CN117923452A - Method for preparing composite sodium ferric pyrophosphate material in large scale - Google Patents
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- 239000000463 material Substances 0.000 title claims abstract description 66
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 34
- XWQGIDJIEPIQBD-UHFFFAOYSA-J sodium;iron(3+);phosphonato phosphate Chemical compound [Na+].[Fe+3].[O-]P([O-])(=O)OP([O-])([O-])=O XWQGIDJIEPIQBD-UHFFFAOYSA-J 0.000 title claims abstract description 24
- 239000002243 precursor Substances 0.000 claims abstract description 60
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 35
- 239000011734 sodium Substances 0.000 claims abstract description 24
- 238000002360 preparation method Methods 0.000 claims abstract description 20
- 239000001488 sodium phosphate Substances 0.000 claims abstract description 16
- 229910000162 sodium phosphate Inorganic materials 0.000 claims abstract description 16
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims abstract description 16
- 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 claims abstract description 9
- 238000000975 co-precipitation Methods 0.000 claims abstract description 9
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- 238000005245 sintering Methods 0.000 claims abstract description 6
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 3
- 238000007580 dry-mixing Methods 0.000 claims abstract description 3
- 239000007790 solid phase Substances 0.000 claims abstract description 3
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000008139 complexing agent Substances 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000011645 ferric sodium diphosphate Substances 0.000 claims description 10
- 235000019851 ferric sodium diphosphate Nutrition 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 239000003963 antioxidant agent Substances 0.000 claims description 7
- 230000003078 antioxidant effect Effects 0.000 claims description 7
- 235000006708 antioxidants Nutrition 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- -1 hydrogen ions Chemical class 0.000 claims 1
- 239000011163 secondary particle Substances 0.000 claims 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 26
- 239000000243 solution Substances 0.000 description 13
- 239000011701 zinc Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000010949 copper Substances 0.000 description 9
- 239000011777 magnesium Substances 0.000 description 9
- 239000005955 Ferric phosphate Substances 0.000 description 4
- 229940032958 ferric phosphate Drugs 0.000 description 4
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 4
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 4
- 238000010532 solid phase synthesis reaction Methods 0.000 description 4
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910017518 Cu Zn Inorganic materials 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000011706 ferric diphosphate Substances 0.000 description 1
- 235000007144 ferric diphosphate Nutrition 0.000 description 1
- CADNYOZXMIKYPR-UHFFFAOYSA-B ferric pyrophosphate Chemical compound [Fe+3].[Fe+3].[Fe+3].[Fe+3].[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O CADNYOZXMIKYPR-UHFFFAOYSA-B 0.000 description 1
- 229940036404 ferric pyrophosphate Drugs 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229960001708 magnesium carbonate Drugs 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229940085991 phosphate ion Drugs 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229940001593 sodium carbonate Drugs 0.000 description 1
- BYTVRGSKFNKHHE-UHFFFAOYSA-K sodium;[hydroxy(oxido)phosphoryl] phosphate;iron(2+) Chemical compound [Na+].[Fe+2].OP([O-])(=O)OP([O-])([O-])=O BYTVRGSKFNKHHE-UHFFFAOYSA-K 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 229940043825 zinc carbonate Drugs 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
Landscapes
- Compounds Of Iron (AREA)
Abstract
The invention discloses a method for preparing a composite ferric sodium phosphate material in a large scale, which comprises the following steps: firstly preparing a doped H yFe(3‑X)MX(PO4)4 precursor by a multi-element coprecipitation method, wherein M is one or a combination of Cr, mn, mg, cu, ni, zn, V and Ti, H is hydrogen ion, the value range of X is 0-1.5, and the value range of y is 0-3; then adding a sodium source and a carbon source into the H yFe(3‑X)MX(PO4)4 doped precursor for solid phase dry mixing uniformly, and then sintering to synthesize the composite sodium ferric pyrophosphate material. The method for preparing the composite sodium ferric pyrophosphate material in large scale can realize the batch preparation of the multi-element doped sodium ferric pyrophosphate material, can obviously reduce the preparation cost of the sodium ferric pyrophosphate material, accurately control the grain size of the precursor material and realize the high specific energy and high rate performance of the material.
Description
Technical Field
The invention relates to a method for preparing a composite ferric sodium pyrophosphate material in a large scale.
Background
The positive polyanion material of the sodium ion battery, such as a composite ferric sodium phosphate material, also called a doped ferric sodium phosphate (NFMPP for short) material, is conventionally prepared by adopting a solid phase method, and has the defects of low sintering temperature, excessive raw material components, insufficient mixing uniformity of raw materials, poor capacity of the material after sintering and the like, so that the batch preparation cannot be realized.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a method for preparing a composite sodium ferric phosphate material in a large scale, which can realize the mass preparation of a multi-element doped sodium ferric phosphate material, can obviously reduce the preparation cost of the sodium ferric phosphate material, accurately control the grain size of a precursor material and realize the high specific energy and high multiplying power performance of the material.
The technical scheme for achieving the purpose is as follows: a method for preparing a composite ferric sodium pyrophosphate material in large scale, which comprises the following steps:
S1, preparing a doped H yFe(3-X)MX(PO4)4 precursor by a multi-element coprecipitation method, wherein M is one or a combination of Cr, mn, mg, cu, ni, zn, V and Ti, H is hydrogen ion or sodium ion, the value range of X is 0-1.5, and the value range of y is 0-3;
s2, adding a sodium source and a carbon source into the H yFe(3-X)MX(PO4)4 doped precursor for solid phase dry mixing uniformly, and then sintering to synthesize the composite ferric sodium phosphate material.
In the above method for preparing the composite ferric sodium pyrophosphate material in large scale, in the step S1, the specific flow of preparing the doped H yFe(3-X)MX(PO4)4 precursor by the multi-component coprecipitation method is as follows:
S11, liquid preparation: jointly dissolving ferrous sulfate heptahydrate and one or more of M element materials into deionized water to obtain a precursor solution A; dissolving phosphoric acid in deionized water to obtain a precursor solution B; dissolving a complexing agent in deionized water to obtain complexing agent precursor liquid C; dissolving an antioxidant in deionized water to obtain a precursor solution D;
s12, a precipitation step: transferring the complexing agent precursor solution C into a reaction kettle to serve as base solution; then, feeding in a first step, respectively dripping the precursor liquid A, the precursor liquid B and the precursor liquid D into a reaction kettle, and synthesizing agglomerate grains with the primary grain diameter of 0.5-1 mu m and the secondary grain diameter of 1-20 mu m after the reaction is completed to form suspension;
S13, dehydration: drying the suspension in the reaction kettle by a centrifugal dryer, and controlling the water content to be less than 1% to obtain a precipitate, wherein the precipitate is a precursor doped with H yFe(3-X)MX(PO4)4.
The method for preparing the composite ferric sodium pyrophosphate material on a large scale comprises the step of preparing the material conforming to (Fe+M) through a multi-element coprecipitation method by one-step operation: (PO 4) in a molar ratio of 3:4, doping H yFe(3-X)MX(PO4)4 precursor.
According to the method for preparing the composite ferric sodium phosphate material in large scale, the antioxidant is added in the preparation process of the H yFe(3-X)MX(PO4)4 -doped precursor, so that ferrous ions are ensured to be in the solution.
The method for preparing the composite ferric sodium pyrophosphate material on a large scale comprises the step of adopting hydrogen peroxide or ascorbic acid as the antioxidant.
The method for preparing the composite ferric sodium pyrophosphate material in large scale comprises the steps of controlling the proportion and PH of complexing agent precursor C and controlling the agglomerate grain size of the H yFe(3-X)MX(PO4)4 precursor, wherein the secondary grain size of the H yFe(3-X)MX(PO4)4 precursor is 1-20 mu m.
The method for preparing the composite ferric sodium pyrophosphate material on a large scale comprises the step of adopting citric acid as the complexing agent.
In the above method for preparing a composite ferric sodium pyrophosphate material on a large scale, in step S2, the doping H yFe(1-X)MX(PO4)4 precursor, sodium source and carbon source, (PO 4): the molar ratio of Na is 1:1 to 1:1.3
The invention relates to a method for preparing a composite sodium ferric pyrophosphate material in large scale, which adopts a two-step method to prepare the sodium ferric pyrophosphate material, adopts a coprecipitation method to prepare a precursor, adds element doping in the precursor preparation process, and adds (Fe+M) in the precursor: (PO 4) in a molar ratio of 3:4, introducing a sodium source through a solid phase method; the preparation method can realize the mass preparation of the multi-element doped sodium ferric pyrophosphate material, can obviously reduce the preparation cost of the sodium ferric pyrophosphate material, accurately control the grain size of the precursor material, and realize the high specific energy and high rate performance of the material.
Drawings
FIG. 1 is an XRD crystal phase diffraction pattern of a composite sodium ferric pyrophosphate material prepared in the example;
fig. 2 is a charge-discharge graph of button cells made of the materials of examples and comparative examples;
fig. 3 is a cycle life chart of a button cell made using the materials of the examples.
Detailed Description
In order to enable those skilled in the art to better understand the technical scheme of the present invention, the following detailed description is provided with reference to the accompanying drawings:
Examples:
The embodiment of the invention relates to a composite sodium ferric pyrophosphate material Na 4Fe2.5Mg0.2Cu0.2Zn0.1(PO4)2P2O7, which is prepared by the following steps:
S1, preparing a ferric pyrophosphate precursor by a multi-component coprecipitation method, wherein the method specifically comprises the following steps:
s11, liquid preparation: 2.5mol of ferrous sulfate heptahydrate, 0.2mol of magnesium sulfate, 0.2mol of copper sulfate and 0.1mol of zinc sulfate are dissolved in 5L of deionized water to obtain an M1 ion solution, namely a precursor solution A; dissolving 4mol of phosphoric acid in 5L of deionized water to obtain a phosphate ion solution, namely a precursor solution B; dissolving 4mol of citric acid in 5L of deionized water to obtain complexing agent precursor liquid C; preparing 5mol of hydrogen peroxide solution (antioxidant) into 5L of aqueous solution to obtain a precursor solution D;
S12, a precipitation step: transferring the complexing agent precursor solution C into a reaction kettle as a base solution, controlling the stirring speed of the reaction kettle at 500r/min, and keeping the temperature of the reaction kettle constant at 40 ℃; then feeding in the first step, adding the precursor liquid A, B and the D liquid into a reaction kettle respectively according to the titration rate of 250ml/min, and preparing an initial crystal nucleus with the synthetic particle size of 0.5-1 mu m after the reaction is completed to form a suspension; controlling the grain size of the doping H 4 Fe2.5Mg0.2Cu0.2Zn0.1(PO4)4 precursor by controlling the proportion and PH of the complexing agent precursor liquid C;
S13, dehydration: drying the suspension in the reaction kettle by a centrifugal dryer, and controlling the water content to be less than 1% to obtain a precipitate M2, wherein the precipitate is a precursor doped with H 4 Fe2.5Mg0.2Cu0.2Zn0.1(PO4)4;
S2, respectively adding the obtained H 4 Fe2.5Mg0.2Cu0.2Zn0.1(PO4)4 doped precursor, 1.5mol Na 2CO3 and 50g composite carbon (conductive agent) into a dry mixer, and carrying out high-speed dispersion and mixing for 30min to obtain a uniformly mixed precursor M3; and sintering the obtained precursor M3, heating to 620 ℃ at a heating rate of 2 ℃/min, and preserving heat for 10 hours to obtain the composite sodium ferric pyrophosphate material Na 4 Fe2.5Mg0.2Cu0.2Zn0.1(PO4)2P2O7.
Comparative example:
Preparing Na 4Fe2.5Mg0.2Cu0.2Zn0.1(PO4)2P2O7 by adopting a solid phase method, ball-milling and mixing a certain amount of ferric phosphate, copper carbonate, magnesium carbonate, zinc carbonate, sodium carbonate and a composite carbon conductive agent according to a stoichiometric ratio for 20 hours to obtain a precursor, heating at a rate of 2 ℃/min, and preserving heat at 620 ℃ for 10 hours to obtain Na 4Fe2.5Mg0.2Cu0.2Zn0.1(PO4)2P2O7 of the comparative example.
To determine the content of each element and the uniformity of doping, the obtained powders of examples and comparative examples were dissolved with acid, respectively, and the content of each element was measured using an inductively coupled plasma spectrometer to confirm whether the doping element completely formed a uniform phase, and the results are shown in table 1:
Table 1, table of contents of each element in the materials of examples and comparative examples:
| Element(s) | Fe | Mg | Cu | Zn |
| Design value | 2.5 | 0.2 | 0.2 | 0.1 |
| Example measurements | 2.49 | 0.2 | 0.19 | 0.1 |
| Comparative example measurement value | 2.49 | 0.17 | 0.16 | 0.05 |
From the results of table 1, it can be seen that the content of each doping element in the examples is almost the same as the material design, but the difference is larger in the comparative examples, mainly because the doping elements in the examples are added in the form of coprecipitation in the precursor, the atomic scale of the doping elements is uniformly distributed, and the solid phase method preparation in the comparative examples hardly reaches the uniformity of the atomic scale.
Referring to fig. 1, the composite sodium iron pyrophosphate material Na4Fe2.5Mg0.2Cu0.2Zn0.1(PO4)2P2O7XRD obtained in the example was subjected to crystal phase diffraction, and it can be seen that the synthetic powder has good crystallization performance.
Referring to fig. 2, according to the valence balancing atoms, the uniformity of the doping elements directly synthesizes the lattice structure of the powder, thereby affecting the sodium ion deintercalation and the specific capacity of the material, and the charge-discharge curves of the button cells made of the materials of the examples and the comparative examples are shown in fig. 2, and it can be seen that the specific capacity of the comparative examples is 100mAh/g, which is less than 15mAh/g than that of the examples.
Referring to fig. 3, the cycle life of the button cell made of the material of the example (sodium metal as the counter electrode) was tested by using a test method of 2 cycles at 0.1C and 300 cycles at 1C, and it can be seen that the number of cycles is approximately 3000 and the capacity of the cell is not substantially attenuated.
According to the preparation method of the example, a series of composite ferric sodium phosphate materials were prepared, and the specific capacities of the different materials were tested, see Table 1.
Table 1, specific volume of different composite ferric sodium phosphate materials:
| Sequence number | Material | Specific capacity (mAh/g) |
| 1 | Na4Fe2.7Cu0.2Zn0.1(PO4)2P2O7 | 110 |
| 2 | Na4Fe2.7Mg0.2Zn0.1(PO4)2P2O7 | 109 |
| 3 | Na4Fe2.9Zn0.1(PO4)2P2O7 | 112 |
| 4 | Na4Fe2.6Mn0.3Ni0.1(PO4)2P2O7 | 108 |
| 5 | Na4Fe2.9Ni0.1(PO4)2P2O7 | 105 |
| 6 | Na4Fe1.8Mn1.2(PO4)2P2O7 | 106 |
| 7 | Na3.4Fe2.9Ti0.2(PO4)2P2O7 | 95 |
In conclusion, the method for preparing the composite ferric sodium phosphate material in large scale can realize the batch preparation of the multi-element doped ferric sodium phosphate material, can obviously reduce the preparation cost of the ferric sodium phosphate material, accurately control the grain size of the precursor material and realize the high specific energy and high multiplying power performance of the material.
It will be appreciated by persons skilled in the art that the above embodiments are provided for illustration only and not for limitation of the invention, and that variations and modifications of the above described embodiments are intended to fall within the scope of the claims of the invention as long as they fall within the true spirit of the invention.
Claims (8)
1. The method for preparing the composite sodium ferric pyrophosphate material on a large scale is characterized by comprising the following steps of:
S1, preparing a doped H yFe(3-X)MX(PO4)4 precursor by a multi-element coprecipitation method, wherein M is one or a combination of Cr, mn, mg, cu, ni, zn, V and Ti, H is hydrogen ions, the value range of X is 0-1.5, and the value range of y is 0-3;
s2, adding a sodium source and a carbon source into the H yFe(3-X)MX(PO4)4 doped precursor for solid phase dry mixing uniformly, and then sintering to synthesize the composite ferric sodium phosphate material.
2. The method for preparing the composite ferric sodium phosphate material on a large scale according to claim 1, wherein the specific flow of preparing the doped H yFe(3-X)MX(PO4)4 precursor by the multi-component coprecipitation method in the step S1 is as follows:
S11, liquid preparation: jointly dissolving ferrous sulfate heptahydrate and one or more of M element materials into deionized water to obtain a precursor solution A; dissolving phosphoric acid in deionized water to obtain a precursor solution B; dissolving a complexing agent in deionized water to obtain complexing agent precursor liquid C; dissolving an antioxidant in deionized water to obtain a precursor solution D;
s12, a precipitation step: transferring the complexing agent precursor solution C into a reaction kettle to serve as base solution; then, feeding in a first step, respectively dripping the precursor liquid A, the precursor liquid B and the precursor liquid D into a reaction kettle, and synthesizing agglomerate grains with the primary grain diameter of 0.5-1 mu m and the secondary grain diameter of 1-20 mu m after the reaction is completed to form suspension;
S13, dehydration: drying the suspension in the reaction kettle by a centrifugal dryer, and controlling the water content to be less than 1% to obtain a precipitate, wherein the precipitate is a precursor doped with H yFe(3-X)MX(PO4)4.
3. The method for preparing the composite ferric sodium phosphate material on a large scale according to claim 1 or2, wherein the preparation method is characterized in that (Fe+M): (PO 4) in a molar ratio of 3:4, doping H yFe(3-X)MX(PO4)4 precursor.
4. The method for preparing the composite ferric sodium phosphate material on a large scale according to claim 1 or 2, wherein an antioxidant is added in the preparation process of the H yFe(3-X)MX(PO4)4 -doped precursor, so that ferrous ions are ensured in the solution.
5. The method for preparing the composite ferric sodium pyrophosphate material on a large scale according to claim 4, wherein the antioxidant is hydrogen peroxide or ascorbic acid.
6. The method for preparing the composite ferric sodium phosphate material on a large scale according to claim 2, wherein the secondary particle size of the H yFe(3-X)MX(PO4)4 doped precursor is 1-20 μm, and the agglomerate particle size of the H yFe(3-X)MX(PO4)4 doped precursor is controlled by controlling the proportion and PH of the complexing agent precursor solution C.
7. The method for preparing the composite ferric sodium pyrophosphate material on a large scale according to claim 2, wherein the complexing agent is citric acid.
8. The method for large-scale preparation of composite ferric sodium phosphate material according to claim 1, wherein in step S2, the doping H yFe(1-X)MX(PO4)4 precursor, sodium source and carbon source, (PO 4): the molar ratio of Na is 1:1 to 1:1.3.
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| CN202410082431.0A CN117923452A (en) | 2024-01-19 | 2024-01-19 | Method for preparing composite sodium ferric pyrophosphate material in large scale |
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