CN114751391A - High-density phosphorylated sodium titanate material, preparation method and application - Google Patents
High-density phosphorylated sodium titanate material, preparation method and application Download PDFInfo
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Abstract
The invention discloses a high-density phosphorylated sodium titanate material, a preparation method and application thereof, and TiO is prepared by2Adding the powder into an alkaline solution, and carrying out hydrothermal reaction to obtain a sodium titanate nanotube material; adding a phosphate radical-containing compound and a sodium titanate nanotube material into a solvent; stirring the mixed solution at a certain temperature to obtain dry powder; under different atmospheres, the dry powder is subjected to heat treatment under certain temperature conditions to obtain the high-density sodium phosphate titanate materialAnd (4) feeding. The specific surface area of the high-density phosphorylated sodium titanate material prepared by the invention is greatly reduced, the compaction density is greatly improved, the reduction of the specific surface area effectively reduces the side reaction between electrode electrolytes, so that the coulomb efficiency and the stability of the material are improved, the volume specific capacity of the material is greatly increased by improving the compaction density, and the practicability of the material is obviously improved.
Description
Technical Field
The invention belongs to the technical field of battery cathode materials, and relates to a high-density sodium phosphate titanate material, and a preparation method and application thereof.
Background
The lithium ion battery has the advantages of high energy density, long cycle life, good safety performance and the like, and is widely applied to the fields of various portable electronic equipment and electric automobiles. The success of lithium ion batteries has also driven the research heat of other secondary ion batteries with similar working mechanisms, among which sodium ion batteries are considered as the most promising energy storage batteries due to the use of sodium element with lower cost and abundant reserves. An important requirement, whether it be an electric vehicle or an energy storage system, is that the battery be able to accept and provide more power for faster charging. The achievement of this requirement requires a breakthrough of the cell material.
The negative electrode material is a key part of the metal ion battery, and directly influences the specific capacity and the rate capability of the metal ion battery. Currently commercialized metal-ion battery negative electrode materials, such as graphite and lithium titanate, are typical intercalation-type materials. In such materials, the diffusion of lithium/sodium ions in the bulk phase is often the rate limiting step of the electrochemical reaction, which determines the rate of charge and discharge. Nanocrystallization of electrode materials is a major strategy to improve the rate capability of materials, because in the nanocrystallized electrode materials electrochemical reactions almost all occur on the surface and near surface of the materials, and the ion diffusion distance is greatly shortened. However, due to the defects of huge specific surface, too low compaction density and the like, the nano electrode material has unsatisfactory coulombic efficiency and volume specific capacity, and directly influences the battery performance of the metal ion battery.
The sodium titanate nano material (the form of the sodium titanate nano material comprises a nano tube, a nano wire and the like) is a typical pseudocapacitance material, most of electrochemical reaction of the sodium titanate nano material occurs on the surface of the nano material, the sodium titanate nano material has the characteristic of quick charge and discharge, all components of the material are earth crust negative electrode elements, the cost is low, the sodium titanate nano material is a promising metal ion battery negative electrode material, and then the sodium titanate nano material has the defects of huge specific surface and low compaction density shared by other nano electrode materials.
Disclosure of Invention
In order to achieve the purpose, the invention provides a high-density sodium phosphate titanate material, a preparation method and application thereof, wherein the specific surface area is greatly reduced, the compaction density is greatly improved, the reduction of the specific surface area effectively reduces the side reaction between electrode electrolytes, the coulomb efficiency and the stability of the material are further improved, the improvement of the compaction density greatly increases the volume specific capacity of the material, the practicability of the material is obviously improved, and the problems in the prior art are solved.
The technical scheme adopted by the invention is that the preparation method of the high-density sodium phosphate titanate material comprises the following steps:
s1: mixing TiO with2Adding 1g of powder into the alkaline solution according to the mass-volume ratio of (10 mL-50 mL), uniformly mixing, transferring into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 5-24 h at the temperature of 100-200 ℃, and cleaning and drying the obtained product to obtain a sodium titanate nanotube material;
S2: adding a phosphate radical-containing compound and a sodium titanate nanotube material into a solvent according to the molar ratio of P to Ti of (0.01-0.2) to 1 to obtain a mixed solution with the concentration of 0.05-2 g/mL; the solvent comprises: one or two of deionized water and absolute ethyl alcohol;
s3: stirring the mixed solution at the temperature of 40-100 ℃ for 0.5-24 h at the rotating speed of 50-500 r/min to obtain dry powder;
s4: and (3) carrying out heat treatment on the dried powder at the temperature of 300-800 ℃ for 10 min-10 h under different atmospheres to obtain the high-density phosphorylated sodium titanate material.
Further, in S1, the alkaline solution includes NaOH aqueous solution, and the concentration of the NaOH aqueous solution is 5 mol/L-10 mol/L.
Further, in S2, the phosphate group-containing compound includes: any one of ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, and orthophosphoric acid.
Further, S2 further includes a step of adding conductive carbon black after adding the sodium titanate nanotube material.
Further, the mass of the conductive carbon black is not more than 25% of the mass of the sodium titanate nanotube material.
Further, the conductive carbon black includes: any one or more of acetylene black, acid-treated acetylene black, graphene oxide and carbon nanotubes.
Further, in S4, the atmosphere includes: air, oxygen, nitrogen or argon.
Further, in S4, the compacted density range of the high-density phosphorylated sodium titanate material is 0.81g/cm3~2.05g/cm3。
Another object of the present invention is to provide a high-density phosphorylated sodium titanate material, which is prepared by the above-mentioned method for preparing a high-density phosphorylated sodium titanate material.
The invention further aims to provide application of the high-density sodium phosphate titanate material in a metal ion battery.
The invention has the beneficial effects that:
(1) the high-density phosphorylated sodium titanate negative electrode material provided by the embodiment of the invention has the advantages that the raw material source is wide and easy to obtain, sodium, titanium, phosphorus and oxygen are all enriched elements, and the high-density phosphorylated sodium titanate negative electrode material is low in cost when used as a metal ion battery negative electrode material.
(2) Compared with the sodium titanate nanotube, the high-density phosphorylated sodium titanate negative electrode material prepared by the embodiment of the invention has the advantages that the specific surface area is greatly reduced from 350m2The/g is reduced to 130m2Less than g, and the compaction density is greatly improved to 0.81g/cm3~2.05g/cm3The reduction of the specific surface area effectively reduces the side reaction between the electrode electrolyte, further improves the coulomb efficiency and the stability of the material, and the improvement of the compaction density greatly increases the volume specific capacity of the material, and obviously improves the practicability of the material.
(3) The high-density phosphorylated sodium titanate negative electrode material and the high-voltage LiNi prepared by the embodiment of the invention0.5Mn1.5O4The full battery formed by the combination of the anode materials has ultrahigh rate performance and cycling stability.
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 embodiments or the prior art descriptions will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 shows sodium titanate nanotubes Na prepared by the method of the present invention2Ti6O13TEM image of (a).
FIG. 2 shows example Na of the present invention2Ti6P0.8O15TEM image of @ C.
FIG. 3 shows example Na of the present invention2Ti6O13And Na2Ti6P0.8O15The nitrogen adsorption and desorption curve of the @ C negative electrode material.
FIG. 4 shows example Na of the present invention2Ti6O13And Na2Ti6P0.8O15SEM picture of @ C.
FIG. 5 shows example Na of the present invention2Ti6O13And Na2Ti6P0.8O15XRD pattern of @ C.
FIG. 6 shows example Na of the present invention2Ti6O13And Na2Ti6P0.8O15Electrochemical rate performance of @ C in half-cells.
FIG. 7 shows examples Na of the present invention2Ti6O13And Na2Ti6P0.8O15@ C long cycle stability performance in half cells.
FIG. 8 shows examples Na of the present invention 2Ti6O13And Na2Ti6P0.8O15The volumetric specific capacity of @ C at different current densities.
FIG. 9 shows example Na of the present invention2Ti6P0.8O15/ LiNi0.5Mn1.5O4Rate capability and cycling stability of the full cell.
FIG. 10 shows example Na of the present invention2Ti6P1.2O16The nitrogen adsorption-desorption curve of (1).
FIG. 11 shows example Na of the present invention2Ti6P1.2O16SEM image of electrode, and the loading amount is 5 mg/cm2。
FIG. 12 shows examples Na of the present invention2Ti6P1.2O16XRD pattern of (a).
FIG. 13 shows example Na of the present invention2Ti6P1.2O16Electrochemical rate capability of (1).
FIG. 14 shows example Na of the present invention2Ti6P1.2O16Volumetric to capacity performance of.
FIG. 15 shows example Na of the present invention2Ti6O13And Na2Ti6P1.2O16Electrochemical rate and cycling performance in the half cell.
FIG. 16 shows example Na of the present invention2Ti6O13And Na2Ti6P0.4O14Electrochemical rate and cycling performance of @ C in half-cells.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in 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 derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The preparation method of the high-density phosphorylated sodium titanate material comprises the following steps:
S1: adding TiO into the mixture2Adding 1g of powder into an alkaline solution according to the mass-volume ratio of (10 mL-50 mL), uniformly mixing, transferring into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 5-24 h at the temperature of 100-200 ℃, and after the reaction is finished, cleaning and drying the obtained precipitate with deionized water to obtain the sodium titanate nanotube material.
Wherein the alkaline solution comprises a NaOH aqueous solution with the concentration of 5-10 mol/L.
S2: adding a phosphate radical-containing compound into a solvent, and then adding a sodium titanate nanotube material to obtain a mixed solution with the concentration of 0.05 g/mL-2 g/mL.
Wherein the molar ratio of P to Ti in the phosphate radical-containing compound and the sodium titanate nanotube material is (0.01-0.2): 1. The phosphate group-containing compound includes: ammonium dihydrogen phosphate, diammonium hydrogen phosphate, orthophosphoric acid, and sodium phosphate. The solvent comprises: deionized water, absolute ethyl alcohol or the mixture of the two in any volume ratio.
Conductive carbon black can be added after the sodium titanate nanotube material is added in the step, and the adding amount of the conductive carbon black is 0-25% of the mass of the sodium titanate nanotube. The conductive carbon black includes: any one or more of acetylene black, acid-treated acetylene black, graphene oxide and carbon nanotubes.
S3: and stirring the mixed solution at the temperature of 40-100 ℃ for 0.5-24 h at the rotating speed of 50-500 r/min to obtain dry powder. When the solvent is absolute ethyl alcohol, stirring for 0.5-10 h at the rotating speed of 50-500 r/min at the temperature of 40-60 ℃ to obtain dry powder.
S4: and (3) carrying out heat treatment on the dried powder at the temperature of 300-800 ℃ for 10 min-10 h under different atmospheres to obtain the high-density phosphorylated sodium titanate material. Wherein the atmosphere comprises: air, oxygen, nitrogen or argon. The dry powder containing conductive carbon black is carried out in an atmosphere of nitrogen or argon.
The heat treatment at 300 ℃ or lower may leave crystal water, which is not favorable for the stability of the product in the operation of the battery, and the heat treatment at 800 ℃ or higher may cause the performance to be degraded due to excessive sintering.
The compacted density range of the high-density phosphorylated sodium titanate material is 0.81g/cm3~2.05g/cm3The increase of the compaction density can bring about the increase of the energy density of the battery volume, and in the application, the control of the compaction density is realized by adjusting the phosphorylation degree. If the compacted density of the high-density phosphorylated sodium titanate material exceeds 2.05g/cm3This may cause the lithium ion transport to be hindered, which may result in a reduction in rate performance.
Example 1
The preparation method of the high-density phosphorylated sodium titanate material comprises the following steps:
(1) 2g of TiO2Adding the nano powder into 60mL of 10mol/L NaOH aqueous solution, uniformly mixing, magnetically stirring for 2 hours at the rotating speed of 500r/min to obtain a mixed suspension, transferring the mixed suspension into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 24 hours at the temperature of 130 ℃, fully cleaning the obtained white precipitate with deionized water after the reaction is finished, and then carrying out vacuum drying at the drying temperature of 70 ℃ for 10 hours to obtain the sodium titanate nanotube Na2Ti6O13The appearance of the nano-tube is shown in figure 1, and the structure is loose.
(2) 0.4g of ammonium dihydrogen phosphate was added to 20mL of anhydrous ethanol, and 2.4g of sodium titanate nanotubes (molar ratio of P: Ti: 0.4: 3) and 0.3g of acid-treated acetylene black were further added to obtain a mixed solution having a concentration of 0.155 g/mL.
The treatment process of the acid treatment of the acetylene black comprises the following steps: under the condition of room temperature, acetylene black is added into nitric acid solution with the concentration of 0.5mol/L according to the mass-volume ratio of 1g:100mL, the mixture is stirred for 24 hours at the rotating speed of 300r/min, and the obtained product is filtered, washed and dried (90 ℃, 10 hours) to obtain the acid-treated acetylene black.
(3) Stirring the mixed solution at 60 deg.C at a rotation speed of 200r/min for 2 hr to obtain dry powder.
(4) Under the nitrogen atmosphere, the dried powder is subjected to heat treatment for 1h at the temperature of 500 ℃ to obtain the high-density sodium phosphate titanate material Na2Ti6P0.8O15@ C, the morphology of which is shown in figure 2, almost disappears, and the density is remarkably improved.
As shown in FIG. 3, the sodium titanate nanotubes Na obtained in this example2Ti6O13Has a specific surface area of 350m2(g), high-density phosphorylated sodium titanate material Na2Ti6P0.8O15Specific surface area of @ C183 m2The specific surface area of the product after densification treatment is obviously reduced.
As shown in FIG. 4, at 5.0mg/cm2In the case of the supported amount of Na, this example Na2Ti6O13The electrode prepared as the negative electrode material had a thickness of 61.6 μm and a compacted density of 0.81g/cm3(ii) a This example Na2Ti6P0.8O15The thickness of an electrode prepared by adopting @ C as a negative electrode material is 37.2 microns, and the compaction density is 1.34g/cm3The thickness of the electrode prepared by taking the product after densification as the cathode material is obviously reduced, and the compaction density is obviously improved.
As shown in FIG. 5, Na obtained in this example2Ti6P0.8O15The degree of crystallization of @ C is significantly weaker than that of sodium titanate nanotubes Na2Ti6O13The diffraction peak intensity is obviously reduced, and the non-crystallization degree is obviously improved.
As shown in the results of electrochemical analysis in FIG. 6, the sodium titanate nanotubes Na obtained in this example2Ti6O13The coulombic efficiency of the first turn of the electrode prepared as the negative electrode material was 69%, and the Na obtained in this example2Ti6P0.8O15The coulombic efficiency of the first turn of the electrode prepared by using @ C as the negative electrode material is 92 percent, and Na2Ti6P0.8O15The specific surface area of @ C is obviously reduced, and the first turn of coulombic efficiency is obviously improved. In addition, Na2Ti6P0.8O15The electrode prepared by adopting @ C as the negative electrode material still maintains extremely high rate capability, still has the specific capacity of 106mAh/g under the super-high current of 10A/g, and is higher than the Na of the sodium titanate nanotube2Ti6O13The specific capacity of (2) is 81 mAh/g.
As shown in the results of the rate capability test of FIG. 7, Na obtained in this example2Ti6P0.8O15The capacity retention rate of an electrode prepared by adopting @ C as a negative electrode material reaches 95% after 2000 cycles at 2A/g, which is far higher than that of a sodium titanate nanotube Na2Ti6O13The electrode is prepared as a negative electrode material.
As shown in the results of the volumetric specific capacity test of FIG. 8, the sodium titanate nanotubes Na obtained in this example2Ti6O13The volumetric specific capacity of the prepared electrode is 166 ampere hours per liter, and the Na obtained in the embodiment is improved due to the fact that the compaction density and the rate capability are improved simultaneously2Ti6P0.8O15The specific volumetric capacity of the electrode prepared at @ C is increased by nearly three times from 166 ampere-hours per liter to 291 ampere-hours per liter.
As shown in FIG. 9, Na obtained in this example2Ti6P0.8O15With @ C as negative electrode and high voltage LiNi0.5Mn1.5O4The material is used as the anode, and the combined full battery has ultrahigh rate performance and cycle stability.
Example 2
The preparation method of the high-density phosphorylated sodium titanate negative electrode material comprises the following steps:
(1) 2g of TiO2Adding the nano powder into 100mL of 8mol/L NaOH aqueous solution, uniformly mixing, magnetically stirring for 5 hours at the rotating speed of 400r/min to obtain a mixed suspension, transferring the mixed suspension into a hydrothermal reaction kettle, preserving heat for 15 hours at the temperature of 160 ℃, fully cleaning the obtained white precipitate with deionized water after the reaction is finished, and then drying in vacuum at the drying temperature of 70 ℃ for 10 hours to obtain the sodium titanate nanotube Na2Ti6O13。
(2) 0.3g of diammonium phosphate and 1g of sodium titanate nanotube material were added to 10mL of absolute ethanol (P: Ti = 0.2: 1) to obtain a mixed solution having a concentration of 0.25 g/mL.
(3) And stirring the mixed solution at the temperature of 60 ℃ for 3 hours at the rotating speed of 350r/min to obtain dry powder.
(4) Carrying out heat treatment on the dried powder for 2h at the temperature of 450 ℃ in the oxygen atmosphere to obtain a high-density sodium phosphate titanate material Na 2Ti6P1.2O16。
This example resulted in the comparison of untreated sodium titanate nanotubesThe high-density phosphorylated sodium titanate material Na2Ti6P1.2O16The specific surface area of (A) is significantly reduced, as shown in FIG. 10, and is only 130m2(ii) in terms of/g. Na obtained in this example2Ti6P1.2O16The electrode prepared as the negative electrode material is at the same 5.0 g/cm2In the case of the load amount, as shown in FIG. 11, the thickness thereof was only 37.2 μm, and the compaction density was increased to 2.05g/cm3. As shown in FIG. 12, Na obtained in this example2Ti6P1.2O16It can be seen in the XRD pattern of (a) that phosphorylation further reduced the intensity of the characteristic diffraction peak, but no new crystalline phase was formed. As shown in FIG. 13, Na obtained in this example2Ti6P1.2O16Has good rate capability. More importantly, the present example yielded Na due to a greatly increased compacted density, as shown in FIG. 142Ti6P1.2O16The volumetric capacity of (a) is increased by approximately three times from 166 to 355 ampere-hours per liter.
Example 3
The preparation method of the high-density phosphorylated sodium titanate material comprises the following steps:
s1: 2g of TiO2Adding the powder into 20mL of NaOH aqueous solution with the concentration of 5mol/L, uniformly mixing, transferring the mixture into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 5 hours at the temperature of 200 ℃, and after the reaction is finished, cleaning and drying the obtained precipitate with deionized water to obtain the sodium titanate nanotube material.
S2: 0.22 g of orthophosphoric acid and 1g of sodium titanate nanotube material (P: Ti = 0.2: 1) were added to 25 mL of deionized water to obtain a mixed solution having a concentration of 0.05 g/mL.
S3: and stirring the mixed solution at the temperature of 90 ℃ for 24 hours at the rotating speed of 500r/min to obtain dry powder.
S4: carrying out heat treatment on the dried powder at the temperature of 800 ℃ for 10min in the air atmosphere to obtain a high-density sodium phosphate titanate material Na2Ti6P1.2O15。
Prepared in this exampleThe compacted density of the high-density phosphorylated sodium titanate electrode is 2.05g/cm3. As shown in fig. 15, the electrochemical rate performance is: the specific capacity is 160mAh/g under the current density of 0.2A/g; the specific capacity is 93mAh/g under the current density of 10A/g. The cycling stability is as follows: the capacity retention rate after 800 cycles under 2A/g is 96%.
Example 4
The preparation method of the high-density phosphorylated sodium titanate material comprises the following steps:
(1) 2g of TiO2Adding the powder into 80mL of 9mol/L NaOH aqueous solution, uniformly mixing, transferring into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 20h at the temperature of 100 ℃, washing the obtained precipitate with deionized water after the reaction is finished, and drying to obtain the sodium titanate nanotube material.
(2) 0.11g of ammonium phosphate and 1g of sodium titanate nanotube material (P: Ti =0.2: 3) were added to 11mL of 50% ethanol aqueous solution, and then 0.1g of acetylene black was added to obtain a mixed solution having a concentration of 0.1 g/mL.
(3) Stirring the mixed solution at 40 deg.C and 50r/min for 5 hr to obtain dry powder.
(4) In the argon atmosphere, the dried powder is subjected to heat treatment for 10 hours at the temperature of 300 ℃ to obtain a high-density sodium phosphate titanate material Na2Ti6P0.4O14@C。
The compacted density of the high-density phosphorylated sodium titanate material prepared in the embodiment is 1.10g/cm-3. As shown in fig. 16, the electrochemical rate performance is: the specific capacity is 163mAh/g under the current density of 0.2A/g, and is 30mAh/g under the current density of 10A/g. The cycling stability is as follows: the capacity retention rate after 1000 cycles under 2A/g is 94%.
Example 5
The preparation method of the high-density phosphorylated sodium titanate material comprises the following steps:
in addition to (2), 0.015g of diammonium phosphate and 1g of sodium titanate nanotube material were added to 10mL of absolute ethanol (P: Ti = 0.01: 1);
the rest is the same as in example 2.
The compacted density of the high-density phosphorylated sodium titanate material prepared in the embodiment is 0.92g/cm 3The electrochemical multiplying power performance is under the current density of 0.2A/g, and the specific capacity is 156 mAh/g; the specific capacity is 28mAh/g under the current density of 10A/g. The capacity retention rate of the composite material after 800 cycles of circulation under the circulation stability of 2A/g is 91%.
Comparative example
The preparation method of the high-density phosphorylated sodium titanate material comprises the following steps:
sodium dihydrogen phosphate is adopted as a phosphating reagent in the step (2) and acetylene black is not added with acid for treatment;
the rest is the same as in example 1.
The phosphorylation reagent adopts sodium dihydrogen phosphate, and the compacted density of the high-density phosphorylation sodium titanate material prepared by the comparative example is 1.85g/cm3The electrochemical multiplying power performance is under 0.2A/g current density, and the specific capacity is 144 mAh/g; the specific capacity is 36mAh/g under the current density of 10A/g. The capacity retention rate is 76% after the circulation stability is 2A/g and 200 circles of circulation. The change in the properties of the product of this comparative example is mainly due to the sodium element of sodium dihydrogen phosphate affecting the ratio of sodium in the product.
All the embodiments in the present specification are described in a related manner, and the same and similar parts among the embodiments may be referred to each other, and each embodiment focuses on the differences from the other embodiments.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.
Claims (10)
1. The preparation method of the high-density phosphorylated sodium titanate material is characterized by comprising the following steps:
s1: adding TiO into the mixture2Adding 1g of powder into the alkaline solution according to the mass-volume ratio of (10 mL-50 mL), uniformly mixing, transferring into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 5-24 h at the temperature of 100-200 ℃, thus obtaining the productCleaning and drying the obtained product to obtain a sodium titanate nanotube material;
s2: adding a phosphate radical-containing compound and a sodium titanate nanotube material into a solvent according to the molar ratio of P to Ti of (0.01-0.2) to 1 to obtain a mixed solution with the concentration of 0.05-2 g/mL; the solvent comprises: one or two of deionized water and absolute ethyl alcohol;
s3: stirring the mixed solution at the temperature of 40-100 ℃ for 0.5-24 h at the rotating speed of 50-500 r/min to obtain dry powder;
s4: and (3) carrying out heat treatment on the dried powder at the temperature of 300-800 ℃ for 10 min-10 h under different atmospheres to obtain the high-density phosphorylated sodium titanate material.
2. The method for preparing the high-density phosphorylated sodium titanate negative electrode material according to claim 1, wherein in S1, the alkaline solution comprises an aqueous NaOH solution, and the concentration of the aqueous NaOH solution is 5-10 mol/L.
3. The method for preparing the high-density phosphorylated sodium titanate negative electrode material according to claim 1, wherein in S2, the phosphate group-containing compound comprises: any one of ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, and orthophosphoric acid.
4. The method for preparing a high-density phosphorylated sodium titanate negative electrode material according to claim 1, characterized in that the step of adding conductive carbon black after adding sodium titanate nanotube material is further included in S2.
5. The preparation method of the high-density phosphorylated sodium titanate negative electrode material according to claim 4, characterized in that the mass of the conductive carbon black is not more than 25% of the mass of the sodium titanate nanotube material.
6. The method for preparing the high-density phosphorylated sodium titanate negative electrode material according to claim 5, wherein the conductive carbon black comprises: any one or more of acetylene black, acid-treated acetylene black, graphene oxide and carbon nanotubes.
7. The method for preparing the high-density phosphorylated sodium titanate negative electrode material according to claim 1, wherein in S4, the atmosphere comprises: air, oxygen, nitrogen or argon.
8. The method for preparing the high-density phosphorylated sodium titanate negative electrode material according to claim 1, wherein in S4, the compacted density range of the high-density phosphorylated sodium titanate material is 0.81g/cm 3~2.05g/cm3。
9. The high-density phosphorylated sodium titanate material is prepared by the preparation method of the high-density phosphorylated sodium titanate material according to any one of claims 1 to 8.
10. The use of the high density phosphorylated sodium titanate material of claim 9 in a metal ion battery.
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