CN114014293B - Preparation method of sodium ion battery material - Google Patents
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Abstract
The invention discloses a preparation method of a sodium ion battery material. Mixing sodium bicarbonate with titanium organic matters, adding ferric phosphate, adding water for pulping, and stirring and mixing to obtain mixed slurry; adding conductive graphite into the mixed slurry, and then adding the mixed slurry into a sand mill for sand milling, wherein the sand milling grain size is 250-300nm; spray drying, high-temperature calcining the obtained dried material, maintaining the calcining process in nitrogen atmosphere, and sieving to remove iron to obtain the sodium ion battery material. The invention combines the advantages of sodium iron phosphate and sodium titanate to form mutual doping, thereby obtaining the material with high capacity and good cycle performance, and the cost of the final material is very low, which is about 50 percent of that of the lithium iron phosphate material, but the capacity is equivalent to that of the lithium iron phosphate, and the competitive advantage is very obvious.
Description
Technical Field
The invention relates to a preparation method of a sodium ion battery material, and belongs to the technical field of new energy materials.
Background
The field of power batteries is increasingly diversified, competition is continuously upgraded, and in the future, the power batteries are mainly used as power batteries of new energy automobiles, and attention is paid to the power batteries along with the heating of the new energy automobile market. At present, due to continuous technological transformation and factors such as raw material price fluctuation, the field of power batteries is new.
Lithium iron phosphate batteries (LFP) and ternary lithium batteries (NCM, positive electrode materials are three materials of nickel cobalt manganese) have been very competitive. The yield of the lithium iron phosphate battery is 5 months of 2021, namely, the first time of reverse super ternary lithium battery. According to the prediction of the industry, the loading capacity of the lithium iron phosphate battery is expected to exceed that of a ternary lithium battery in 6 months, and the champion baby seat in the power battery market is regained. It is expected that the loading of the lithium iron power battery will be equal to the loading of the ternary power battery in autumn throughout year 2021, while 2022 will fully exceed the ternary power battery. At present, the conventional process comprises the steps of preparing liquid phase to prepare ferric phosphate, washing, drying and calcining to obtain anhydrous ferric phosphate, generating wastewater containing ammonia nitrogen, sulfate radical and phosphate radical, treating the wastewater, adding lithium source, carbon source and the like into the obtained anhydrous ferric phosphate, and grinding, drying and calcining.
However, as the equivalent price of lithium source increases, there is a great influence on the cost of lithium iron phosphate, 9 months 2021, and the price of lithium iron phosphate increases to 9-10 tens of thousands/ton, so that a lower cost material is urgently needed to replace the lithium iron phosphate material.
And the sodium battery material does not need lithium salt, so the cost is greatly reduced. However, common sodium battery materials have certain problems, namely, the sodium iron phosphate has low capacity, but the cyclic life of the sodium iron phosphate is long, the layered oxide has high capacity, and the cyclic life of the sodium iron phosphate is short.
Disclosure of Invention
Aiming at the existing problems, the invention provides a preparation method of a sodium ion battery material, which combines the advantages of sodium iron phosphate and sodium titanate to form mutual doping, so that the material with high capacity and good cycle performance is obtained, the cost of the final material is very low, which is about 50% of that of a lithium iron phosphate material, but the capacity is equivalent to that of the lithium iron phosphate, and the competitive advantage is very obvious.
The invention solves the technical problems by the following technical means:
the invention relates to a preparation method of a sodium ion battery material, which comprises the following steps: xNaTiO 2 .yNaFePO 4 The molar ratio of x to y is 0.7-0.8:0.2-0.3; the preparation method comprises the following steps:
1) Mixing sodium bicarbonate with titanium organic matters, adding ferric phosphate (the preparation of the ferric phosphate can be put in the first step), then adding water for pulping, and then stirring and mixing to obtain mixed slurry; the preparation method of the ferric phosphate comprises the following steps: calcining slag generated by yellow phosphorus smelting in a high-temperature air atmosphere after ball milling at 500-700 ℃ for 4-6 hours, adding phosphoric acid solution into the rest materials for dissolution after magnetic separation, filtering, adding ammonia water into the obtained filtrate, adjusting pH to 1.8-2.2 to obtain ferric phosphate dihydrate, filtering, drying, crushing and deironing to obtain ferric phosphate dihydrate, concentrating and crystallizing the filtrate obtained by filtering to obtain ammonium phosphate compound fertilizer;
2) Adding conductive graphite into the mixed slurry, and then adding the mixed slurry into a sand mill for sand milling, wherein the sand milling grain size is 250-300nm;
3) Spray drying, high-temperature calcining the obtained dried material, maintaining the calcining process in nitrogen atmosphere, and sieving to remove iron to obtain the sodium ion battery material.
In the step (1), the iron-phosphorus ratio of the ferric phosphate is 1.0-1.05;1 and BET is in the range of 30 to 50m 2 Per g, a primary particle diameter of 30-60nm and a D50 of 3-10 μm.
The ball milling process is carried out by adopting a ball mill, wherein the grinding balls adopt zirconia balls with the diameter of 1-3cm, then sieving is carried out, 200-mesh undersize products are taken for calcination, and the oversize products return to carry out ball milling; calcining by adopting a rotary kiln; the concentration of the phosphoric acid solution is 0.5-1mol/L, and the solid-liquid mass ratio is 1:3-4.
The organic compound of titanium in the step (1) is a non-hydrolytic and water-soluble titanium organic compound.
In the step (1), the molar ratio of sodium bicarbonate to titanium organic matters to ferric phosphate is 1:0.7-0.8:0.2-0.3, and the mass fraction of water in the mixed slurry is 60-70%.
The mass of the conductive graphite added in the step (2) is 0.2-0.5% of the mass of the mixed slurry; before adding the conductive graphite into the mixed slurry, adding the conductive graphite into water, mixing and stirring, putting into a sand mill for grinding until the particle size is 100-150nm, pouring the slurry into the mixed slurry, and then grinding.
And (3) carrying out spray drying in the step (3), wherein the D50 of the obtained spray-dried material is 3-10 mu m.
In the step (3), the whole calcination period is 25-30h, the heating rate is 80-120 ℃/h, then the temperature of the first heat preservation area is 750 ℃, the heat preservation time is 1h, then the heat preservation temperature is 550-600 ℃ for 5-6h, then the material temperature is reduced to be less than or equal to 100 ℃, then the material is discharged, the gas in the furnace is continuously pumped away by an induced draft fan, meanwhile, the nitrogen is continuously supplied in the furnace, the purity of the nitrogen is more than or equal to 99.999%, the moisture mass fraction of the nitrogen is lower than 0.1ppm, the humidity content of the heat preservation section is maintained to be lower than 5ppm, and the furnace pressure in the whole sintering furnace is 60-100Pa.
And in the screening process, an 80-150-mesh ultrasonic vibration screen is adopted for screening, an electromagnetic iron remover is adopted for iron removal, the material is discharged after iron removal is less than or equal to 1ppm of magnetic substances, and vacuum packaging is carried out, so that the sodium ion battery is obtained.
The sodium battery material adopts the layered oxide and polyanion composite sodium battery material, namely, the advantage of high energy density of the layered oxide is utilized, the advantage of stability of the polyanion is utilized, the layered oxide is coated on the polyanion, a small amount of titanium is doped into NaFePO4, the ionic conductivity is improved, meanwhile, the conductive graphite is used for coating an inorganic carbon source, the inorganic carbon source has higher conductivity than an organic carbon source, but the inorganic carbon source has the problem of difficult uniform coating, so that the organic titanium source is also adopted, carbon is pyrolyzed in the pyrolysis process of the organic titanium source, the inorganic carbon is coated in a place where the inorganic carbon is not coated, the coating uniformity is improved, and the electronic conductivity is further improved.
Meanwhile, the iron phosphate adopts slag generated by smelting yellow phosphorus, is industrial waste, has low price, contains iron, phosphorus and other elements, mainly takes iron-phosphorus alloy as a main material, is calcined at high temperature to obtain iron phosphate and other iron-phosphorus compounds, is reacted with phosphoric acid to obtain ferric dihydrogen phosphate, and is subjected to pH adjustment to obtain the iron phosphate, wherein the obtained filtrate is the ammonium phosphate compound fertilizer. The preparation process of the iron phosphate has low cost and high utilization rate of each component.
The chemical reaction equation during calcination:
FeP+2O 2 ----FePO 4
during the phosphoric acid dissolution process:
FePO 4 +2H 3 PO 4 ---Fe(H 2 PO4) 3
during the process of adjusting the pH value:
Fe(H 2 PO 4 ) 3 +4NH 3 .H 2 O---FePO 4 .2H 2 O+2(NH 4 ) 2 HPO 4 +2H 2 O
the invention has the beneficial effects that: the advantages of the sodium iron phosphate and the sodium titanate are combined to form mutual doping, so that the material with high capacity and good cycle performance is obtained, the cost of the final material is very low, which is about 50% of that of the lithium iron phosphate material, but the capacity is equivalent to that of the lithium iron phosphate, and the competitive advantage is very obvious.
Drawings
Fig. 1 is an SEM of example 1 of the present invention.
Fig. 2 is an SEM of example 2 of the present invention.
Fig. 3 is an SEM of example 3 of the present invention.
Detailed Description
The invention will be described in detail below with reference to fig. 1 and the specific examples: the molecular formula of the sodium ion battery material is as follows: xNaTiO 2 .yNaFePO 4 The molar ratio of x to y is 0.7-0.8:0.2-0.3; the preparation method comprises the following steps:
1) Mixing sodium bicarbonate with titanium organic matters, adding ferric phosphate, adding water for pulping, and stirring and mixing to obtain mixed slurry;
2) Adding conductive graphite into the mixed slurry, and then adding the mixed slurry into a sand mill for sand milling, wherein the sand milling grain size is 250-300nm;
3) Spray drying, high-temperature calcining the obtained dried material, maintaining the calcining process in nitrogen atmosphere, and sieving to remove iron to obtain the sodium ion battery material.
In the step (1), the preparation method of the ferric phosphate comprises the following steps: calcining slag generated by yellow phosphorus smelting in a high-temperature air atmosphere after ball milling at 500-700 ℃ for 4-6 hours, adding phosphoric acid solution into the rest materials for dissolution after magnetic separation, filtering, adding ammonia water into the obtained filtrate, adjusting pH to 1.8-2.2 to obtain ferric phosphate dihydrate, filtering, drying, crushing and deironing to obtain ferric phosphate dihydrate, concentrating and crystallizing the filtrate obtained by filtering to obtain ammonium phosphate compound fertilizer; the iron-phosphorus ratio of the ferric phosphate is 1.0-1.05;1 and BET is in the range of 30 to 50m 2 Per g, a primary particle diameter of 30-60nm and a D50 of 3-10 μm.
The ball milling process is carried out by adopting a ball mill, wherein the grinding balls adopt zirconia balls with the diameter of 1-3cm, then sieving is carried out, 200-mesh undersize products are taken for calcination, and the oversize products return to carry out ball milling; calcining by adopting a rotary kiln; the concentration of the phosphoric acid solution is 0.5-1mol/L, and the solid-liquid mass ratio is 1:3-4.
The organic compound of titanium in the step (1) is a non-hydrolytic and water-soluble titanium organic compound.
In the step (1), the molar ratio of sodium bicarbonate to titanium organic matters to ferric phosphate is 1:0.7-0.8:0.2-0.3, and the mass fraction of water in the mixed slurry is 60-70%.
The mass of the conductive graphite added in the step (2) is 0.2-0.5% of the mass of the mixed slurry; before adding the conductive graphite into the mixed slurry, adding the conductive graphite into water, mixing and stirring, putting into a sand mill for grinding until the particle size is 100-150nm, pouring the slurry into the mixed slurry, and then grinding.
And (3) carrying out spray drying in the step (3), wherein the D50 of the obtained spray-dried material is 3-10 mu m.
In the step (3), the whole calcination period is 25-30h, the heating rate is 80-120 ℃/h, then the temperature of the first heat preservation area is 750 ℃, the heat preservation time is 1h, then the heat preservation temperature is 550-600 ℃ for 5-6h, then the material temperature is reduced to be less than or equal to 100 ℃, then the material is discharged, the gas in the furnace is continuously pumped away by an induced draft fan, meanwhile, the nitrogen is continuously supplied in the furnace, the purity of the nitrogen is more than or equal to 99.999%, the moisture mass fraction of the nitrogen is lower than 0.1ppm, the humidity content of the heat preservation section is maintained to be lower than 5ppm, and the furnace pressure in the whole sintering furnace is 60-100Pa.
And in the screening process, an 80-150-mesh ultrasonic vibration screen is adopted for screening, an electromagnetic iron remover is adopted for iron removal, the material is discharged after iron removal is less than or equal to 1ppm of magnetic substances, and vacuum packaging is carried out, so that the sodium ion battery is obtained.
Example 1
A preparation method of a sodium ion battery material comprises the following steps: 0.75NaTiO 2 .0.25NaFePO 4 . The preparation method comprises the following steps:
1. mixing sodium bicarbonate with titanium organic matters, adding ferric phosphate, adding water for pulping, and stirring and mixing to obtain mixed slurry;
2. adding conductive graphite into the mixed slurry, and then adding the mixed slurry into a sand mill for sand milling, wherein the sand milling grain size is 280nm;
3. spray drying, calcining the obtained dried material, maintaining the calcining process in nitrogen atmosphere, and sieving to remove iron to obtain the sodium ion battery material.
The preparation method of the ferric phosphate comprises the following steps: and (3) ball milling slag generated in yellow phosphorus smelting, calcining the slag in a high-temperature air atmosphere, carrying out magnetic separation on the obtained material at the calcining temperature of 600 ℃, adding phosphoric acid into the rest material to dissolve the rest material, filtering the obtained filtrate, returning the filtrate, adding ammonia water, adjusting the pH value to 2, obtaining ferric phosphate dihydrate, filtering, drying, crushing and removing iron to obtain ferric phosphate dihydrate, and concentrating and crystallizing the filtered filtrate to obtain the ammonium phosphate compound fertilizer. The iron-phosphorus ratio of the iron phosphate is 1.02;1, and BET at 42m2/g, primary particle size of 46nm, and D50 at 7 μm;
the organic compound of titanium is a non-hydrolytic and water-soluble organic compound of titanium;
the molar ratio of the sodium bicarbonate to the titanium in the titanium organic matter is 1:0.75:0.25, and the mass fraction of water in the mixed slurry is 63%.
The mass of the conductive graphite added in the step (2) is 0.42% of the mass of the mixed slurry. Before adding the conductive graphite into the mixed slurry, adding the conductive graphite into water, mixing and stirring, putting into a sand mill, grinding until the particle size is 123nm, pouring the slurry into the mixed slurry, and grinding;
the spray-drying process in step (3) gave a spray-dried material having a D50 of 4.6. Mu.m.
In the calcination process, the whole calcination period is 28 hours, the temperature rising rate is 135 ℃/h, then the temperature of the first heat preservation area is 750 ℃, the heat preservation time is 1 hour, then the heat preservation temperature is 650 ℃ for 6 hours, and then the material is discharged after being cooled to the temperature less than or equal to 100 ℃.
And in the screening process, a 100-mesh ultrasonic vibration screen is adopted for screening, an electromagnetic iron remover is adopted for iron removal, the material is discharged after iron removal is less than or equal to 1ppm of magnetic substances, and the sodium ion battery is obtained through vacuum packaging.
Detection data of the finally obtained sodium battery material:
data at compaction density of 2.5T pressure. The test pressure of the internal resistance of the powder is 10MPa.
From the detection data, the product has higher discharge capacity, high compaction density, low internal resistance of powder, low magnetic substance and good product performance;
the BET is moderate, the 10C discharge capacity is high, and the rate performance is excellent. The sodium battery material obtained in the embodiment is used for preparing a soft-package battery core of 3Ah, a negative electrode is made of hard carbon, and the battery core is circulated at 25 ℃ according to 0.5C for 500 weeks, and the capacity retention rate is 93%. The cycle performance is excellent.
As shown in fig. 1, the secondary particle size is spherical from SEM, and the primary particle size is about 120-150nm, and the structure is compact, so that the processability is good and the electrical property is excellent.
Example 2
The molecular formula of the sodium ion battery material is as follows: 0.8NaTiO 2 .0.2NaFePO 4 The preparation method comprises the following steps:
1) Mixing sodium bicarbonate with titanium organic matters, adding ferric phosphate, adding water for pulping, and stirring and mixing to obtain mixed slurry;
2) Adding conductive graphite into the mixed slurry, and then adding the mixed slurry into a sand mill for sand milling, wherein the sand milling grain size is 280nm;
3) Spray drying, high-temperature calcining the obtained dried material, maintaining the calcining process in nitrogen atmosphere, and sieving to remove iron to obtain the sodium ion battery material.
In the step (1), the preparation method of the ferric phosphate comprises the following steps: calcining slag generated by yellow phosphorus smelting in a high-temperature air atmosphere after ball milling, adding phosphoric acid solution into the rest materials for dissolution after magnetic separation of the obtained materials, filtering, adding ammonia water into the obtained filtrate, adjusting the pH value to be 1.9, obtaining ferric phosphate dihydrate, filtering, drying, crushing and removing iron to obtain ferric phosphate dihydrate, and concentrating and crystallizing the filtrate obtained by filtering to obtain the ammonium phosphate compound fertilizer; the iron-phosphorus ratio of the ferric phosphate is 1.03;1 and BET at 42m 2 Per g, primary particle diameter 40nm, and D50 at 8.4. Mu.m.
The ball milling process is carried out by adopting a ball mill, wherein the grinding balls adopt zirconia balls with the diameter of 1cm, then sieving is carried out, 200 meshes of undersize products are taken for calcination, and oversize products are returned for ball milling; calcining by adopting a rotary kiln; the concentration of the phosphoric acid solution is 0.8mol/L, and the solid-liquid mass ratio is 1:4.
The organic compound of titanium in the step (1) is triisostearyl isopropyl titanate.
In the step (1), the molar ratio of sodium bicarbonate to titanium organic matters to ferric phosphate is 1:0.8:0.2, and the mass fraction of water in the mixed slurry is 60%.
The mass of the conductive graphite added in the step (2) is 0.4% of the mass of the mixed slurry; before adding the conductive graphite into the mixed slurry, adding the conductive graphite into water, mixing and stirring, putting into a sand mill for grinding until the particle size is 130nm, pouring the slurry into the mixed slurry, and grinding.
The spray-drying process in step (3) gave a spray-dried material having a D50 of 6.2. Mu.m.
In the step (3), the whole calcination period is 28 hours, the heating rate is 100 ℃/h, then the temperature of the first heat preservation area is 750 ℃, the heat preservation time is 1 hour, then the heat preservation temperature is 550 ℃ for 5 hours, then the temperature is reduced to be less than or equal to 100 ℃, the materials are discharged, the gas in the furnace is continuously pumped away by adopting a draught fan, meanwhile, nitrogen is continuously supplied in the furnace, the purity of the nitrogen is more than or equal to 99.999%, the moisture mass fraction of the nitrogen is lower than 0.1ppm, the humidity content of a heat preservation section is maintained to be lower than 5ppm, and the furnace pressure in the whole sintering furnace is 80Pa.
And in the screening process, an 80-mesh ultrasonic vibration screen is adopted for screening, an electromagnetic iron remover is adopted for iron removal, the material is discharged after iron removal is less than or equal to 1ppm of magnetic substances, and the sodium ion battery is obtained through vacuum packaging.
Detection data of the finally obtained sodium battery material:
as shown in fig. 2, the SEM of the sodium battery material obtained in this example has a small primary particle diameter.
Example 3
The molecular formula of the sodium ion battery material is as follows: 0.7NaTiO 2 .0.3NaFePO 4 The method comprises the steps of carrying out a first treatment on the surface of the The preparation method comprises the following steps:
1) Mixing sodium bicarbonate with titanium organic matters, adding ferric phosphate, adding water for pulping, and stirring and mixing to obtain mixed slurry;
2) Adding conductive graphite into the mixed slurry, and then adding the mixed slurry into a sand mill for sand milling, wherein the sand milling grain size is 250nm;
3) Spray drying, high-temperature calcining the obtained dried material, maintaining the calcining process in nitrogen atmosphere, and sieving to remove iron to obtain the sodium ion battery material.
In the step (1), the preparation method of the ferric phosphate comprises the following steps: calcining slag generated by yellow phosphorus smelting in a high-temperature air atmosphere after ball milling, wherein the calcining temperature is 680 ℃ and the calcining time is 5 hours, adding phosphoric acid solution into the rest materials for dissolving after magnetic separation, filtering, adding ammonia water into the obtained filtrate, adjusting the pH value to be 1.9, obtaining ferric phosphate dihydrate, filtering, drying, crushing and deironing to obtain ferric phosphate dihydrate, concentrating and crystallizing the filtered filtrate to obtain the ammonium phosphate compound fertilizer; the iron-phosphorus ratio of the iron phosphate is 1.04;1 and BET at 45m 2 Per g, a primary particle diameter of 30nm and a D50 of 5.8. Mu.m.
The ball milling process is carried out by adopting a ball mill, wherein the grinding balls adopt zirconia balls with the diameter of 3cm, then sieving is carried out, 200 meshes of undersize products are taken for calcination, and oversize products are returned for ball milling; calcining by adopting a rotary kiln; the concentration of the phosphoric acid solution is 0.9mol/L, and the solid-liquid mass ratio is 1:3.5.
The organic compound of titanium in the step (1) is chelate titanate.
In the step (1), the molar ratio of sodium bicarbonate to titanium organic matters to ferric phosphate is 1:0.7:0.3, and the mass fraction of water in the mixed slurry is 70%.
The mass of the conductive graphite added in the step (2) is 0.35% of the mass of the mixed slurry; before adding the conductive graphite into the mixed slurry, adding the conductive graphite into water, mixing and stirring, putting into a sand mill for grinding until the particle size is 120nm, pouring the slurry into the mixed slurry, and grinding.
The spray-drying process in step (3) gave a spray-dried material having a D50 of 6.1. Mu.m.
In the step (3), the whole calcination period is 30 hours, the heating rate is 85 ℃/h, then the temperature of the first heat preservation area is 750 ℃, the heat preservation time is 1 hour, then the heat preservation temperature is 600 ℃ for 6 hours, then the temperature is reduced to be less than or equal to 100 ℃, the materials are discharged, the gas in the furnace is continuously pumped away by adopting a draught fan, meanwhile, nitrogen is continuously supplied in the furnace, the purity of the nitrogen is more than or equal to 99.999%, the moisture mass fraction of the nitrogen is lower than 0.1ppm, the humidity content of a heat preservation section is maintained to be lower than 5ppm, and the furnace pressure in the whole sintering furnace is 70Pa.
And in the screening process, a 150-mesh ultrasonic vibration screen is adopted for screening, an electromagnetic iron remover is adopted for iron removal, the material is discharged after iron removal is less than or equal to 1ppm of magnetic substances, and the sodium ion battery is obtained through vacuum packaging.
Detection data of the finally obtained sodium battery material:
as shown in fig. 2, the SEM of the sodium battery material obtained in this example has a small primary particle diameter.
Finally, it is noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered by the scope of the claims of the present invention.
Claims (9)
1. A preparation method of a sodium ion battery material is characterized by comprising the following steps: the molecular formula of the sodium ion battery material is as follows: xNaTiO 2 .yNaFePO 4 The molar ratio of x to y is 0.7-0.8:0.2-0.3; the preparation method comprises the following steps:
1) Mixing sodium bicarbonate with titanium organic matters, adding ferric phosphate, adding water for pulping, and stirring and mixing to obtain mixed slurry; the preparation method of the ferric phosphate comprises the following steps: calcining slag generated by yellow phosphorus smelting in a high-temperature air atmosphere after ball milling at 500-700 ℃ for 4-6 hours, adding phosphoric acid solution into the rest materials for dissolution after magnetic separation, filtering, adding ammonia water into the obtained filtrate, adjusting pH to 1.8-2.2 to obtain ferric phosphate dihydrate, filtering, drying, crushing and deironing to obtain ferric phosphate dihydrate, concentrating and crystallizing the filtrate obtained by filtering to obtain ammonium phosphate compound fertilizer;
2) Adding conductive graphite into the mixed slurry, and then adding the mixed slurry into a sand mill for sand milling, wherein the sand milling grain size is 250-300nm;
3) Spray drying, high-temperature calcining the obtained dried material, maintaining the calcining process in nitrogen atmosphere, and sieving to remove iron to obtain the sodium ion battery material.
2. The method for preparing the sodium ion battery material according to claim 1, wherein the method comprises the following steps: the iron-phosphorus ratio of the ferric phosphate in the step (1) is 1.0-1.05;1 and BET is in the range of 30 to 50m 2 Per g, a primary particle diameter of 30-60nm and a D50 of 3-10 μm.
3. The method for preparing the sodium ion battery material according to claim 2, wherein the method comprises the following steps: the ball milling process is carried out by adopting a ball mill, wherein the grinding balls adopt zirconia balls with the diameter of 1-3cm, then sieving is carried out, 200-mesh undersize products are taken for calcination, and the oversize products return to carry out ball milling; calcining by adopting a rotary kiln; the concentration of the phosphoric acid solution is 0.5-1mol/L, and the solid-liquid mass ratio is 1:3-4.
4. The method for preparing the sodium ion battery material according to claim 1, wherein the method comprises the following steps: the organic compound of titanium in the step (1) is a non-hydrolytic and water-soluble titanium organic compound.
5. The method for preparing the sodium ion battery material according to claim 1, wherein the method comprises the following steps: in the step (1), the molar ratio of sodium bicarbonate to titanium organic matters to ferric phosphate is 1:0.7-0.8:0.2-0.3, and the mass fraction of water in the mixed slurry is 60-70%.
6. The method for preparing the sodium ion battery material according to claim 1, wherein the method comprises the following steps: the mass of the conductive graphite added in the step (2) is 0.2-0.5% of the mass of the mixed slurry; before adding the conductive graphite into the mixed slurry, adding the conductive graphite into water, mixing and stirring, putting into a sand mill for grinding until the particle size is 100-150nm, pouring the slurry into the mixed slurry, and then grinding.
7. The method for preparing the sodium ion battery material according to claim 1, wherein the method comprises the following steps: and (3) carrying out spray drying in the step (3), wherein the D50 of the obtained spray-dried material is 3-10 mu m.
8. The method for preparing the sodium ion battery material according to claim 1, wherein the method comprises the following steps: in the step (3), the whole calcination period is 25-30h, the heating rate is 80-120 ℃/h, then the temperature of the first heat preservation area is 750 ℃, the heat preservation time is 1h, then the heat preservation temperature is 550-600 ℃ for 5-6h, then the material temperature is reduced to be less than or equal to 100 ℃, then the material is discharged, the gas in the furnace is continuously pumped away by an induced draft fan, meanwhile, the nitrogen is continuously supplied in the furnace, the purity of the nitrogen is more than or equal to 99.999%, the moisture mass fraction of the nitrogen is lower than 0.1ppm, the humidity content of the heat preservation section is maintained to be lower than 5ppm, and the furnace pressure in the whole sintering furnace is 60-100Pa.
9. The method for preparing the sodium ion battery material according to claim 1, wherein the method comprises the following steps: and in the screening process, an 80-150-mesh ultrasonic vibration screen is adopted for screening, an electromagnetic iron remover is adopted for iron removal, the material is discharged after iron removal is less than or equal to 1ppm of magnetic substances, and vacuum packaging is carried out, so that the sodium ion battery is obtained.
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