at 750 ℃ to obtain the lithium iron phosphate.
The lithium iron phosphate prepared from the iron phosphate of examples 1 to 3 and comparative examples 1 to 4 described above was subjected to a performance test, and the results are shown in table 1:
TABLE 1
As can be seen from a comparison of the data of examples 1-3 in table 1, the compacted density of the lithium iron phosphate prepared from the iron phosphate formed increases with the increase of the concentration of phosphoric acid.
As can be seen by comparing the data of the example 1 and the comparative examples 1 to 4 in the table 1, the 1,2-propylene glycol is used as the surfactant, and the lithium iron phosphate prepared from the formed iron phosphate with the large single crystal octahedron morphology has the highest compaction density which is 2.58g/cm 3 . In conclusion, the single-crystal octahedral iron phosphate prepared by the preparation method disclosed by the invention has the advantages of strong product performance stability and higher compaction density.
Therefore, the preparation method disclosed by the invention has the advantages that no precipitator is added in the whole process, the cost of the adopted raw materials is low, the whole solution system can be recycled, the preparation cost is reduced, the product is high-purity monocrystalline iron phosphate, the appearance is octahedral monocrystalline, no impurity phase exists, the purity is high, the granularity is small, the high-compaction density is realized, and the preparation method can be used for preparing Gao Yashi lithium iron phosphate.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. A preparation method of battery-grade single crystal iron phosphate is characterized by comprising the following steps:
s1, adding an iron source into a phosphoric acid solution to be fully dissolved to obtain iron-phosphorus liquid;
s2, adding hydrogen peroxide and 1,2-propylene glycol into the iron-phosphorus liquid, stirring and reacting for 10-30min at normal temperature, heating and stirring and reacting for 3-6h at 70-100 ℃, standing, aging and filtering after the reaction is finished, washing and drying the obtained filter cake, and sintering at high temperature to obtain the iron-phosphorus composite filter cake.
2. The method for preparing battery-grade monocrystalline iron phosphate according to claim 1, wherein the iron source is at least one of iron pieces, iron filings and iron slag.
3. The method for preparing battery-grade monocrystalline iron phosphate according to claim 2, wherein the carbon content in the iron sheet, the iron filings and the iron slag is less than or equal to 3%.
4. The method for preparing battery-grade monocrystalline iron phosphate according to claim 1, characterized in that the mass fraction of the phosphoric acid solution is 30-60wt%; the mass ratio of the iron source to the phosphoric acid solution is 1: (3-6).
5. The preparation method of the battery-grade monocrystalline iron phosphate according to claim 1, wherein the ratio of the iron source to hydrogen peroxide is 1g: (1-2) mL, wherein the mass fraction of the hydrogen peroxide is 20-30wt%; the mass ratio of the iron source to 1,2-propanediol is 1: (0.05-0.1).
6. The preparation method of battery grade single crystal iron phosphate according to claim 1, characterized in that the dissolving temperature in S1 is 50-70 ℃ and the time is 20-30h.
7. The method for preparing battery-grade monocrystalline iron phosphate according to claim 1, wherein in S2, the stirring speed is 200-500rpm.
8. The method for preparing battery-grade monocrystalline iron phosphate according to claim 1, wherein in S2, the standing and aging time is 10-30min.
9. The preparation method of battery grade single crystal iron phosphate according to claim 1, characterized in that in S2, the high-temperature sintering temperature is 600-800 ℃ and the time is 5-10h.
10. A battery grade single crystal iron phosphate, characterized by being produced by the production method according to any one of claims 1 to 9.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012172839A1 (en) * | 2011-06-17 | 2012-12-20 | Ｊｆｅケミカル株式会社 | Method for manufacturing lithium iron phosphate |
| CN104817059A (en) * | 2015-04-29 | 2015-08-05 | 江西东华科技园有限责任公司 | Method for preparing battery-grade iron phosphate from reaction between iron powder and phosphoric acid |
| CN114031060A (en) * | 2021-12-08 | 2022-02-11 | 华东理工大学 | Preparation method of battery-grade anhydrous iron phosphate with lamellar structure |
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| WO2012172839A1 (en) * | 2011-06-17 | 2012-12-20 | Ｊｆｅケミカル株式会社 | Method for manufacturing lithium iron phosphate |
| CN104817059A (en) * | 2015-04-29 | 2015-08-05 | 江西东华科技园有限责任公司 | Method for preparing battery-grade iron phosphate from reaction between iron powder and phosphoric acid |
| CN114031060A (en) * | 2021-12-08 | 2022-02-11 | 华东理工大学 | Preparation method of battery-grade anhydrous iron phosphate with lamellar structure |
Non-Patent Citations (1)
| Title |
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| 马晓丽: "羟基磷酸铁的可控制备及其电化学性能研究", 中国优秀硕士学位论文全文数据库 工程科技I辑, no. 09, pages 020 - 206 * |
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