CN113060713A - Preparation of Na by homogeneous phase method4Fe3(PO4)2(P2O7) Method and application of - Google Patents
Preparation of Na by homogeneous phase method4Fe3(PO4)2(P2O7) Method and application of Download PDFInfo
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Abstract
The invention discloses a homogeneous phase method for preparing Na4Fe3(PO4)2(P2O7) The preparation method comprises the following steps: mixing a carbon source, an iron source, a sodium source and a phosphorus source according to a certain stoichiometric ratio, adding an organic solvent, and sanding to form a homogeneous dispersion system; spray drying to obtain precursor, and sintering in inert atmosphere to obtain Na4Fe3(PO4)2(P2O7) And (3) powder. The method of the invention can obviously improve Na4Fe3(PO4)2(P2O7) The agglomeration phenomenon of the micro-nano powder improves the morphology and the electrical property of the powder, and the used organic solvent can be recovered by a cooling systemThe secondary utilization is realized, the latent heat of vaporization of the organic solvent is far lower than that of water, and the heating power consumption is saved. Na produced by the invention4Fe3(PO4)2(P2O7) Compared with the existing transition metal oxide, Prussian blue and vanadium polyanion compound cathode materials, the cathode material has the advantages of lower cost, better cycle stability, greenness and no pollution, and can provide an ideal cathode for commercial sodium-ion batteries.
Description
Technical Field
The invention belongs to the technical field of preparation of battery electrode material powder, and particularly relates to a homogeneous phase method for preparing Na4Fe3(PO4)2(P2O7) The method and the application thereof.
Background
In order to deal with energy and environmental problems caused by excessive consumption of fossil fuels, renewable energy sources such as solar energy and wind energy are incorporated into the construction of smart grids in various countries around the world. However, the intermittency and instability of renewable energy sources make it unfavorable for accessing the power grid, so electrochemical energy storage becomes the key for efficient utilization of renewable energy sources. The installed capacity of the energy storage system is large, and high requirements are provided for the efficiency, safety and economy of the electrochemical energy storage technology. The working principle of the sodium ion battery is similar to that of the lithium ion battery, and the sodium salt is richer in reserve, simple to exploit and more advantageous in large-scale application.
The types and abundance of sodium ion cathode materials include oxides, prussian blue and polyanions, but the polyanion type cathode material is undoubtedly the best choice in terms of abundance of resources, overall cost of the material, electrochemical performance of the material and environmental sustainability. Wherein, Na4Fe3(PO4)2(P2O7) Has received a great deal of attention in view of its good structural stability and environmental friendliness. However, in order to obtain pure phase Na4Fe3(PO4)2(P2O7) It must be ensured that all precursor salts reach the nano-scaleMixing uniformly. Wet homogeneous sand grinding combined with spray drying is an effective method for realizing the batch preparation of spherical powder with uniform particle size, but the method is about synthesizing Na4Fe3(PO4)2(P2O7) There are few reports on the industrial popularization of powder.
Disclosure of Invention
In order to realize the uniform dispersion of precursor salt on the nano scale, improve the purity and the electrical property of powder and promote the industrialized popularization and application of materials, the invention provides a homogeneous method for preparing Na4Fe3(PO4)2(P2O7) The method comprises the following steps:
(1) respectively weighing a sodium source, an iron source, a phosphorus source and a carbon source according to the stoichiometric ratio, and adding an organic solvent for dispersing;
(2) putting the dispersion liquid into a sand mill, adding a sand grinding medium, and performing wet-method sand grinding for 2-10 h, wherein the particle size is controlled to be 1-0.1 mu m;
(3) transferring the sanded reaction liquid into a spray dryer for spray granulation;
(4) sintering the sprayed powder in an inert atmosphere at the sintering temperature of 400-650 ℃ for 4-15 h to obtain the Na4Fe3(PO4)2(P2O7) And (3) powder.
Preferably, the sodium source in step (1) comprises one or more of inorganic sodium salt, organic sodium salt, metallic sodium and sodium oxide.
Further preferably, the inorganic sodium salt comprises at least one of trisodium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium pyrophosphate, trisodium monohydrogen pyrophosphate, disodium dihydrogen pyrophosphate, monosodium monohydrogen pyrophosphate, sodium carbonate and sodium bicarbonate; the organic sodium salt comprises at least one of sodium acetate, sodium oxalate and sodium citrate; the sodium oxide comprises at least one of sodium oxide and sodium peroxide.
Preferably, the iron source in step (1) includes one or more of ferric nitrate, ferric oxide, ferroferric oxide, ferric phosphate, ferrous oxalate, ferrous acetate and ferrous carbonate.
Preferably, the source of phosphorus in step (1) comprises one or more of phosphoric acid, a phosphate and a pyrophosphate.
Further preferably, the phosphate comprises one or more of sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate; the pyrophosphate comprises one or more of sodium pyrophosphate, trisodium monohydrogen pyrophosphate, disodium dihydrogen pyrophosphate and monosodium trihydrogen pyrophosphate.
Preferably, the carbon source in step (1) includes one or more of graphite, activated carbon, carbon nanotubes, graphene, and one or more of common organic carbonaceous materials including citric acid, glucose, sucrose, and the like.
Preferably, the organic solvent in step (1) includes one or more of methanol, ethanol, propanol, isopropanol, acetone, methyl butanone, methyl isobutyl ketone, diethyl ether and ethylene glycol dimethyl ether.
Preferably, the sanding manner of the sand mill in the step (2) comprises one of a disc type, a pin-and-rod type and a turbine type.
Preferably, the grinding medium in step (2) comprises one or more of natural sand, glass beads, steel beads, zirconia beads, zirconium silicate beads and agate beads.
Preferably, the sintering atmosphere in step (4) includes one of argon, nitrogen, argon-hydrogen gas mixture, and nitrogen-hydrogen gas mixture.
Preferably, the sintering temperature zone in the step (4) comprises all temperatures in 400-650 ℃ and various temperature rising and reducing gradients.
According to another aspect of the present invention, there is provided said homogeneous process for the preparation of Na4Fe3(PO4)2(P2O7) The application of the positive electrode material in the sodium ion battery is as follows: with Na4Fe3(PO4)2(P2O7) As a positive electrode active material, Super P is a conductive agent, PVDF is a binder, the Super P and the PVDF are mixed according to the mass ratio of 8:1:1, a current collector is an aluminum foil, and a positive electrode is formedA pole; the electrolyte is 1mol/L sodium perchlorate-EC/DEC (1: 1) 5% FEC, Celgard is used as a diaphragm, a metal sodium sheet is used as a negative electrode, and the sodium ion battery is assembled in an argon atmosphere with the oxygen partial pressure of less than 0.1 ppm.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
1. compared with the prior art, the method adopts the combination of wet homogeneous sanding and spray drying to prepare Na4Fe3(PO4)2(P2O7) The method can realize the uniform dispersion of the precursor salt on the nanometer scale and improve the purity and the electrical property of the powder. XRD result shows that Na prepared by homogeneous phase method4Fe3(PO4)2(P2O7) Belongs to the orthorhombic system, Pn21a space group; SEM photograph analysis shows that the Na prepared by the method provided by the invention4Fe3(PO4)2(P2O7) The powder is spherical particles with uniform particle size distribution. The battery performance test result shows that Na4Fe3(PO4)2(P2O7) The specific capacity reaches 110 mAh/g; after 5000 times of charge-discharge cycles, the specific capacity is still kept above 92.3 percent, and the lithium ion battery can be used as an electrode material to be applied to a sodium ion battery.
2. The full-battery positive electrode is prepared by adopting the sanding-spray drying process which is low in cost and simple in process, the industrial popularization is easy, the large-scale production of the positive electrode material is realized, the granularity of particles obtained by sanding-spray is uniform, the sphericity is high, and the full-battery positive electrode can be prepared by changing materials easily in the next production link.
3. The raw materials used by the invention comprise a sodium source, an iron source, a phosphorus source and a carbon source which are cheap and easily available and are widely distributed; the organic solvent such as ethanol is used as a grinding medium and a drying medium, the required heating power consumption is low, the solvent can be repeatedly recycled after a solvent cooling and recycling system is arranged, the environment is not polluted, the cost is saved, and the method has the characteristics of simplicity, reliability and low cost, and has a good industrial application prospect.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It is obvious that the drawings in the following description are only some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
FIG. 1 shows a positive electrode active material Na prepared in example 1 of the present invention4Fe3(PO4)2(P2O7) Scanning electron microscopy of (a).
FIG. 2 shows a positive electrode active material Na prepared in example 1 of the present invention4Fe3(PO4)2(P2O7) XRD pattern of (a).
Fig. 3 is a charge-discharge curve diagram of the sodium ion battery prepared in example 1 of the present invention.
Fig. 4 is a charge-discharge curve diagram of the sodium ion battery prepared in example 2 of the present invention.
Fig. 5 is a charge-discharge curve diagram of the sodium ion battery prepared in example 3 of the present invention.
Fig. 6 is a graph of the cycling profile at 10C current density for the sodium ion battery prepared in example 1 of the present invention.
Detailed Description
In the following, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
A positive electrode active material with chemical formula of Na4Fe3(PO4)2(P2O7) The preparation method of the positive active material comprises the following steps:
with sodium pyrophosphate Na4P2O7、FePO4、CH3COONa and citric acid are used as raw materials, and ethanol is used as a solvent. Wherein, sodium pyrophosphate Na4P2O7Is both a sodium source and a phosphorus source, FePO4Is iron source, sodium acetate CH3COONa is used as a sodium supplement source, and citric acid is used as a carbon source;
4.4605 g of Na4P2O7·10 H2Adding O, 9.06 g of FePO4, 3.2808g of sodium acetate and 8.4056g of citric acid monohydrate into 500mL of 95% ethanol, ball-milling for 3h at the rotating speed of 20rpm, sanding for 3h at 2000rpm, feeding at 80% air inlet speed, 130 ℃ air inlet temperature and 0.5% feeding speed, and spray-drying to obtain a precursor;
then putting the precursor in argon atmosphere, calcining for 15h at the temperature of 400 ℃ to obtain Na4Fe3(PO4)2(P2O7). And assembling the button cell in a glove box with water oxygen below 0.01 ppm.
FIG. 1 shows a positive electrode active material Na prepared in this example4Fe3(PO4)2(P2O7) The scanning electron microscope picture of (2) shows that the powder is in a similar spherical shape and the particle size of the product is controllable. FIG. 2 shows a positive electrode active material Na prepared in this example4Fe3(PO4)2(P2O7) XRD pattern of (a). As can be seen from fig. 3, the reversible capacity of the button half cell assembled by using the material prepared in the present embodiment as the positive electrode material at 0.2C reaches 112mAh/g, as can be seen from fig. 6, the reversible capacity of the assembled button half cell at 10C reaches 75mAh/g, and the capacity retention rate is still above 92.3% after 5000 cycles.
Example 2
A positive electrode active material with chemical formula of Na3Fe2(PO4)2(P2O7) The preparation method of the positive active material comprises the following steps:
with NaH2PO4、Fe2O3Citric acid is used as a raw material, and acetone is used as a solvent. Wherein, NaH2PO4Is both a sodium source and a phosphorus source, Fe2O3As a source of ironGlucose is a carbon source;
18.7212 g NaH2PO4、7.185g Fe2O312.6084 g of glucose is dispersed in 400mL of 95% acetone, ball milled for 3h at the rotating speed of 20rpm, then sanded for 3h at 2000rpm, and then fed at 80% of air inlet speed, 130 ℃ of air inlet temperature and 0.5% of feeding speed for spray drying to obtain a precursor;
then putting the precursor in nitrogen atmosphere, calcining at 500 ℃ for 10 h to obtain Na4Fe3(PO4)2(P2O7). And assembling the button cell in a glove box with water oxygen below 0.01 ppm.
As can be seen from FIG. 4, Na produced in this example4Fe3(PO4)2(P2O7) The reversible capacity of the button half cell assembled as the positive active material reaches 99mAh/g at 0.2 ℃.
Example 3
A positive electrode active material with chemical formula of Na4Fe3(PO4)2(P2O7) The preparation method of the positive active material comprises the following steps:
with sodium pyrophosphate Na4P2O7、FePO4Sodium acetate CH3COONa and cane sugar are used as raw materials, and ethyl ether is used as a solvent. Wherein, sodium pyrophosphate Na4P2O7Is both a sodium source and a phosphorus source, FePO4Is iron source, sodium acetate CH3COONa is used as a sodium supplement source, and citric acid is used as a carbon source;
8.921 g of Na4P2O7·10 H2Adding O, 18.12 g of FePO4, 6.5616g of sodium acetate and 16.8112 g of citric acid monohydrate into 500mL of anhydrous ether, ball-milling for 3h at the rotating speed of 20rpm, sanding for 3h at 2000rpm, feeding at 80% of air inlet speed, 130 ℃ of air inlet temperature and 0.5% of feeding speed, and spray-drying to obtain a precursor;
then putting the precursor into a mixed atmosphere of argon and hydrogen, and calcining for 4 hours at the temperature of 650 ℃ to obtain Na4Fe3(PO4)2(P2O7). And assembling the button cell in a glove box with water oxygen below 0.01 ppm.
As can be seen from FIG. 5, Na prepared in this example4Fe3(PO4)2(P2O7) The reversible capacity of the button half cell assembled as the positive active material reaches 97mAh/g under 0.2C.
Claims (11)
1. Preparation of Na by homogeneous phase method4Fe3(PO4)2(P2O7) The method is characterized by comprising the following steps:
(1) respectively weighing a sodium source, an iron source, a phosphorus source and a carbon source according to the stoichiometric ratio, and adding an organic solvent for dispersing;
(2) placing the dispersion liquid into a sand mill, adding a sand milling medium, and performing wet-process sand milling for 2-10 hours, wherein the particle size is controlled to be 1-0.1 mu m;
(3) transferring the sanded reaction liquid into a spray dryer for spray granulation;
(4) sintering the sprayed powder in an inert atmosphere at the sintering temperature of 400-650 ℃ for 4-15 h to obtain the Na4Fe3(PO4)2(P2O7) And (3) powder.
2. A homogeneous process for the preparation of Na as claimed in claim 14Fe3(PO4)2(P2O7) The method of (2), wherein the sodium source in step (1) comprises one or more of inorganic sodium salt, organic sodium salt, metallic sodium and sodium oxide; the inorganic sodium salt comprises at least one of trisodium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium pyrophosphate, trisodium monohydrogen pyrophosphate, disodium dihydrogen pyrophosphate, monosodium dihydrogen pyrophosphate, sodium carbonate and sodium bicarbonate; the organic sodium salt comprises at least one of sodium acetate, sodium oxalate and sodium citrate; the sodium oxide comprises at least one of sodium oxide and sodium peroxide.
3. A process as claimed in claim 1Homogeneous method for preparing Na4Fe3(PO4)2(P2O7) The method is characterized in that the iron source in the step (1) comprises one or more of ferric nitrate, ferric oxide, ferroferric oxide, ferric phosphate, ferrous oxalate, ferrous acetate and ferrous carbonate.
4. A homogeneous process for the preparation of Na as claimed in claim 14Fe3(PO4)2(P2O7) The method of (2), wherein the phosphorus source in step (1) comprises one or more of phosphoric acid, a phosphate salt, and a pyrophosphate salt; the phosphate comprises one or more of sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, ammonium dihydrogen phosphate and diammonium hydrogen phosphate; the pyrophosphate comprises one or more of sodium pyrophosphate, trisodium monohydrogen pyrophosphate, disodium dihydrogen pyrophosphate and monosodium trihydrogen pyrophosphate.
5. A homogeneous process for the preparation of Na as claimed in claim 14Fe3(PO4)2(P2O7) The method of (2), wherein the carbon source in step (1) comprises one or more of graphite, activated carbon, carbon nanotubes, graphene, and one or more of citric acid, glucose, and sucrose.
6. A homogeneous process for the preparation of Na as claimed in claim 14Fe3(PO4)2(P2O7) The method of (2), wherein the organic solvent in step (1) comprises one or more of methanol, ethanol, propanol, isopropanol, acetone, methyl butanone, methyl isobutyl ketone, diethyl ether, and ethylene glycol dimethyl ether.
7. A homogeneous process for the preparation of Na as claimed in claim 14Fe3(PO4)2(P2O7) The method is characterized in that the sanding manner of the sand mill in the step (2) comprises a disc type, a pin type and a turbine typeOne kind of (1).
8. A homogeneous process for the preparation of Na as claimed in claim 14Fe3(PO4)2(P2O7) The method of (2), wherein the grinding medium in step (2) comprises one or more of natural sand, glass beads, steel beads, zirconia beads, zirconium silicate beads and agate beads.
9. A homogeneous process for the preparation of Na as claimed in claim 14Fe3(PO4)2(P2O7) The method of (4), wherein the sintering atmosphere in step (4) comprises one of argon, nitrogen, argon-hydrogen gas mixture, and nitrogen-hydrogen gas mixture.
10. A homogeneous process for the preparation of Na as claimed in claim 14Fe3(PO4)2(P2O7) The method is characterized in that the sintering temperature zone in the step (4) comprises all temperatures in 400-650 ℃ and various temperature rising and reducing gradients.
11. Na according to any one of claims 1 to 104Fe3(PO4)2(P2O7) The application of (1) is characterized in that the sodium ion battery positive electrode material is applied to a sodium ion battery.
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| CN114597385A (en) * | 2022-03-14 | 2022-06-07 | 湖北万润新能源科技股份有限公司 | Iron-based composite phosphate positive electrode material, preparation method thereof, positive plate and sodium ion battery |
| CN114620702A (en) * | 2022-03-14 | 2022-06-14 | 湖北万润新能源科技股份有限公司 | Preparation method of positive electrode material, positive plate and sodium ion battery |
| CN114597385B (en) * | 2022-03-14 | 2023-02-21 | 湖北万润新能源科技股份有限公司 | Iron-based composite phosphate positive electrode material, preparation method thereof, positive plate and sodium ion battery |
| WO2023174130A1 (en) * | 2022-03-14 | 2023-09-21 | 湖北万润新能源科技股份有限公司 | Iron-based composite phosphate positive electrode material and preparation method therefor, positive plate and sodium ion battery |
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