CN114914413A - Carbon-coated sodium ferrous fluorophosphate material, preparation thereof and application thereof in sodium ion battery - Google Patents

Carbon-coated sodium ferrous fluorophosphate material, preparation thereof and application thereof in sodium ion battery Download PDF

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CN114914413A
CN114914413A CN202210440489.9A CN202210440489A CN114914413A CN 114914413 A CN114914413 A CN 114914413A CN 202210440489 A CN202210440489 A CN 202210440489A CN 114914413 A CN114914413 A CN 114914413A
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carbon
sodium
ferrous
fluorophosphate
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CN114914413B (en
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张治安
王旭
赖延清
李劼
盖晓臣
李仕豪
贺亮
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Hunan Nabang New Energy Co ltd
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Central South University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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 belongs to the technical field of sodium ion batteries, and particularly discloses a preparation method of a carbon-coated sodium ferrous fluorophosphate material, which comprises the steps of carrying out spray drying-roasting treatment on raw material slurry containing an iron source, a phosphorus source, a fluorine source, a sodium source and an organic carbon source, or carrying out spray pyrolysis treatment to obtain carbon composite precursor particles; and then placing the precursor particles in an atmosphere containing volatile organic compounds and performing vapor deposition carbon treatment at the temperature of 200-350 ℃ to prepare the carbon-coated sodium ferrous fluorophosphate material. The invention also comprises the material prepared by the preparation method and the application of the material in a sodium ion battery. The preparation method can effectively solve the problems of impurity phase, non-uniform carbon coating structure, non-ideal conductivity and the like in the preparation process of the sodium ferrous fluorophosphate, and can effectively improve the electrochemical performance of the sodium ferrous fluorophosphate.

Description

Carbon-coated sodium ferrous fluorophosphate material, preparation thereof and application thereof in sodium ion battery
The technical field is as follows:
the invention belongs to the technical field of sodium ion battery materials, and particularly relates to the technical field of positive active materials of sodium ion batteries.
The background art comprises the following steps:
lithium ion batteries have been widely used in portable electronic products due to their advantages of high energy density, long cycle life, and the like. With the development of society, the demand for energy storage is strong. However, the limited lithium resource limits the further development of the lithium ion battery, and a suitable energy storage system needs to be developed urgently. Abundant sodium resources and reaction mechanisms similar to those of lithium ion batteries make sodium ion batteries stand out, and iron-based phosphates are the most widely researched.
Na 2 FePO 4 The crystal structure of the F material exhibits a layered structure, dioctahedral [ Fe ] 2 O 7 F 2 ]The unit is made of coplanar FeO 4 F 2 Octahedron composed of F atoms connected in chain form and connected with PO 4 The tetrahedron junctions form layers with two-dimensional ion channels that diffuse easily. Layered Na 2 FePO 4 F has higher theoretical specific capacity (124mAh g) -1 ) And a stable charge-discharge platform (3.0V), and extremely small volume change (less than 4%), and is a sodium ion battery anode material with great commercial prospect. But Na 2 FePO 4 F has low electronic and ionic conductivity, and these inherent disadvantages limit Na 2 FePO 4 F, further development of commercialization.
The traditional modification method is to carry out carbon coating on sodium ferrous fluorophosphate, and comprises the steps of utilizing an organic carbon source to crack at high temperature to form a carbon coating layer and directly adding an inorganic carbon source to mix for carbon compounding. In the two composite coatings, the organic carbon source is uniformly coated, but the carbon material has low graphitization degree and low electronic conductivity due to low reaction temperature, while the inorganic carbon source is difficult to be uniformly coated, and both coatings have certain limitations. In a word, the compounding of the organic carbon source and the inorganic carbon source at present is difficult to realize the low-temperature preparation of the uniform carbon-coated coating layer, the electrochemical performance of the material needs to be further improved, and the commercialization is difficult.
The invention content is as follows:
to solve the problem of sodium ferrous fluorophosphate (Na) 2 FePO 4 F) The invention provides a preparation method of a carbon-coated sodium ferrous fluorophosphate material, aiming at overcoming the problem that the sodium ferrous fluorophosphate is easy to have impurity phases, improving the carbon coating structure and the electronic and sodium ion conductivity and improving the electrochemical performance of a sodium ion battery under the mild precondition.
The second purpose of the invention is to provide the carbon-coated sodium ferrous fluorophosphate material prepared by the preparation method and the application thereof in the sodium ion battery.
The third purpose of the invention is to provide a sodium ion battery containing the carbon-coated sodium ferrous fluorophosphate material and components thereof.
Different from other phosphate materials, the impurity phase easily appears in the ferrous sodium fluorophosphate preparation process, and ion and electron conductivity are unsatisfactory, carry out carbon cladding to it and can improve its conductivity to a certain extent, however, traditional carbon cladding means need comparatively strict condition usually, can further aggravate ferrous sodium fluorophosphate's impurity phase and generate, influence crystal structure, be unfavorable for the promotion of wholeness ability on the contrary. Aiming at the problems that the carbon coating form, the conductivity and the phase purity of the product are difficult to be considered and the electrochemical performance is not ideal in the carbon coating process of the sodium ferrous fluorophosphate, the invention provides the following preparation method:
a preparation method of a carbon-coated sodium ferrous fluorophosphate material comprises the steps of carrying out spray drying-roasting treatment or spray pyrolysis treatment on raw material slurry containing an iron source, a phosphorus source, a fluorine source, a sodium source and an organic carbon source to obtain carbon composite precursor particles; the roasting temperature is 550-650 ℃; the temperature of spray pyrolysis is 550-650 ℃;
and then placing the precursor particles in an atmosphere containing volatile organic compounds and performing vapor deposition carbon treatment at the temperature of 200-350 ℃ to prepare the carbon-coated sodium ferrous fluorophosphate material.
The research of the invention finds that the raw materials and the organic carbon source are subjected to spray drying-roasting treatment or spray pyrolysis treatment in advance, and then are matched with subsequent vapor deposition carbon treatment, so that the synergy can be realized unexpectedly, the phase purity and the crystal structure of the sodium ferrous fluorophosphate can be effectively controlled under mild conditions, the composite form of the carbon material can be effectively improved, the graphitization degree can be improved, the internal-to-external conductive network of the sodium ferrous fluorophosphate and the carbon material can be improved, the electrochemical performance of the prepared material can be synergistically improved, and particularly the electrochemical performance of the material under high magnification can be obviously improved.
In the invention, the iron source is at least one of phosphate and organic acid salt of ferrous iron and/or ferric iron ions; preferably at least one of ferric phosphate and ferrous oxalate dihydrate;
preferably, the phosphorus source is at least one of phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate and iron phosphate;
preferably, the fluorine source is at least one of sodium fluoride and ammonium fluoride;
preferably, the sodium source is at least one of sodium carbonate, sodium bicarbonate, sodium organic acid salt, sodium oxide and sodium hydroxide;
preferably, the organic carbon source is a water-soluble organic substance, and more preferably at least one of glucose, citric acid, starch, ascorbic acid, cyclodextrin and polyethylene glycol;
preferably, the solvent in the feedstock slurry comprises water; other water-soluble organic solvents are also permissible; in view of the cost of disposal, the solvent is preferably water.
Preferably, in the raw material slurry, Na: fe: p: the element molar ratio of F is 1.9-2.1: 0.9-1.1: 1: 1; further, the stoichiometric ratio may be used.
Preferably, the weight ratio of the organic carbon source to the iron source is 1: 1-10; more preferably 1:2 to 4.
In the invention, the particle size D50 of solid particles in the raw material slurry is less than or equal to 300 nm;
in the invention, the solid content in the raw material slurry is 30-60 wt.%;
preferably, the raw material slurry is obtained by pulping, ball milling and sand milling of the raw materials.
In the invention, the raw material slurry can be subjected to spray drying and then to roasting treatment, so that the sodium ferrous fluorophosphate/C precursor material can be obtained.
In the invention, the inlet temperature of the spray drying process is 180-270 ℃, and the preferred inlet temperature is 200-240 ℃; the spraying rate is preferably 20-40 ml/min.
Preferably, the roasting atmosphere is a protective atmosphere;
preferably, the roasting temperature is 550-600 ℃, and the heat preservation time is 4-16 h, preferably 10-15 h;
in another embodiment of the present invention, the precursor material is prepared by subjecting the raw material slurry to spray pyrolysis.
Preferably, the temperature of spray pyrolysis is 550-600 ℃; the spraying rate is preferably 20-40 ml/min. The research of the invention finds that the spray pyrolysis process is adopted and matched with the condition control, so that the spray pyrolysis process can be unexpectedly cooperated with the subsequent gas-phase carbon deposition process, the control of the impure phase of the sodium ferrous fluorophosphate is facilitated, the carbon composite form and the graphitization degree are improved, and the electrochemical performance of the prepared material is facilitated.
In the invention, under the spray drying-roasting or spray pyrolysis process with the participation of the organic carbon source, the subsequent gas phase carbon deposition process is further creatively combined, and the synergistic effect can be brought on the aspects of the heterogeneous phase control of the sodium ferrous fluorophosphate material, the compounding mode of the carbon material, the graphitization degree and the performance of the sodium ion battery. The research of the invention also finds that the further control of the temperature and the components of the volatile gas source in the treatment process can further improve the synergy, further improve the pure phase, the carbon composite form and the morphology of the prepared material and the electrochemical performance of the material.
The volatile organic matter is gaseous organic matter at the temperature of 200-350 ℃;
preferably, the volatile organic compound is C 1 ～C 6 Alkane, C 2 ～C 6 Olefin of (C) 2 ～C 6 Alkyne of (2), C 4 ～C 10 At least one of the ethers of (a).
Said C 1 ～C 6 The alkane is C 1 ～C 6 For example, the straight-chain or branched alkyl group of (a) may be at least one of methane, ethane, propane, and isopropane; said C 2 ～C 6 The olefin (b) is a mono-or diene having the above carbon number, and may be at least one of ethylene, propylene and the like. Said C 2 ～C 6 The alkyne of (3) may be at least one of acetylene, propyne, and the like. Said C 4 ～C 6 The ether of (b) is preferably a symmetrical or asymmetrical ether, for example diethyl ether, dibutyl ether.
More preferably, the volatile organic compound contains C 2 ～C 6 Olefin of (C) 4 ～C 8 An ether of (4). The research of the invention finds that the optimal atmosphere can realize process synergy, is beneficial to further controlling the impurity phase of the components and is further beneficial to improving the electrochemical performance of the prepared material.
Preferably, the atmosphere containing the volatile organic compounds also contains a diluent gas;
preferably, the diluent gas is at least one of nitrogen and inert gas;
preferably, in the atmosphere containing the volatile organic compounds, the volume content of the volatile organic compounds is greater than or equal to 10%; preferably 10 to 30%.
According to the invention, under the innovation of precursor particle preparation, the calcination treatment under the air source and the combined control of temperature are further matched, so that the crystal phase purity, the crystal structure and the electrochemical performance of the prepared material can be further improved in a synergistic manner.
Preferably, the treatment time of vapor deposition carbon is 0.5-2 h.
Further preferably, the vapor deposition carbon stage comprises a first stage heat treatment process at 200-250 ℃ and a second stage heat treatment process at 300-350 ℃. The time of the first stage heat treatment process and the time of the second stage heat treatment process can be 0.5-1 h respectively.
The invention relates to a more specific preparation method of a uniform carbon-coated sodium ferrous fluorophosphate cathode active material, which comprises the following steps:
step (1): dissolving an iron source, a phosphorus source, a fluorine source, a sodium source and an organic carbon source serving as raw materials in an organic solvent or deionized water, and stirring to obtain a suspension A, wherein the solid content of the suspension is controlled to be 30-60%;
step (2): transferring the suspension A into a ball mill, and performing ball milling to obtain a suspension B; wherein, the granularity of the slurry after ball milling is D50 < 2 μm, and the ball milling medium is preferably zirconia balls.
And (3): transferring the suspension B into a sand mill, and sanding to obtain a suspension C; the particle size of the ground slurry after sanding is D50 < 300nm, and preferably, the rotating speed of the sand mill is 1500-2400 rpm.
And (4): carrying out spray drying on the suspension C to obtain a spherical precursor; wherein the inlet temperature of the spray drying is 180-270 ℃, and the spraying speed is 20-40 ml/min.
And (5): transferring the precursor into a sealed ventilating atmosphere furnace, and sintering to obtain carbon-coated sodium ferrous fluorophosphate; in the step 5, the sintering temperature is 550-600 ℃, and preferably, the heat preservation time is 4-16 h.
And (6): and (5) introducing a volatile organic gas source, and carrying out heat preservation treatment at 200-350 ℃ to obtain the uniform carbon-coated sodium ferrous fluorophosphate material.
The invention also provides a uniform carbon-coated sodium ferrous fluorophosphate material prepared by the method.
The invention also provides the application of the carbon-coated sodium ferrous fluorophosphate material in the preparation of sodium ion batteries;
preferably, the lithium ion battery is used as a positive electrode active material for preparing a sodium ion battery.
The invention also provides a sodium ion battery anode material which comprises the uniform carbon-coated ferrous sodium fluorophosphate anode material prepared at low temperature.
Preferably, the positive electrode material further comprises a binder and a conductive agent. The binder and the conductive agent may be materials known in the industry, for example, the binder may be PVDF and the conductive agent may be acetylene black. The content of each component can also be adjusted based on the existing means, for example, the content of the binder is 5 to 15 wt%; the content of the conductive agent is, for example, 5 to 15 wt%, and the balance is the active material.
The invention also comprises a sodium ion battery anode which comprises the carbon-coated sodium ferrous fluorophosphate anode material; preferably, the cathode comprises the carbon-coated sodium ferrous fluorophosphate cathode material.
The invention has the following remarkable characteristics:
aiming at the problems that the carbon coating form, the conductivity and the phase purity of the product are difficult to consider in the carbon coating process of sodium ferrous fluorophosphate, and the electrochemical performance is not ideal, the invention innovatively carries out spray drying-roasting or spray pyrolysis treatment on the raw material and the organic carbon source in advance, then coordinates with vapor deposition treatment, and further coordinates with the combined control of the treatment process, can realize synergy, can effectively control the impure phase problem of the sodium ferrous fluorophosphate prepared by carbon coating, is beneficial to improving the carbon compounding mode under mild conditions, improves the graphitization degree, improves the conductive network, and can synergistically improve the electrochemical performance of the prepared material in a sodium ion battery.
The method has the advantages of low cost, large-scale production, environmental friendliness, simple operation and excellent industrial application prospect.
Drawings
FIG. 1 is an XRD pattern of carbon-coated sodium ferrous fluorophosphate obtained in step (6) of example 1;
Detailed Description
Example 1
(1) Weighing 90.01Kg of ferric phosphate, 25.05Kg of sodium fluoride, 50.13Kg of sodium bicarbonate and 34.80Kg of glucose as an iron source, a phosphorus source, a fluorine source, a sodium source and an organic carbon source (namely, mixing Na, Fe, P and F according to a stoichiometric molar ratio (Na, Fe, P, F and 2: 1: 1: 1), dissolving in 200L of water, and stirring to obtain a suspension A, wherein the solid content of the suspension A is controlled to be 50%;
(2) transferring the suspension A into a ball mill at the rotating speed of 500rpm, and controlling the particle size to D50 less than 2 mu m after ball milling for 5 hours to obtain suspension B;
(3) transferring the suspension B into a sand mill at the rotating speed of 2000rpm, controlling the particle size to D50 < 300nm after sanding for 1h to obtain suspension C
(4) Spray drying the suspension C, controlling the inlet temperature to be 200 ℃ and the flow to be 35 ml/min; obtaining a spherical precursor;
(5) transferring the precursor into a rotary kiln, calcining for 10h at 600 ℃ in a nitrogen atmosphere, and sintering to obtain carbon-coated ferrous sodium fluorophosphate (precursor particles);
(6) then introducing mixed gas of nitrogen and propylene as a heat treatment gas source in a volume ratio of 9:1, and sintering at 320 ℃ (sintering temperature) for 1h to obtain uniform carbon-coated ferrous sodium fluorophosphate (XRD is shown in figure 1).
Example 2
The only difference compared to example 1 is that the glucose in step (1) was replaced by an equal weight of citric acid and the other steps were not changed. The roasting temperature in the step (5) is 550 ℃, and the time is 14 h.
Example 3
Compared with the example 1, the difference is only that the iron phosphate in the step (1) is changed into ferrous oxalate and ammonium dihydrogen phosphate (wherein the molar amounts of Fe and P are the same as the example 1), and other steps are not changed.
Example 4
The only difference compared to example 1 is that in step (4) the spray drying was replaced by spray pyrolysis and the other steps were not changed. For example, the temperature of spray pyrolysis was 600 ℃ and the flow rate was the same as in example 1.
Example 5
Compared with the example 1, the difference is that the sintering temperature in the step (6) is 200 ℃, the time is 2h, and other steps are not changed.
Example 6
Compared with the example 1, the difference is only that in the mixed gas of nitrogen and propylene in the step (6), the volume ratio of the nitrogen to the propylene is 7:3, and the other steps are not changed.
Example 7
The only difference compared to example 1 is that the source of the heat treatment gas in step (6) is nitrogen-butyl ether: (butyl ether content is 10%) and other steps are unchanged.
Example 8
Compared with the example 1, the difference is only that the heat treatment gas source in the step (6) is nitrogen: propylene: the mixed gas of the butyl ether (the volume ratio is 90:5:5) and other steps are not changed.
Example 9
Compared with the example 1, the difference is only that in the step (6), the first-stage sintering is carried out for 0.5h at 200 ℃ in advance, and then the second-stage sintering is carried out for 0.5h under the heat preservation of 320 ℃, and other steps are not changed.
Comparative example 1
The only difference compared with example 1 is that the spray drying treatment of step (4) was not performed, but the drying treatment was performed using conventional oven drying, and the other steps were not changed.
Comparative example 2
The only difference compared to example 1 is that step (5) was sintered at 500 ℃ in a nitrogen atmosphere, and the other steps were not changed.
Comparative example 3
The only difference compared to example 1 is that step (5) was sintered at 700 ℃ in a nitrogen atmosphere, and the other steps were unchanged.
Comparative example 4
Compared with the example 1, the difference is that no propylene is added into the heat treatment gas source in the step (6), pure nitrogen is adopted, and other steps are not changed.
Comparative example 5
The only difference compared to example 1 is that step (1) does not add an organic carbon source and the other steps are unchanged.
Comparative example 6
Compared with example 1, the only difference is that the heat treatment of the gas phase organic matter in step (6) is not adopted, but the conventional liquid phase composite post heat treatment carbon-coating process is adopted, for example, the different steps are: performing solid-phase ball milling and mixing on the ferrous sodium fluorophosphate/C material prepared in the step (5) and glucose (the weight ratio of the glucose to the ferrous sodium fluorophosphate/C is 1: 10) in solvent water, drying, and calcining for 10 hours at 320 ℃ in a nitrogen atmosphere.
Comparative example 7
The only difference compared with example 1 is that the sintering temperature in step (6) becomes 400 ℃, and the other steps do not change.
The electrical performance of the ferrous sodium fluorophosphate prepared in each example and comparative example was tested:
the test comprises the following main steps:
(1) a battery case of 2032 model is utilized, the positive electrode is a prepared pole piece of sodium ferrous fluorophosphate, the current collector is aluminum foil, and active substances (the final prepared materials in each embodiment and proportion): conductive carbon (acetylene black): PVDF 7: 2: 1, a negative electrode is made of sodium metal, a fiber diaphragm (model Whatman Grade GF/D) and an electrolyte of 1M NaClO4 (pure PC + 5% FEC) are used for charging the battery;
(2) standing for 12h, setting a multiplying power charging program, wherein the multiplying power is 1C, the voltage interval is 2.0V-4.0V, the circulating temperature is room temperature, and circulating for 1000 circles;
(3) the theoretical specific capacity value of the sodium ferrous fluorophosphate is 124 mAh/g;
the test results are shown in table 1:
Figure BDA0003614906740000081
Figure BDA0003614906740000091
therefore, by adopting the preparation process, the spray-roasting (or spray pyrolysis) -vapor deposition carbon combined process and the combined control of the sintering temperature and the vapor treatment temperature, the synergy can be realized unexpectedly, and the better electrochemical performance can be obtained.

Claims (10)

1. A preparation method of a carbon-coated sodium ferrous fluorophosphate material is characterized in that raw material slurry containing an iron source, a phosphorus source, a fluorine source, a sodium source and an organic carbon source is subjected to spray drying-roasting treatment or spray pyrolysis treatment to obtain carbon composite precursor particles; the roasting temperature is 550-650 ℃; the temperature of spray pyrolysis is 550-650 ℃;
and then placing the precursor particles in an atmosphere containing volatile organic compounds and performing vapor deposition carbon treatment at the temperature of 200-350 ℃ to prepare the carbon-coated sodium ferrous fluorophosphate material.
2. The method for preparing a carbon-coated sodium ferrous fluorophosphate material according to claim 1, wherein the iron source is at least one of a phosphate and an organic acid salt of ferrous iron and/or ferric iron; preferably at least one of ferric phosphate and ferrous oxalate dihydrate;
preferably, the phosphorus source is at least one of phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate and iron phosphate;
preferably, the fluorine source is at least one of sodium fluoride and ammonium fluoride;
preferably, the sodium source is at least one of sodium carbonate, sodium bicarbonate, organic acid salt of sodium, sodium oxide and sodium hydroxide;
preferably, the organic carbon source is a water-soluble organic substance, and more preferably at least one of glucose, citric acid, starch, ascorbic acid, cyclodextrin and polyethylene glycol;
preferably, the solvent in the feedstock slurry comprises water;
preferably, in the raw material slurry, Na: fe: p: the element molar ratio of F is 1.9-2.1: 0.9-1.1: 1: 1;
preferably, the weight ratio of the organic carbon source to the iron source is 1: 1 to 10.
3. The method for preparing a carbon-coated sodium ferrous fluorophosphate material according to claim 1, wherein the particle size D50 of the solid particles in the raw material slurry is not more than 300 nm;
preferably, the solid content in the raw material slurry is 30-60 wt.%;
preferably, the raw material slurry is obtained by pulping, ball milling and sand milling of the raw materials.
4. The method for preparing a carbon-coated sodium ferrous fluorophosphate material according to claim 1, wherein the inlet temperature of the spray drying process is 180-270 ℃; the spraying rate is preferably 20-40 ml/min.
5. The method for preparing a carbon-coated sodium ferrous fluorophosphate material according to claim 1, wherein the roasting atmosphere is a protective atmosphere;
preferably, the roasting temperature is 550-600 ℃, and the heat preservation time is 4-16 h;
preferably, the particle size of the precursor material is 10 to 20 μm.
6. The method for preparing the carbon-coated sodium ferrous fluorophosphate material according to claim 1, wherein the temperature of spray pyrolysis is 550 to 600 ℃; the spraying rate is preferably 20-40 ml/min.
7. The method for preparing a carbon-coated sodium ferrous fluorophosphate material according to claim 1, wherein the volatile organic compounds are gaseous organic compounds at a temperature of 200-350 ℃;
preferably, the volatile organic compound is C 1 ～C 6 Alkane of C 2 ～C 6 Olefin of C 2 ～C 6 Alkyne of (2), C 4 ～C 10 At least one of the ethers of (a);
more preferably, the volatile organic compound contains C 2 ～C 6 Olefin of (C) 4 ～C 8 An ether of (a);
preferably, the atmosphere containing the volatile organic compounds also contains a diluent gas;
preferably, the diluent gas is at least one of nitrogen and inert gas;
preferably, in the atmosphere containing the volatile organic compounds, the volume content of the volatile organic compounds is greater than or equal to 10%; preferably 10-30%;
preferably, the vapor deposition carbon stage comprises a first stage heat treatment process at 200-250 ℃ and a second stage heat treatment process at 300-350 ℃.
8. The carbon-coated sodium ferrous fluorophosphate material prepared by the preparation method of any one of claims 1 to 7.
9. The use of the carbon-coated sodium ferrous fluorophosphate material according to claim 8, which is used as a positive active material of a sodium ion battery;
preferably, the material is used as a positive active material for preparing a sodium ion battery;
further preferably, the material is used as a positive electrode active material for preparing a positive electrode of a sodium ion battery.
10. A sodium ion battery comprising the carbon-coated sodium ferrous fluorophosphate material according to claim 8;
preferably, the positive electrode comprises the carbon-coated sodium ferrous fluorophosphate material.
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