CN114751391B - High-density phosphorylated sodium titanate material, preparation method and application - Google Patents

High-density phosphorylated sodium titanate material, preparation method and application Download PDF

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CN114751391B
CN114751391B CN202210373686.3A CN202210373686A CN114751391B CN 114751391 B CN114751391 B CN 114751391B CN 202210373686 A CN202210373686 A CN 202210373686A CN 114751391 B CN114751391 B CN 114751391B
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sodium
sodium titanate
phosphorylated
titanate
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CN114751391A (en
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朱晓波
童卓雅
贾传坤
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Changsha University of Science and Technology
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Abstract

The invention discloses a high-density phosphorylated sodium titanate material, a preparation method and application thereof, and TiO (titanium dioxide) 2 Adding the powder into an alkaline solution, and performing hydrothermal reaction to obtain a sodium titanate nanotube material; adding a phosphate-containing compound and sodium titanate nanotube material into a solvent; stirring the mixed solution at a certain temperature to obtain dry powder; and (3) carrying out heat treatment on the dry powder under different atmospheres at a certain temperature to obtain the high-density sodium phosphorylate titanate material. The specific surface area of the high-density sodium phosphorylate titanate material prepared by the method is greatly reduced, the compaction density is greatly improved, the side reaction between electrode electrolytes is effectively reduced by the reduction of the specific surface area, the coulomb efficiency and stability of the material are further improved, the volume specific capacity of the material is greatly increased by the improvement of the compaction density, and the practicability of the material is remarkably improved.

Description

High-density phosphorylated sodium titanate material, preparation method and application
Technical Field
The invention belongs to the technical field of battery cathode materials, and relates to a high-density sodium phosphorylate titanate material, 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 that are similar in operation mechanism, with sodium ion batteries being considered as the most promising energy storage batteries due to the lower cost of use and the abundant reserves of sodium elements. 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 breakthrough of the battery material.
The cathode material is a key component of the metal ion battery, and directly influences the specific capacity and the multiplying power performance of the metal ion battery. Currently commercial metal ion battery anode materials, such as graphite and lithium titanate, are typical intercalation materials. In such materials, the diffusion of lithium/sodium ions in the bulk phase is often the rate limiting step in the electrochemical reaction, determining the rate of charge and discharge. Nanocrystallization of electrode materials is a major strategy for improving the rate capability of the materials, because electrochemical reactions in nanocrystallized electrode materials almost all occur on the surface and near-surface of the materials, and the ion diffusion distance is greatly shortened. However, the nano electrode material has the defects of large specific surface area, low compaction density and the like, so that the coulomb efficiency and the volume specific capacity of the nano electrode material are not ideal, and the battery performance of the metal ion battery is directly influenced.
The sodium titanate nano material (the form of which comprises a nano tube, a nano wire and the like) is a typical pseudo-capacitance material, most of electrochemical reaction occurs on the surface of the nano material, the nano material has the characteristic of rapid charge and discharge, all components of the material are crust negative electrode elements, the cost is low, and the nano material is a promising metal ion battery negative electrode material, and then the nano material has the defects of huge specific surface and low compaction density which are common to other nano electrode materials.
Disclosure of Invention
In order to achieve the above purpose, the invention provides a high-density sodium phosphorylate 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 side reactions between electrode electrolytes, the coulomb efficiency and stability of the material are further improved, the volume specific capacity of the material is greatly increased due to the improvement of the compaction density, 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 phosphorylate titanate material comprises the following steps:
s1: tiO is mixed with 2 Adding 1g (10-50 mL) of powder into an alkaline solution according to the mass-volume ratio, uniformly mixing, transferring into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 5-24 h at the temperature of 100-200 ℃, and washing and drying the obtained product to obtain a sodium titanate nanotube material;
s2: adding a phosphate-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): 1 to obtain a mixed solution with the concentration of 0.05 g/mL-2 g/mL; the solvent comprises: either or both of deionized water and absolute ethyl alcohol;
s3: stirring the mixed solution at the temperature of 40-100 ℃ for 0.5-24 hours at the rotating speed of 50-500 r/min to obtain dry powder;
s4: and (3) carrying out heat treatment on the dry powder at the temperature of 300-800 ℃ for 10 min-10 h under different atmospheres to obtain the high-density sodium phosphorylate titanate material.
Further, in S1, the alkaline solution comprises an aqueous NaOH solution, and the concentration of the aqueous NaOH solution is 5-10 mol/L.
Further, in S2, the phosphate-containing compound includes: ammonium phosphate, monoammonium phosphate, diammonium phosphate, and orthophosphoric acid.
Further, in S2, the method 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.
Still further, the conductive carbon black includes: acetylene black, acid-treated acetylene black, graphene oxide, or carbon nanotubes.
Further, in S4, the atmosphere includes: air, oxygen, nitrogen or argon.
Further, in S4, the compacted density of the high-density sodium phosphorylated titanate material is in the range of 0.81g/cm 3 ~2.05g/cm 3 。
The invention also aims at providing a high-density sodium phosphorylate titanate material, such as the high-density sodium phosphorylate titanate material prepared by the preparation method.
It is still another object of the present invention to provide the use of the above-described high density phosphorylated sodium titanate material in metal ion batteries.
The beneficial effects of the invention are as follows:
(1) The high-density phosphorylated sodium titanate negative electrode material has wide and easily available raw material sources, and sodium, titanium, phosphorus and oxygen are all enrichment elements, and the high-density phosphorylated sodium titanate negative electrode material has low cost when being used as a metal ion battery negative electrode material.
(2) Compared with the sodium titanate nanotube, the specific surface area of the high-density phosphorylated sodium titanate anode material prepared by the embodiment of the invention is greatly reduced from 350m 2 The/g is reduced to 130m 2 The compaction density is greatly increased to 0.81g/cm under/g 3 ~2.05g/cm 3 The reduction of the specific surface area effectively reduces side reactions between electrode electrolytes, so that the coulomb efficiency and 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 remarkably improved.
(3) The high-density sodium phosphorylate titanate anode material prepared by the embodiment of the invention and the high-voltage LiNi 0.5 Mn 1.5 O 4 The full battery formed by combining the anode materials has ultrahigh rate performance and cycle stability.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 shows sodium titanate nanotubes Na prepared according to the example of the present invention 2 Ti 6 O 13 Is a TEM image of (1).
FIG. 2 is an example of the invention Na 2 Ti 6 P 0.8 O 15 TEM image of @ C.
FIG. 3 is an example of the invention Na 2 Ti 6 O 13 And Na (Na) 2 Ti 6 P 0.8 O 15 Nitrogen adsorption and desorption curves of @ C anode material.
FIG. 4 is an example of the invention Na 2 Ti 6 O 13 And Na (Na) 2 Ti 6 P 0.8 O 15 SEM image of @ C.
FIG. 5 is an example of the invention Na 2 Ti 6 O 13 And Na (Na) 2 Ti 6 P 0.8 O 15 XRD pattern of @ C.
FIG. 6 is an example of the invention Na 2 Ti 6 O 13 And Na (Na) 2 Ti 6 P 0.8 O 15 Electrochemical rate performance in half cell @ C.
FIG. 7 is an example of the invention Na 2 Ti 6 O 13 And Na (Na) 2 Ti 6 P 0.8 O 15 Long cycle stability performance of @ C in half-cell.
FIG. 8 is an example of the invention Na 2 Ti 6 O 13 And Na (Na) 2 Ti 6 P 0.8 O 15 The volumetric specific capacity of @ C at different current densities.
FIG. 9 is an example of the invention Na 2 Ti 6 P 0.8 O 15 / LiNi 0.5 Mn 1.5 O 4 Rate performance and cycling stability of the full cell.
FIG. 10 is an example of the invention Na 2 Ti 6 P 1.2 O 16 Nitrogen adsorption and desorption curves of (3).
FIG. 11 is an example of the invention Na 2 Ti 6 P 1.2 O 16 SEM image of electrode with 5 mg/cm loading 2 。
FIG. 12 is an example Na of the present invention 2 Ti 6 P 1.2 O 16 Is a XRD pattern of (C).
FIG. 13 is an example Na of the present invention 2 Ti 6 P 1.2 O 16 Electrochemical rate performance of (c).
FIG. 14 is an example Na of the present invention 2 Ti 6 P 1.2 O 16 Volumetric specific capacity performance of (c).
FIG. 15 is an example of the invention Na 2 Ti 6 O 13 And Na (Na) 2 Ti 6 P 1.2 O 16 Electrochemical rate and cycling performance in half-cells.
FIG. 16 is an example Na of the present invention 2 Ti 6 O 13 And Na (Na) 2 Ti 6 P 0.4 O 14 Electrochemical rate and cycling performance in half cell @ C.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The preparation method of the high-density phosphorylated sodium titanate material comprises the following steps:
s1: tiO is mixed with 2 Adding 1g (10-50 mL) of powder into an alkaline solution according to the mass-volume ratio, uniformly mixing, transferring into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 5-24 h at the temperature of 100-200 ℃, and washing and drying the obtained precipitate with deionized water after the reaction is finished to obtain the sodium titanate nanotube material.
Wherein the alkaline solution comprises NaOH aqueous solution with the concentration of 5 mol/L-10 mol/L.
S2: and adding the phosphate-containing compound into a solvent, and then adding the sodium titanate nanotube material to obtain a mixed solution with the concentration of 0.05 g/mL-2 g/mL.
Wherein the mole ratio of the phosphate-containing compound to the P and Ti in the sodium titanate nanotube material is (0.01-0.2): 1. The phosphate-containing compound includes: any one of monoammonium phosphate, diammonium phosphate, orthophosphoric acid and sodium phosphate. The solvent comprises: any one or two of deionized water and absolute ethyl alcohol are mixed with ethanol water solution in any volume ratio.
In the step, conductive carbon black can be added after the sodium titanate nanotube material is added, and the addition amount of the conductive carbon black is 0-25% of the mass of the sodium titanate nanotube. The conductive carbon black includes: acetylene black, acid-treated acetylene black, graphene oxide, or carbon nanotubes.
S3: and stirring the mixed solution at the temperature of 40-100 ℃ for 0.5-24 hours 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 hours at the rotating speed of 50-500 r/min under the temperature condition of 40-60 ℃ to obtain dry powder.
S4: and (3) carrying out heat treatment on the dry powder at the temperature of 300-800 ℃ for 10 min-10 h under different atmospheres to obtain the high-density sodium phosphorylate titanate material. Wherein the atmosphere comprises: air, oxygen, nitrogen or argon. The dry powder containing conductive carbon black is required to be carried out under an atmosphere of nitrogen or argon.
The heat treatment at 300 c or less may leave crystal water, which is detrimental to the stability of the product in battery operation, and the heat treatment at 800 c or more may cause performance degradation due to excessive sintering.
The compaction density range of the high-density sodium phosphorylate titanate material is 0.81g/cm 3 ~2.05g/cm 3 The increase in the compacted density may lead to an increase in the volumetric energy density of the battery, in which case the compacted density is controlled by adjusting the degree of phosphorylation. If the compacted density of the high-density sodium phosphorylate titanate material exceeds 2.05g/cm 3 The lithium ion transmission is blocked, and the rate performance is reduced.
Example 1
The preparation method of the high-density phosphorylated sodium titanate material comprises the following steps:
(1) 2g of TiO 2 Adding the nano powder into 60mL of 10mol/L NaOH aqueous solution, uniformly mixing, magnetically stirring for 2 hours at a rotating speed of 500r/min, then obtaining mixed suspension, transferring the mixed suspension into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 24 hours at a temperature of 130 ℃, fully cleaning the obtained white precipitate with deionized water after the reaction is finished, then carrying out vacuum drying at a drying temperature of 70 ℃ for 10 hours to obtain sodium titanate nanotube Na 2 Ti 6 O 13 The appearance of the nano-tube structure is shown in figure 1, and the nano-tube structure is loose.
(2) 0.4g of monoammonium phosphate is added into 20mL of absolute ethyl alcohol, 2.4g of sodium titanate nanotube (molar ratio of P to Ti is 0.4:3) and 0.3g of acid are added to treat acetylene black, and a mixed solution with the concentration of 0.155g/mL is obtained.
The treatment process of the acetylene black by acid treatment comprises the following steps: at 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 to 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 ℃ for 10 hours) to obtain the acid-treated acetylene black.
(3) Stirring the mixed solution at a temperature of 60 ℃ for 2 hours at a rotating speed of 200r/min to obtain dry powder.
(4) Under nitrogen atmosphere, carrying out heat treatment on the dry powder for 1h at the temperature of 500 ℃ to obtain a high-density sodium phosphorylate titanate material Na 2 Ti 6 P 0.8 O 15 The morphology of the @ C is shown in figure 2, the morphology of the hollow nano tube almost disappears, and the compactness is obviously improved.
As shown in FIG. 3, the sodium titanate nanotubes Na obtained in this example 2 Ti 6 O 13 Is 350m 2 High density phosphorylated sodium titanate material Na/g 2 Ti 6 P 0.8 O 15 Specific surface area of @ C is 183m 2 And/g, the specific surface area of the product after densification is obviously reduced.
As shown in FIG. 4, in5.0mg/cm 2 In the case of the loading amount of (2), na of the present embodiment 2 Ti 6 O 13 The thickness of the electrode prepared as the negative electrode material was 61.6 μm and the compacted density was 0.81g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Example Na 2 Ti 6 P 0.8 O 15 The thickness of the electrode prepared with @ C as the negative electrode material was 37.2 microns and the compacted density was 1.34g/cm 3 The thickness of the electrode prepared by taking the product after densification as the negative electrode material is obviously reduced, and the compaction density is obviously improved.
As shown in FIG. 5, na obtained in this example 2 Ti 6 P 0.8 O 15 The crystallization degree of @ C is obviously weaker than that of sodium titanate nanotube Na 2 Ti 6 O 13 The intensity of diffraction peak is obviously reduced, and the amorphization degree is obviously improved.
As shown in the electrochemical analysis results of FIG. 6, sodium titanate nanotubes Na obtained in this example 2 Ti 6 O 13 The initial coulomb efficiency of the electrode prepared as the negative electrode material was 69%, and Na obtained in this example 2 Ti 6 P 0.8 O 15 The initial coulomb efficiency of the electrode prepared by taking @ C as the anode material is 92%, na 2 Ti 6 P 0.8 O 15 The specific surface area of the @ C is obviously reduced, and the first-circle coulomb efficiency is obviously improved. In addition, na 2 Ti 6 P 0.8 O 15 The electrode prepared by taking @ C as the negative electrode material still maintains extremely high rate capability, still has specific capacity of 106mAh/g under 10A/g of ultra-large current, and is higher than sodium titanate nanotube Na 2 Ti 6 O 13 A specific capacity of 81 mAh/g.
As shown in the results of the rate performance test of FIG. 7, na obtained in this example 2 Ti 6 P 0.8 O 15 The capacity retention rate of the electrode prepared by taking @ C as the anode material reaches 95% after 2000 cycles at 2A/g, which is far higher than that of sodium titanate nanotube Na 2 Ti 6 O 13 An electrode prepared as a negative electrode material.
As shown in the volume specific capacity test results of FIG. 8, the sodium titanate nanotubes Na obtained in this example 2 Ti 6 O 13 The prepared electrode has a volume specific capacity of 166 ampere hours per liter, and the Na obtained in the embodiment is obtained due to the improvement of the compaction density and the multiplying power performance 2 Ti 6 P 0.8 O 15 The volume specific capacity of the electrodes prepared at @ C was increased by approximately three times per liter from 166 ampere hours to 291 ampere hours.
As shown in FIG. 9, na obtained in this example 2 Ti 6 P 0.8 O 15 @C is used as a negative electrode, and high voltage LiNi 0.5 Mn 1.5 O 4 The material is used as the positive electrode, and the combined full battery has ultrahigh rate performance and cycle stability.
Example 2
The preparation method of the high-density sodium phosphorylate titanate negative electrode material comprises the following steps:
(1) 2g of TiO 2 Adding the nano powder into 100mL of NaOH aqueous solution with the concentration of 8mol/L, uniformly mixing, magnetically stirring for 5 hours at the rotating speed of 400r/min, then obtaining 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 sodium titanate nanotube Na 2 Ti 6 O 13 。
(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), yielding a mixture with a concentration of 0.25 g/mL.
(3) Stirring the mixed solution at a temperature of 60 ℃ for 3 hours at a rotating speed of 350r/min to obtain dry powder.
(4) Under the oxygen atmosphere, carrying out heat treatment on the dry powder for 2 hours at the temperature of 450 ℃ to obtain the high-density sodium phosphorylate titanate material Na 2 Ti 6 P 1.2 O 16 。
Compared with untreated sodium titanate nanotubes, the high-density phosphorylated sodium titanate material Na obtained in the embodiment 2 Ti 6 P 1.2 O 16 The specific surface area of (2) is significantly reduced, as shown in FIG. 10, by only 130m 2 And/g. Na obtained in this example 2 Ti 6 P 1.2 O 16 The electrode made as the negative electrode material was similarly 5.0. 5.0 g/cm 2 In the case of the load, as shown in FIG. 11, the thickness thereof was only 37.2. Mu.m, and the compaction density was increased to 2.05g/cm 3 . As shown in FIG. 12, na obtained in this example 2 Ti 6 P 1.2 O 16 As can be seen in the XRD pattern of (c), phosphorylation further reduced the intensity of the characteristic diffraction peak, but no new crystalline phase was generated. As shown in FIG. 13, na obtained in this example 2 Ti 6 P 1.2 O 16 Has good multiplying power performance. More importantly, due to the greatly improved compaction density, as shown in FIG. 14, the Na obtained in this example 2 Ti 6 P 1.2 O 16 The volume specific capacity of (2) is increased from 166 ampere hours to 355 ampere hours by approximately three times per liter.
Example 3
The preparation method of the high-density phosphorylated sodium titanate material comprises the following steps:
s1: 2g of TiO 2 Adding the powder into 20mL of NaOH aqueous solution with the concentration of 5mol/L, uniformly mixing, transferring into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 5h at the temperature of 200 ℃, and washing and drying the obtained precipitate by deionized water after the reaction is finished to obtain the sodium titanate nanotube material.
S2: 0.22 g orthophosphoric acid and 1g sodium titanate nanotube material (P: ti=0.2:1) were added to 25 mL deionized water to give a mixture having a concentration of 0.05 g/mL.
S3: stirring the mixed solution at a temperature of 90 ℃ for 24 hours at a rotating speed of 500r/min to obtain dry powder.
S4: under the air atmosphere, carrying out heat treatment on the dry powder for 10min at the temperature of 800 ℃ to obtain the high-density sodium phosphorylate titanate material Na 2 Ti 6 P 1.2 O 15 。
The high density sodium phosphorylated titanate electrode prepared in this example had a compacted density of 2.05g/cm 3 . As shown in fig. 15, the electrochemical rate performance is: at a current density of 0.2A/g,the specific capacity is 160mAh/g; the specific capacity was 93mAh/g at a current density of 10A/g. The cycle stability is as follows: the capacity retention after 800 cycles at 2A/g was 96%.
Example 4
The preparation method of the high-density phosphorylated sodium titanate material comprises the following steps:
(1) 2g of TiO 2 Adding 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 ℃, and washing and drying the obtained precipitate with deionized water after the reaction is finished 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 a 50% aqueous ethanol solution, and 0.1g of acetylene black was further added to obtain a mixed solution having a concentration of 0.1 g/mL.
(3) Stirring the mixed solution at a temperature of 40 ℃ and a rotating speed of 50r/min for 5 hours to obtain dry powder.
(4) Under the argon atmosphere, carrying out heat treatment on the dry powder for 10 hours at the temperature of 300 ℃ to obtain the high-density sodium phosphorylate titanate material Na 2 Ti 6 P 0.4 O 14 @C。
The high density phosphorylated sodium titanate material prepared in this example had a compacted density of 1.10g/cm -3 . As shown in fig. 16, the electrochemical rate performance is: the specific capacity was 163mAh/g at a current density of 0.2A/g and 30mAh/g at a current density of 10A/g. The cycle stability is as follows: the capacity retention after 1000 cycles at 2A/g was 94%.
Example 5
The preparation method of the high-density phosphorylated sodium titanate material comprises the following steps:
except for (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 remainder was the same as in example 2.
The high density sodium phosphorylated titanate material prepared in this example had a compacted density of 0.92g/cm 3 The electrochemical rate performance is 0.2A/g current density, and the specific capacity is 156mAh/g; the specific capacity was 28mAh/g at a current density of 10A/g. The cycle stability was 2A/g and the capacity retention after 800 cycles was 91%.
Comparative example
The preparation method of the high-density phosphorylated sodium titanate material comprises the following steps:
except that in the step (2), sodium dihydrogen phosphate is adopted as the phosphorylation reagent, and no acid is added to treat acetylene black;
the remainder was the same as in example 1.
The sodium dihydrogen phosphate is adopted as the phosphating reagent, and the compaction density of the high-density sodium phosphorylate titanate material prepared by the comparative example is 1.85g/cm 3 The electrochemical rate performance is 0.2A/g current density, and the specific capacity is 144mAh/g; the specific capacity was 36mAh/g at a current density of 10A/g. The cycle stability was 2A/g and the capacity retention after 200 cycles was 76%. 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 proportion of sodium in the product.
In this specification, each embodiment is described in a related manner, and identical and similar parts of each embodiment are all referred to each other, and each embodiment mainly describes differences from other embodiments.
The foregoing description is only of the preferred embodiments of the present invention and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention are included in the protection scope of the present invention.

Claims (8)

1. The preparation method of the high-density phosphorylated sodium titanate material is characterized by comprising the following steps of:
s1: tiO is mixed with 2 Adding 1g (10-50 mL) of powder into an alkaline solution according to the mass-volume ratio, uniformly mixing, transferring into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 5-24 h at the temperature of 100-200 ℃, and washing and drying the obtained product to obtain a sodium titanate nanotube material;
s2: adding a phosphate-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): 1 to obtain a mixed solution with the concentration of 0.05 g/mL-2 g/mL; the solvent comprises: either or both of deionized water and absolute ethyl alcohol;
s3: stirring the mixed solution at the temperature of 40-100 ℃ for 0.5-24 hours at the rotating speed of 50-500 r/min to obtain dry powder;
s4: carrying out heat treatment on the dry powder at the temperature of 300-800 ℃ for 10 min-10 h under different atmospheres to obtain a high-density sodium phosphorylate titanate material;
in S2, the phosphate-containing compound includes: any one of ammonium phosphate, monoammonium phosphate, diammonium phosphate, and orthophosphoric acid;
s2, adding conductive carbon black after adding the sodium titanate nanotube material.
2. The method for preparing a high-density phosphorylated sodium titanate material according to claim 1, wherein in S1, the alkaline solution comprises an aqueous NaOH solution with a concentration of 5mol/L to 10mol/L.
3. The method of claim 1, wherein the conductive carbon black is no more than 25% of the mass of the sodium titanate nanotube material.
4. The method of preparing a high density phosphorylated sodium titanate material of claim 1, wherein the conductive carbon black comprises: acetylene black, acid-treated acetylene black, graphene oxide, or carbon nanotubes.
5. The method of preparing a high density phosphorylated sodium titanate material of claim 1, wherein in S4, the atmosphere comprises: air, oxygen, nitrogen or argon.
6. The homography of claim 1The preparation method of the density phosphorylated sodium titanate material is characterized in that in S4, the compaction density range of the high-density phosphorylated sodium titanate material is 0.81g/cm 3 ~2.05g/cm 3 。
7. The high-density sodium phosphorylate titanate material prepared by the preparation method of the high-density sodium phosphorylate titanate material according to any one of claims 1-6.
8. Use of the high density phosphorylated sodium titanate material of claim 7 in a metal ion battery.
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