CN116946998B - Synthesis process of ferric phosphate and synthesized ferric phosphate - Google Patents
Synthesis process of ferric phosphate and synthesized ferric phosphate Download PDFInfo
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- CN116946998B CN116946998B CN202311007507.5A CN202311007507A CN116946998B CN 116946998 B CN116946998 B CN 116946998B CN 202311007507 A CN202311007507 A CN 202311007507A CN 116946998 B CN116946998 B CN 116946998B
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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 117
- 238000000034 method Methods 0.000 title claims abstract description 39
- 230000008569 process Effects 0.000 title claims abstract description 23
- 239000005955 Ferric phosphate Substances 0.000 title abstract description 51
- 229940032958 ferric phosphate Drugs 0.000 title abstract description 51
- 229910000399 iron(III) phosphate Inorganic materials 0.000 title abstract description 51
- 230000015572 biosynthetic process Effects 0.000 title abstract description 15
- 238000003786 synthesis reaction Methods 0.000 title abstract description 15
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims abstract description 71
- 150000003839 salts Chemical class 0.000 claims abstract description 32
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 30
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 75
- 229910000398 iron phosphate Inorganic materials 0.000 claims description 65
- 235000006408 oxalic acid Nutrition 0.000 claims description 25
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- 238000001816 cooling Methods 0.000 claims description 20
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical group [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 19
- 150000007524 organic acids Chemical class 0.000 claims description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 10
- 230000002194 synthesizing effect Effects 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 7
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 7
- 239000011976 maleic acid Substances 0.000 claims description 7
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 7
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 5
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 5
- 150000002505 iron Chemical class 0.000 claims description 5
- 239000001630 malic acid Substances 0.000 claims description 5
- 235000011090 malic acid Nutrition 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 abstract description 45
- 239000000463 material Substances 0.000 abstract description 28
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 16
- 229910052742 iron Inorganic materials 0.000 abstract description 13
- 239000012621 metal-organic framework Substances 0.000 abstract description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 8
- 230000001105 regulatory effect Effects 0.000 abstract description 5
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 150000003009 phosphonic acids Chemical class 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 42
- 239000000047 product Substances 0.000 description 37
- 238000009826 distribution Methods 0.000 description 26
- 238000004458 analytical method Methods 0.000 description 16
- 239000011259 mixed solution Substances 0.000 description 16
- 238000005303 weighing Methods 0.000 description 15
- 239000003446 ligand Substances 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 238000005406 washing Methods 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 235000003891 ferrous sulphate Nutrition 0.000 description 4
- 239000011790 ferrous sulphate Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- -1 iron ions Chemical class 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000008055 phosphate buffer solution Substances 0.000 description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 239000013297 MIL-127 Substances 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229960002089 ferrous chloride Drugs 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 238000003921 particle size analysis Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 239000013291 MIL-100 Substances 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- VYIGFALZSKQAPJ-UHFFFAOYSA-L [Fe+2].[O-]P([O-])=O Chemical compound [Fe+2].[O-]P([O-])=O VYIGFALZSKQAPJ-UHFFFAOYSA-L 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- PFPIMAZLJXJVAN-UHFFFAOYSA-K iron(3+);triperchlorate;hydrate Chemical compound O.[Fe+3].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O PFPIMAZLJXJVAN-UHFFFAOYSA-K 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000009489 vacuum treatment Methods 0.000 description 1
- 239000002351 wastewater Substances 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
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- 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
- C01P2006/12—Surface area
-
- 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 provides a synthesis process of ferric phosphate and synthesized ferric phosphate thereof, which belong to the field of new energy materials. According to the invention, the metal organic framework material containing phosphonic acid groups and iron elements is directly synthesized for the first time, and the characteristics of ordered structure of the metal organic framework material are utilized, so that the obtained ferric phosphate is not easy to agglomerate after roasting, the synthesis method is simple and efficient, the content of ferric salt and organic phosphoric acid is simply regulated, and the particle size and specific surface area of the ferric phosphate can be regulated and controlled by selecting different organic phosphonic acids, so that the large-scale production is facilitated.
Description
Technical Field
The invention belongs to the field of advanced chemical materials, and particularly relates to a synthesis process of ferric phosphate and the synthesized ferric phosphate.
Background
Iron phosphate is an important raw material for preparing lithium iron phosphate, and the physical and chemical properties of the iron phosphate such as element composition, particle size and the like are important to the final lithium iron phosphate performance. The preparation of ferric phosphate is mainly prepared by taking soluble ferric salt and phosphate as raw materials through a coprecipitation method. The existing mainstream ferric phosphate preparation process is to prepare battery-grade ferric phosphate by taking ferrous sulfate as an iron source, phosphoric acid or phosphate as a phosphorus source, hydrogen peroxide as an auxiliary agent, regulating pH by adopting ammonium salt or alkali, and performing coprecipitation, curing, washing and other processes. However, the process flow is longer, ammonium sulfate byproducts are generated, a large amount of water is needed for repeated washing in order to remove sulfate radical in the product, a large amount of waste water containing sulfuric acid is generated, and the quality of the obtained ferric phosphate is not high, and the main characteristics are that the ferric phosphate is easy to agglomerate, the particle size distribution is uneven, the specific surface area is small, and the like.
CN116409763a discloses a method for preparing high purity ferric phosphate from wet crude phosphoric acid, which comprises the following steps: (1) Mixing ferrous sulfate solution, crude phosphoric acid and oxidant to obtain a precipitation precursor solution; (2) The pre-precipitation solution is subjected to first temperature rising and first heat preservation precipitation, and solid-liquid separation is carried out to obtain crude ferric phosphate; (3) redissolving the crude ferric phosphate to obtain refined solution; (4) And carrying out second temperature rising and second temperature keeping precipitation on the refined solution, carrying out solid-liquid separation, and washing the solid phase to obtain the high-purity ferric phosphate. The method can adopt low-value raw materials with high impurity content, has simple preparation process and is hopeful to greatly reduce the preparation cost of the ferric phosphate, but the problems of agglomeration of the ferric phosphate, uneven particle size distribution and small specific surface area are not solved.
CN115231539a discloses a preparation method of high-purity ferric phosphate, which mainly aims to solve the problems that in the traditional wet process for preparing ferric phosphate, the reaction process needs to adjust the PH and control the reaction speed, the ions involved in the reaction often cause high requirements for subsequent washing and impurity removal, and the prepared ferric phosphate material has low purity and low yield.
CN115385317a discloses a method for preparing mesoporous nano ferric phosphate by pseudomorphic transformation, which uses MOFs as a coordination compound to easily form Fe 3+ And the iron phosphate is prepared by the principle of strong interaction with phosphate ions. The method comprises the steps of preparing iron-based metal organic frame Materials (MOFs) through the reaction and assembly of specific metal ferric salts and organic matters, carrying out the treatments of crushing, stirring, standing and the like, reacting with phosphate buffers with different concentrations to obtain a crude product of hydrated ferric phosphate, and washing and drying to obtain ferric phosphate powder. The obtained ferric phosphate is mesoporous ferric phosphate crystal with narrower pore size distribution, and meanwhile, the original crystal form is maintained, and the natural pseudomorphic transformation process is met. However, the preparation process of the method is complex, the obtained ferric phosphate crystal is unstable, and the preparation process is time-consuming.
In order to solve the problems of the existing iron phosphate synthesis process, such as uneven particle size, easy agglomeration, large specific surface area and the like of the synthesized iron phosphate, the invention provides an iron phosphate synthesis process which adopts soluble ferric salt as a raw material, adopts organic phosphonic acid as a ligand, synthesizes an iron organic phosphonic acid metal organic framework material under a hydrothermal condition, and then roasting under an air atmosphere to obtain uniformly dispersed iron phosphate, wherein the obtained iron phosphate is not easy to agglomerate, has uniform particle size and narrow particle size distribution, and has good application prospect.
Disclosure of Invention
The invention provides a synthesis process of ferric phosphate, which adopts soluble ferric salt as a raw material, adopts organic phosphonic acid as a ligand, synthesizes an iron organic phosphonic acid metal organic framework material under a hydrothermal condition, and then is roasted in an air atmosphere to obtain uniformly dispersed ferric phosphate, wherein the obtained ferric phosphate is not easy to agglomerate, has uniform particle size and narrow particle size distribution. The obtained lithium iron phosphate prepared from the ferric phosphate has more excellent performance.
The invention provides a synthesis process of ferric phosphate, which comprises the steps of mixing soluble ferric salt and an organic phosphonic acid solution, adding the organic acid, uniformly stirring, transferring to a high-pressure reaction kettle for hydrothermal reaction, naturally cooling, taking out a product, and drying and roasting to obtain the ferric phosphate.
Further, the soluble ferric salt is ferric chloride, ferric sulfate, ferric nitrate, ferrous sulfate, ferrous chloride, ferrous nitrate, ferrous acetate, ferric acetate and ferric oxalate, and the soluble ferric salt is ferric salt or ferrous salt. Providing an iron source for iron phosphonate synthesis.
Further, the organic phosphonic acid is organic monophosphonic acid, organic biphosphonic acid, organic triphosphonic acid, further, the organic phosphonic acid is One or more of the following. The organic phosphoric acid provides an organic acid ligand for metal organic framework synthesis and further provides a phosphine source for synthesizing ferric phosphate.
Further, the organic acid is one or more of acetic acid, oxalic acid, maleic acid, malic acid and citric acid, and the organic acid plays roles in stabilizing iron ions and reducing in a reaction system.
Further, the molar ratio of phosphine element in the organic phosphoric acid to iron element in the soluble iron salt is 1.2-10:1, preferably 1.2-8:1, preferably 1.2-6:1, further preferably 1.5-3:1.
Further, the molar usage ratio of the organic acid to the organic phosphoric acid is 1:10-20, preferably 1:10-15; further preferably 1:10-12.
Further, the drying temperature is 80-120 ℃.
Further, the hydrothermal temperature is 120-180deg.C, more preferably 120-160deg.C, and still more preferably 140-150deg.C. The hydrothermal time is 6-24 hours, more preferably 6-18 hours, and still more preferably 8-12 hours.
Further, the firing temperature is 400 to 600 ℃, more preferably 450 to 550 ℃, still more preferably 500 to 550 ℃. The roasting time is 2-6 hours, further 2-4 hours and further 3-4 hours.
In a second aspect, the invention provides an iron phosphate, the iron phosphate being obtainable by the process of the invention.
The synthesis process of the invention firstly generates the metal organic framework compound of the iron and the organic phosphoric acid, and then the metal organic framework compound is roasted in the air atmosphere to obtain the highly dispersed ferric phosphate, and the ferric phosphate has high purity, narrow particle size distribution, uniform size and large specific surface area. Can meet the requirement of strict raw material supply on the particle size distribution of the ferric phosphate. The energy density of the lithium iron phosphate battery can be improved.
According to the invention, the metal organic framework material containing phosphonic acid groups and iron elements is directly synthesized for the first time, and the characteristics of ordered structure of the metal organic framework material are utilized, so that the obtained ferric phosphate after roasting is not easy to agglomerate, and the particle sizes are similar. The synthesis method is simple and efficient, the content of ferric salt and organic phosphonic acid is simply adjusted, and the particle size and specific surface area of the ferric phosphate can be regulated and controlled by selecting different organic phosphonic acids, so that the method is favorable for large-scale production.
The iron phosphate synthesized by the method can meet the production of high-requirement lithium iron phosphate batteries, can obtain relatively high energy density, and ensures that products have better consistency.
Detailed Description
Those skilled in the art can, with the benefit of this disclosure, suitably modify the process parameters to achieve this. It is expressly noted that all such similar substitutions and modifications will be apparent to those skilled in the art, and are deemed to be included in the present invention. While the invention has been described with reference to preferred embodiments, it will be apparent to those skilled in the relevant art that variations and modifications can be made in the invention described herein without departing from the spirit or scope of the invention. The invention is further illustrated by the following specific examples, which should not be construed as limiting the invention.
The terms "comprising," "including," "having," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.
The phrase "consisting of …" excludes any unspecified element, step or component. If used in a claim, such phrase will cause the claim to be closed, such that it does not include materials other than those described, except for conventional impurities associated therewith. When the phrase "consisting of …" appears in a clause of the claim body, rather than immediately following the subject, it is limited to only the elements described in that clause; other elements are not excluded from the stated claims as a whole.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range.
In some examples, the approximating language may correspond to the precision of an instrument for measuring the value. In the present specification and claims, the range limitations may be combined and/or interchanged, such ranges including all the sub-ranges contained therein if not expressly stated.
The indefinite articles "a" and "an" preceding an element or component of the invention are not limited to the requirement (i.e. the number of occurrences) of the element or component. Thus, the use of "a" or "an" should be interpreted as including one or at least one, and the singular reference of an element or component includes the plural reference unless the amount clearly dictates otherwise.
The description of the terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., herein describe means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, schematic representations of the above terms are not necessarily for the same embodiment or example. The technical features of the respective embodiments of the present invention may be combined with each other as long as they do not collide with each other.
The materials and equipment used in the present invention are commercially available or are those commonly used in the art, and the methods described in the examples are those commonly used in the art unless otherwise specified.
The following will specifically describe in connection with specific embodiments:
the invention provides a synthesis process of ferric phosphate, which comprises the steps of mixing soluble ferric salt and an organic phosphonic acid solution, adding the organic acid, uniformly stirring, transferring to a high-pressure reaction kettle for hydrothermal reaction, naturally cooling, taking out a product, and drying and roasting to obtain the ferric phosphate. The whole synthesis process is simple and easy to regulate and control.
Further, the soluble ferric salt is ferric chloride, ferric sulfate, ferric nitrate, ferrous sulfate, ferrous chloride, ferrous nitrate, ferrous acetate, ferric acetate and ferric oxalate, and the soluble ferric salt is ferric salt or ferrous salt. The soluble ferric salt provides an iron source for synthesizing the ferric phosphonate, and the ferric salt mainly reacts with the organic phosphonic acid to form an organic ligand in a hydrothermal process.
Further, the organic phosphonic acid is organic monophosphonic acid, organic biphosphonic acid, organic tri-tetra-polyphosphonic acid, and further, the organic phosphonic acid is One or more of the following.
The organic phosphonic acid provides an organic acid ligand for synthesizing a metal organic framework, further provides a phosphine source for synthesizing ferric phosphate, and the organic ligand formed by the organic phosphonic acid and the iron is of a metal organic framework structure, is orderly arranged, and further forms uniform ferric phosphate particles after calcination, so that the product consistency is good.
In some embodiments, the metal organic framework material structure formed by different organic phosphonic acid ligands is different, the particle size of the ferric phosphate obtained by roasting is different, and the preferred organic phosphonic acid ligands areThe obtained ferric phosphate has large specific surface area and good uniformity of particle size.
Further, the organic acid is one or more of acetic acid, oxalic acid, maleic acid, malic acid and citric acid, and plays a role in stabilizing iron ions in the reaction system.
In some embodiments, the organic acid is maleic acid and citric acid, and the obtained ferric phosphate has good particle size uniformity.
Further, the molar ratio of elemental phosphorus in the organophosphonic acid to elemental iron in the soluble iron salt is 1.2-10:1, preferably 1.2-8:1, preferably 1.2-6:1, and more preferably 1.5-3:1. In some embodiments, the iron phosphate particles obtained by final calcination have good uniformity properties when the molar ratio of the elements of the organic phosphonic acid to the soluble iron salt is 1.5-3:1.
In some embodiments, the molar ratio of organic acid to organic phosphonic acid is 1:10-20, preferably 1:10-15; further preferably 1:10-12.
In some embodiments, the drying temperature is 80-120 ℃.
In some embodiments, the hydrothermal temperature is 120-180 ℃, further preferably 120-160 ℃, further preferably 140-150 ℃. The hydrothermal time is 6-24 hours, more preferably 6-18 hours, and still more preferably 8-12 hours.
In some embodiments, the firing temperature is 400-600 ℃, further preferably 450-550 ℃, further 500-550 ℃. The roasting time is 2-6 hours, further 2-4 hours and further 3-4 hours.
The following description is made in connection with specific examples, which are merely selected examples among numerous examples, and embodiments of the present invention are not limited to the following implementations:
example 1
Weighing ferric oxalate and organic phosphonic acid according to the element molar ratio of the organic phosphonic acid to the soluble ferric salt of 2:1Mixing the two materials, and adding oxalic acid and organic phosphonic acid +.>Oxalic acid is added in the molar dosage ratio of 1:10, the mixed solution is transferred into a high-pressure reaction kettle after being stirred uniformly, the hydrothermal temperature is kept at 150 ℃ for reaction for 8 hours, the product is taken out after natural cooling and dried at 100 ℃, and then the product is roasted for 4 hours at 550 ℃ in an air atmosphere, so that an iron phosphate sample is obtained.
The particle size distribution and specific surface of the iron phosphate were characterized, and the data obtained by analysis are shown in table 1.
The particle size distribution is analyzed by adopting a laser particle size analysis method, a proper amount of molecular ferric phosphate sample is added into a proper amount of deionized water, the sample is ensured to be uniformly dispersed in the suspension, the concentration of the suspension is regulated to be 0.5% -1%, the sample is obtained, the sample is filled into a sample cell, the particle size analysis is carried out by a Topsizer Plus laser particle size analyzer, and the data of D10, D50, D90 and D100 are analyzed, wherein the specific data are shown in Table 1.
The specific surface area of iron phosphate is measured by BET method, iron phosphate sample is ground into fine powder, the sample is put into vacuum tank or vacuum bottle, pretreatment is carried out under proper vacuum condition, gas and moisture adsorbed on the surface of powder are removed usually by high temperature annealing or vacuum suction, the sample after vacuum treatment is put into specific surface area analyzer, the gas used is nitrogen, and under low temperature and high vacuum condition, the gas is gradually pressurized to enter the sample for adsorption until equilibrium adsorption is reached, and the graph of gas adsorption amount and relative steam pressure (P/P0) is drawn according to the data of adsorption isotherm, thus obtaining specific surface area data, see in Table 1.
Example 2
Weighing ferric oxalate and organic phosphonic acid according to the element molar ratio of the organic phosphonic acid to the soluble ferric salt of 2:1Mixing the two materials, and adding oxalic acid and organic phosphonic acid +.>Oxalic acid is added in the molar dosage ratio of 1:10, the mixed solution is transferred into a high-pressure reaction kettle after being stirred uniformly, the hydrothermal temperature is kept at 150 ℃ for reaction for 8 hours, the product is taken out after natural cooling and dried at 100 ℃, and then the product is roasted for 4 hours at 550 ℃ in an air atmosphere, so that an iron phosphate sample is obtained.
The particle size distribution and specific surface of the iron phosphate were characterized, and the data obtained by analysis are shown in table 1.
Example 3
Weighing ferric oxalate and organic phosphonic acid according to the element molar ratio of the organic phosphonic acid to the soluble ferric salt of 2:1Mixing the twoHomogenizing, and adding oxalic acid and organic phosphonic acid>Oxalic acid is added in the molar dosage ratio of 1:10, the mixed solution is transferred into a high-pressure reaction kettle after being stirred uniformly, the hydrothermal temperature is kept at 150 ℃ for reaction for 8 hours, the product is taken out after natural cooling and dried at 100 ℃, and then the product is roasted for 4 hours at 550 ℃ in an air atmosphere, so that an iron phosphate sample is obtained.
The particle size distribution and specific surface of the iron phosphate were characterized, and the data obtained by analysis are shown in table 1.
Example 4
Weighing ferric oxalate and organic phosphonic acid according to the element molar ratio of the organic phosphonic acid to the soluble ferric salt of 2:1Mixing the two materials, and adding oxalic acid and organic phosphonic acid +.>Oxalic acid is added in the molar dosage ratio of 1:10, the mixed solution is transferred into a high-pressure reaction kettle after being stirred uniformly, the hydrothermal temperature is kept at 150 ℃ for reaction for 8 hours, the product is taken out after natural cooling and dried at 100 ℃, and then the product is roasted for 4 hours at 550 ℃ in an air atmosphere, so that an iron phosphate sample is obtained.
The particle size distribution and specific surface of the iron phosphate were characterized, and the data obtained by analysis are shown in table 1.
Example 5
Weighing ferric oxalate and organic phosphonic acid according to the element molar ratio of the organic phosphonic acid to the soluble ferric salt of 2:1Mixing the two materials, and adding acetic acid and organic phosphonic acid +.>Acetic acid is added in the molar dosage ratio of 1:10, and stirring is carried outAnd after being uniform, the mixed solution is transferred into a high-pressure reaction kettle, the hydrothermal temperature is kept at 150 ℃ for reaction for 8 hours, the product is taken out and dried at 100 ℃ after natural cooling, and then the product is roasted for 4 hours at 550 ℃ in an air atmosphere, so that an iron phosphate sample is obtained.
The particle size distribution and specific surface of the iron phosphate were characterized, and the data obtained by analysis are shown in table 1.
Example 6
Weighing ferric oxalate and organic phosphonic acid according to the element molar ratio of the organic phosphonic acid to the soluble ferric salt of 2:1Mixing the two materials, and adding maleic acid and organic phosphonic acid>Maleic acid is added in the molar dosage ratio of 1:10, the mixed solution is transferred into a high-pressure reaction kettle after being stirred uniformly, the hydrothermal temperature is kept at 150 ℃ for reaction for 8 hours, the product is taken out after natural cooling and dried at 100 ℃, and then the product is roasted for 4 hours at 550 ℃ in an air atmosphere, so that an iron phosphate sample is obtained.
The particle size distribution and specific surface of the iron phosphate were characterized, and the data obtained by analysis are shown in table 1.
Example 7
Weighing ferric oxalate and organic phosphonic acid according to the element molar ratio of the organic phosphonic acid to the soluble ferric salt of 2:1Mixing the two materials, and adding malic acid and organic phosphonic acid>Malic acid is added in the molar dosage ratio of 1:10, the mixed solution is transferred into a high-pressure reaction kettle after being stirred uniformly, the hydrothermal temperature is kept at 150 ℃ for reaction for 8 hours, the product is taken out after natural cooling and dried at 100 ℃, and then the product is roasted for 4 hours at 550 ℃ in an air atmosphere, so that an iron phosphate sample is obtained.
The particle size distribution and specific surface of the iron phosphate were characterized, and the data obtained by analysis are shown in table 1.
Example 8
Weighing ferric oxalate and organic phosphonic acid according to the element molar ratio of the organic phosphonic acid to the soluble ferric salt of 2:1Mixing the two materials, and adding citric acid and organic phosphonic acid>Adding citric acid into the mixture in a molar dosage ratio of 1:10, uniformly stirring, transferring the mixed solution into a high-pressure reaction kettle, keeping the hydrothermal temperature at 150 ℃ for reaction for 8 hours, naturally cooling, taking the product, drying at 100 ℃, and roasting the product at 550 ℃ for 4 hours in an air atmosphere to obtain the iron phosphate sample.
The particle size distribution and specific surface of the iron phosphate were characterized, and the data obtained by analysis are shown in table 1.
Example 9
Weighing ferric oxalate and organic phosphonic acid according to the element molar ratio of the organic phosphonic acid to the soluble ferric salt of 2:1Mixing the two materials, and adding sulfuric acid and organic phosphonic acid +.>Adding sulfuric acid into the mixture in a molar dosage ratio of 1:10, uniformly stirring, transferring the mixed solution into a high-pressure reaction kettle, keeping the hydrothermal temperature at 150 ℃ for reaction for 8 hours, naturally cooling, taking the product, drying at 100 ℃, and roasting the product at 550 ℃ for 4 hours in an air atmosphere to obtain the iron phosphate sample.
The particle size distribution and specific surface of the iron phosphate were characterized, and the data obtained by analysis are shown in table 1.
Example 10
According to organic phosphinesThe iron oxalate and the organic phosphonic acid are weighed according to the element molar ratio of 1:1 of the acid to the soluble ferric saltMixing the two materials, and adding oxalic acid and organic phosphonic acid +.>Oxalic acid is added in the molar dosage ratio of 1:10, the mixed solution is transferred into a high-pressure reaction kettle after being stirred uniformly, the hydrothermal temperature is kept at 150 ℃ for reaction for 8 hours, the product is taken out after natural cooling and dried at 100 ℃, and then the product is roasted for 4 hours at 550 ℃ in an air atmosphere, so that an iron phosphate sample is obtained.
The particle size distribution and specific surface of the iron phosphate were characterized, and the data obtained by analysis are shown in table 1.
Example 11
Weighing ferric oxalate and organic phosphonic acid according to the element mol ratio of the organic phosphonic acid and the soluble ferric salt of 1.2:1Mixing the two materials, and adding oxalic acid and organic phosphonic acid +.>Oxalic acid is added in the molar dosage ratio of 1:10, the mixed solution is transferred into a high-pressure reaction kettle after being stirred uniformly, the hydrothermal temperature is kept at 150 ℃ for reaction for 8 hours, the product is taken out after natural cooling and dried at 100 ℃, and then the product is roasted for 4 hours at 550 ℃ in an air atmosphere, so that an iron phosphate sample is obtained.
The particle size distribution and specific surface of the iron phosphate were characterized, and the data obtained by analysis are shown in table 1.
Example 12
Weighing ferric oxalate and organic phosphonic acid according to the element mol ratio of the organic phosphonic acid and the soluble ferric salt of 1.5:1Both are combinedMixing uniformly, and adding oxalic acid and organic phosphonic acid>Oxalic acid is added in the molar dosage ratio of 1:10, the mixed solution is transferred into a high-pressure reaction kettle after being stirred uniformly, the hydrothermal temperature is kept at 150 ℃ for reaction for 8 hours, the product is taken out after natural cooling and dried at 100 ℃, and then the product is roasted for 4 hours at 550 ℃ in an air atmosphere, so that an iron phosphate sample is obtained.
The particle size distribution and specific surface of the iron phosphate were characterized, and the data obtained by analysis are shown in table 1.
Example 13
Weighing ferric oxalate and organic phosphonic acid according to the element molar ratio of the organic phosphonic acid to the soluble ferric salt of 3:1Mixing the two materials, and adding oxalic acid and organic phosphonic acid +.>Oxalic acid is added in the molar dosage ratio of 1:10, the mixed solution is transferred into a high-pressure reaction kettle after being stirred uniformly, the hydrothermal temperature is kept at 150 ℃ for reaction for 8 hours, the product is taken out after natural cooling and dried at 100 ℃, and then the product is roasted for 4 hours at 550 ℃ in an air atmosphere, so that an iron phosphate sample is obtained.
The particle size distribution and specific surface of the iron phosphate were characterized, and the data obtained by analysis are shown in table 1.
Example 14
Weighing ferric oxalate and organic phosphonic acid according to the element molar ratio of the organic phosphonic acid to the soluble ferric salt of 6:1Mixing the two materials, and adding oxalic acid and organic phosphonic acid +.>Oxalic acid is added in the molar dosage ratio of 1:10,and after being stirred uniformly, transferring the mixed solution into a high-pressure reaction kettle, keeping the hydrothermal temperature at 150 ℃ for reaction for 8 hours, naturally cooling, taking a product, drying at 100 ℃, and roasting the product at 550 ℃ for 4 hours in an air atmosphere to obtain an iron phosphate sample.
The particle size distribution and specific surface of the iron phosphate were characterized, and the data obtained by analysis are shown in table 1.
Example 15
Weighing ferric oxalate and organic phosphonic acid according to the element molar ratio of the organic phosphonic acid to the soluble ferric salt of 8:1Mixing the two materials, and adding oxalic acid and organic phosphonic acid +.>Oxalic acid is added in the molar dosage ratio of 1:10, the mixed solution is transferred into a high-pressure reaction kettle after being stirred uniformly, the hydrothermal temperature is kept at 150 ℃ for reaction for 8 hours, the product is taken out after natural cooling and dried at 100 ℃, and then the product is roasted for 4 hours at 550 ℃ in an air atmosphere, so that an iron phosphate sample is obtained.
The particle size distribution and specific surface of the iron phosphate were characterized, and the data obtained by analysis are shown in table 1.
Example 16
Weighing ferric oxalate and organic phosphonic acid according to the element molar ratio of the organic phosphonic acid to the soluble ferric salt of 10:1Mixing the two materials, and adding oxalic acid and organic phosphonic acid +.>Oxalic acid is added in the molar dosage ratio of 1:10, the mixed solution is transferred into a high-pressure reaction kettle after being stirred uniformly, the hydrothermal temperature is kept at 150 ℃ for reaction for 8 hours, the product is taken out after natural cooling and dried at 100 ℃, and then the product is roasted for 4 hours at 550 ℃ in an air atmosphere, so that an iron phosphate sample is obtained.
The particle size distribution and specific surface of the iron phosphate were characterized, and the data obtained by analysis are shown in table 1.
Comparative example
Preparation experiments were performed with reference to the protocol of example 2 of the prior art CN115385317a, 1.18g of iron (III) perchlorate hydrate, 1.19g of bis (3, 5-dicarboxyphenyl) azo, 150mL of n, n-dimethylformamide, 1mL of 5M hydrofluoric acid were weighed, the reactant starting materials were sonicated, stirred until completely dissolved, transferred into a teflon lined reaction vessel, and reacted for 3 days at 150 ℃. After the reaction is finished, naturally cooling to room temperature, washing twice by adopting DMF, washing twice by adopting ethanol, and finally washing once by adopting deionized water. After natural air drying, brown powder MIL-127 (Fe) is obtained.
Taking 1g of dried MIL-127 (Fe) powder, crushing for 8s by a high-frequency crusher at 24000rpm, taking 500ml of commercial 0.1mol/L isotonic Phosphate Buffer Solution (PBS) with pH of 7.4, soaking MIL-100 (Fe) in the phosphate buffer solution, ultrasonically dissolving for 20min, magnetically stirring for 24h at normal temperature, standing for 30min, observing that the color of the powder is gradually changed from brown to pale yellow, alternately washing with deionized water and ethanol for 3 times, and vacuum drying for 12h to obtain the nano mesoporous ferric phosphate.
Data were measured by the method of example 1 of the present invention, and the obtained data are shown in table 1.
TABLE 1 physical parameters of iron phosphate
The performance test of the iron phosphate of examples 1-4 shows that the ligand species of the organic phosphonic acid has an effect on both the particle size and specific surface area of the iron phosphate, and that all the particle sizes of the iron phosphate are relatively uniform in comparison with the ligand from experimental dataThe ligand has the best particle size uniformity and relatively large specific surface area.
The performance tests of the iron phosphate of examples 5-8 show that the kind of organic acid has an effect on both the particle size and specific surface area of the iron phosphate, and that all the particle sizes of the iron phosphate are relatively uniform from the experimental data, wherein the iron phosphate obtained by using the organic acid maleic acid and citric acid as organic acid ligands has a more uniform particle size distribution and a large specific surface area. The data in examples 5-9 and 9 show that the uniformity of particle size obtained by the adjustment of the sulfuric acid of the inorganic acid is poor compared with that of the organic acid, the specific surface area is large, and the organic acid is required to be used for preparation, so that the preparation performance of the organic acid is better than that of the inorganic acid.
Examples 10-16 compare the effect of different P/fe ratios on iron phosphate synthesis, and from experimental data it can be seen that the P/fe ratio also has an effect on both the particle size and specific surface area of the iron phosphate, with the specific surface area of the iron phosphate increasing first and then decreasing as P/fe increases.
Examples 1-8, 11-16 are compared with comparative examples, the particle diameter distribution of the iron phosphate synthesized by the method is narrower, the specific surface area is larger, the synthesis process is mainly adopted, the steps are relatively simple, the reaction conditions are easy to control, and the method is more suitable for large-scale production.
The above description of the embodiments is only for aiding in the understanding of the method of the present invention and its core ideas. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims.
Claims (6)
1. A process for synthesizing iron phosphate includes such steps as mixing iron salt with organic phosphonic acid solution, adding organic acid, stirring, hydrothermal reaction in high-pressure reactor, natural cooling, drying and calcining to obtain iron phosphate、/>、/>、/>One or more of the following; the organic acid is one or more of acetic acid, oxalic acid, maleic acid, malic acid and citric acid; the ferric salt is ferric oxalate.
2. The process for synthesizing iron phosphate according to claim 1, wherein the molar ratio of the phosphorus element in the organic phosphonic acid to the iron element in the iron salt is 1.2-10:1.
3. The process for synthesizing iron phosphate according to claim 1, wherein the molar ratio of said organic acid to said organic phosphonic acid is 1:10-20.
4. The process for synthesizing iron phosphate according to claim 1, wherein the hydrothermal temperature is 120-180 ℃; the hydrothermal time is 6-24h.
5. The process for synthesizing iron phosphate according to claim 1, wherein the drying temperature is 80-120 ℃.
6. The process for synthesizing iron phosphate according to claim 1, wherein the roasting temperature is 400-600 ℃; the roasting time is 2-6h.
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