CN110611087A

CN110611087A - Composite material with antimony or bismuth uniformly distributed in titanium-based compound and preparation method and application thereof

Info

Publication number: CN110611087A
Application number: CN201910651445.9A
Authority: CN
Inventors: 杨剑; 潘军; 钱逸泰
Original assignee: Shandong University
Current assignee: Shandong University
Priority date: 2019-07-18
Filing date: 2019-07-18
Publication date: 2019-12-24
Anticipated expiration: 2039-07-18
Also published as: CN110611087B

Abstract

The invention relates to a composite material with antimony or bismuth uniformly distributed in a titanium-based compound, and a preparation method and application thereof. The synthesis method has universality and is not only suitable for SbPO₄The method is suitable for Sb oxides, Sb sulfides and Bi phosphates, and the obtained composite material is prepared by uniformly distributing antimony or bismuth in a titanium-based compound and has a pudding-shaped structure. The material is used as a negative electrode material of a sodium ion battery and has good cycle and rate performance. At 0.5Ag^‑1The capacity retention rate of 93% is also obtained after 1000 cycles. Provides theoretical support for the large-scale production of the metal and titanium-based composite material. The structural material can be used as an electrode material and can also be applied to other fields.

Description

Composite material with antimony or bismuth uniformly distributed in titanium-based compound and preparation method and application thereof

The technical field is as follows:

the invention provides a composite material with antimony or bismuth uniformly distributed in a titanium-based compound, and a preparation method and application thereof, and belongs to the technical field of synthesis methods and sodium-ion batteries.

Background art:

sodium ion batteries are one of the most promising new batteries due to the abundant sodium resources, similar working principles to lithium ion batteries, and inexpensive aluminum foil current collectors. Although sodium ion batteries can draw on the empirical methods available for lithium ion batteries, the difference in atomic structures between sodium and lithium does not mean that all electrode materials function well in sodium ion batteries. The large size and heavy mass of sodium ions greatly increases the diffusion energy barrier and volume change during discharge/charge, causing rapid decay in cycling performance. Therefore, the search for suitable electrode materials remains a key to sodium ion battery applications.

To date, a wide variety of materials have been explored for use as negative electrode materials in sodium ion batteries, e.g., hard carbon, TiO₂，MoSe₂， Cu₂S, Sn, Sb, etc. Hard carbon materials and titanium dioxide materials as intercalation materials have the advantages of ease of preparation, low cost, stable cycling, long life, etc., however, they exhibit limited reversible capacity, particularly at high current densities. For Sn and Sb, due to their high capacity (Sn, 847mAh g)^-1(ii) a And Sb, 660mAh g^-1) The problem of limited reversible capacity is solved by the alloying reaction; moreover, they are relatively hard carbon and TiO₂Exhibit excellent electron conductivity. Have lower operating potentials relative to transition metal sulfides and selenides, and thus have higher energy and power densities when assembling a full cell. The disadvantage is that large volume changes are induced during cycling, destroying the structural integrity, resulting in reduced cycling stability.

In order to solve the respective defects of the materials, researchers complement the advantages and the disadvantages of the cathode material of an alloy mechanism and the coupling of an embedded reaction type cathode material; however, most of the research efforts so far have focused on how to combine Sn or Sb with carbon materials. Coupling to Ti-based oxides has rarely been studied due to poor electrical conductivity. In fact, Ti-based oxides have some advantages over carbon, such as: high binding affinity to the electrode, excellent thermal stability to carbon and moderate discharge potential. Therefore, for the Ti-based phaseResearch on composite materials of oxides is necessary. The applicant synthesizes the well-defined Sb/TiO through a simple experimental process₂Nanotubes, which are repeatedly discharged/charged 1000 cycles in lithium ion batteries and sodium ion batteries, have high capacity retention. However, the volume energy density will be significantly reduced due to the excessive internal voids of the nanotubes. The applicant improves the technology to prepare the Sb @ Ti-P-O nanowire with the egg shell structure, wherein the porous Sb nanorod is used as an egg yolk, and the amorphous Ti-P-O nanotube is used as an egg shell. Although the space utilization and reversible capacity are improved, the lifetime is only 0.5Ag^-1About 200 cycles.

Therefore, balancing cycle life and space utilization is a significant challenge; how to enable the Ti-based oxide and Sb/Bi composite material to have high capacity retention rate, good cycle and rate performance and high space utilization rate, and the composite material becomes an excellent cathode material of a sodium-ion battery, which becomes a great challenge at present.

The invention content is as follows:

in order to solve the existing technical problems, the invention provides a composite material with antimony or bismuth uniformly distributed in a titanium-based compound, a preparation method and application thereof; the composite material has a pudding-shaped structure, and the structure is used as a negative electrode material of a sodium ion battery, so that high space utilization rate and long cycle life are realized. At 0.5Ag^-1After 1000 cycles under the current density, the capacity retention rate of the catalyst is 93 percent.

In order to solve the technical problems, the invention is realized by the following technical scheme:

the composite material with antimony or bismuth uniformly distributed in the titanium-based compound is c-Sb @ a-TiPO_x、 c-Sb@a-TiO₂Or c-Bi @ a-TiPO_xComposite material, c-Sb @ a-TiPO_xCrystalline Sb is uniformly distributed in amorphous titanium phosphate, c-Sb @ a-TiO₂Crystalline Sb is uniformly distributed in amorphous titanium dioxide, c-Bi @ a-TiPO_xThe crystalline Bi is uniformly distributed in the amorphous titanium phosphate and is in a pudding-shaped structure.

Preferred according to the invention are c-Sb @ a-TiPO_x、c-Sb@a-TiO₂Or c-Bi @ a-TiPO_xThe lengths of the two layers are all 0.5-1 um.

The invention also provides a preparation method of the composite material with antimony or bismuth uniformly distributed in the titanium-based compound.

A preparation method of a composite material with antimony or bismuth uniformly distributed in a titanium-based compound comprises the following steps:

dispersing an antimony source or a bismuth source in a solvent, adding tetrabutyl titanate (TBT) and ammonia water for hydrolysis, and carrying out heat treatment for 1-6h at 300-600 ℃ under the protection of inert gas after hydrolysis reaction to obtain the composite material with antimony or bismuth uniformly distributed in a titanium-based compound.

Preferably, according to the invention, the solvent is ethanol.

According to the invention, the mass-to-volume ratio of the antimony or bismuth source to the solvent is preferably (0.1-0.5): (30-50), unit: g/mL.

According to the invention, the ratio of the addition amount of The Butyl Titanate (TBT) to the volume of the solvent is: 0.6-1:40, wherein the volume ratio of the addition amount of the ammonia water to the solvent is as follows: 0.1-0.5:40.

According to the invention, the hydrolysis temperature is preferably 40-70 ℃ and the hydrolysis time is preferably 3-5 h.

Preferably, according to the invention, the inert gas is argon.

According to the invention, the heat treatment temperature is 400-550 ℃, and the heat treatment time is 4-6 h.

According to the invention, the preferred antimony source is SbPO₄、Sb₂O₃Or Sb₂S₃When the antimony source is Sb₂O₃Or Sb₂When S is used, the obtained composite material is c-Sb @ a-TiO₂Composite material, when the antimony source is SbPO₄Then the obtained composite material is c-Sb @ a-TiPO_xA composite material.

Preferably, the bismuth source is BiPO₄The obtained composite material is c-Bi @ a-TiPO_xA composite material.

Sb₂O₃、Sb₂S₃、BiPO₄Are all commercial products.

According to a preferred embodiment of the invention, the SbPO₄Is prepared by the following method: reacting SbCl₃Dispersing in ethylene glycol, adding a phosphorus source, heating for dissolving, and carrying out hydrothermal reaction at 120-200 ℃ for 4-6 h; centrifuging a reaction product after the hydrothermal reaction, and then sequentially washing with ethanol, washing with water and drying in vacuum to obtain SbPO₄。

Further preferably, the phosphorus source is NH₄H₂PO₄。

Further preferred, SbCl₃The molar ratio of the added amount of the phosphorus source to the phosphorus source is 1 (1-3).

Further preferably, the heating dissolution temperature is 60 to 70 ℃.

Further preferred, SbCl₃Mass to volume ratio to ethylene glycol: (0.1-0.3): (30-50), unit: g/mL.

Further preferably, the vacuum drying temperature is 50-70 ℃, and the drying time is 10-14 h.

The application of the composite material with antimony or bismuth uniformly distributed in the titanium-based compound is applied to a sodium ion battery and used as a negative active material of the sodium ion battery.

According to the invention, the preferable specific application method is as follows:

(1) mixing a composite material with antimony or bismuth uniformly distributed in a titanium-based compound, a conductive agent and a binder according to a mass ratio of 7:2:1, adding water, grinding into slurry, coating the slurry on a copper foil, drying, rolling and cutting to obtain a negative plate, wherein the mass of the composite material with antimony or bismuth uniformly distributed in the titanium-based compound per unit area is 1.0-1.5 mg cm^-2；

(2) And assembling the negative plate, the positive plate, the diaphragm, the electrolyte and the shell to obtain the sodium-ion battery.

According to the invention, the electrolyte is preferably NaClO₄Solutions in propylene carbonate, NaClO₄The concentration of (A) is 1 mol/L; the membrane material was Whatman GF/F glass microfiber.

According to the invention, the sodium sheet in the sodium-ion battery is preferably used as a counter electrode.

The positive plate, the adhesive and the conductive agent adopt the conventional positive plate, adhesive and conductive agent in the field.

The principle of the invention is as follows:

the invention uses SbPO₄、Sb₂O₃、Sb₂S₃Or BiPO₄The method comprises the following steps of taking ethanol as a solvent as a raw material, hydrolyzing butyl titanate in ammonia water to obtain a precursor, calcining at high temperature to obtain a composite material with antimony or bismuth uniformly distributed in a titanium-based compound, applying the material to a negative electrode material of a sodium-ion battery to obtain excellent electrochemical performance, wherein the synthesis method has universality, and three different composite materials can be prepared under the same conditions of the method, namely: c-Sb @ a-TiPO_x、c-Sb@a-TiO₂Or c-Bi @ a-TiPO_xA composite material.

The composite material with antimony or bismuth uniformly distributed in the titanium-based compound has the following remarkable characteristics:

1. the synthesis method of the invention has universality, and three different composite materials can be prepared under the same conditions of the method, namely: c-Sb @ a-TiPO_x、c-Sb@a-TiO₂Or c-Bi @ a-TiPO_xA composite material.

2. The synthetic method can be confirmed by an in-situ/ex-situ technology, a first principle and a comparative experiment; with c-Sb @ a-TiPO_xComposite materials, SbPO₄Reacting in tetrabutyl titanate and ammonia water to obtain a-SbTiPO_xThe precursor is doped with titanium, the bond length of an Sb-O bond can be stretched, the substance can also absorb a certain amount of ammonia molecules, and the generated ammonia molecules play a certain reduction role in the later calcining process to obtain a final product of a pudding-shaped c-Sb @ a-TiPO_xNamely, crystalline Sb is uniformly distributed in amorphous titanium phosphate; likewise c-Sb @ a-TiO₂Or c-Bi @ a-TiPO_xThe composite material can also be confirmed by in-situ/ex-situ technology, first-order principle and comparative experiment.

3. The composite material obtained by the invention is applied to sodium ion batteries, and has good cycle and rate performance. At 0.5Ag^-1The kinetics of the electrochemical reaction were analyzed by constant current intermittent titration (GITT) and electrochemical alternating current impedance (EIS) at 1000 cycles with 93% capacity retention.

Description of the drawings:

FIG. 1 shows a-SbTiPO prepared in example 1 of the present invention_xScanning electron micrographs (a) and high-resolution transmission electron micrographs (b) of the precursor material and X-ray photoelectron spectroscopy (c, d) diagrams.

FIG. 2 shows c-Sb @ a-TiPO prepared in example 1 of the present invention_xX-ray photoelectron spectrum (a), scanning electron microscope picture (b), high-resolution transmission electron microscope picture (c) and element distribution diagram (d) of the composite material product.

FIG. 3 shows c-Sb @ a-TiPO prepared in example 1 of the present invention_xAnalysis chart of the formation process of the product; a is XRD diffraction patterns under different temperatures, b and c are in-situ thermogravimetry-mass spectrometry, d is the XRD diffraction patterns under different reaction conditions, and e is the structural change before and after the first-order principle calculation reaction.

FIG. 4 shows c-Sb @ a-TiPO prepared in example 1 of the present invention_xElectrochemical properties and kinetic analysis maps of the material; a is a rate performance graph, b is a GITT test graph, c is a reaction resistance graph, and d is a long-cycle test graph.

FIG. 5 shows c-Sb @ a-TiO prepared in example 2 of the present invention₂XRD diffraction pattern and scanning electron microscope photo of the material, a is XRD diffraction pattern, and b is scanning electron microscope photo.

FIG. 6 shows c-Sb @ a-TiO prepared in example 3 of the present invention₂The XRD diffraction pattern and the scanning electron microscope picture of the material are shown in the picture a, the XRD diffraction pattern picture and the scanning electron microscope picture.

FIG. 7 shows c-Bi @ a-TiPO prepared in example 4 of the present invention_xXRD diffraction pattern and scanning electron microscope photo of the material, a is XRD diffraction pattern, and b is scanning electron microscope photo.

The specific implementation mode is as follows:

the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings and the embodiments, 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 raw materials in the examples are all commercial products.

Example 1

SbPO₄The preparation method comprises the following steps:

(1) 1mmol of SbCl₃Dispersing in 40ml of ethylene glycol, adding 2mmol of ammonium dihydrogen phosphate, and heating and dissolving at 70 ℃ to obtain a mixed solution;

(2) transferring the mixed solution into a stainless steel reaction kettle, and carrying out hydrothermal reaction for 4h at 120 ℃;

(3) centrifuging the product after reaction, washing with ethanol and water for several times, and drying in a vacuum drying oven at 60 deg.C for 12h to obtain SbPO₄。

c-Sb@a-TiPO_xThe preparation of the composite material comprises the following steps:

1) 0.2g of SbPO₄Dispersing in 40ml ethanol, adding 0.4ml LNH₃H₂O, 0.8mL TBT, and reacting for 5h at 55 ℃ to obtain a-SbTiPO_xA precursor;

2) centrifuging the product, washing with ethanol and water, drying in a vacuum drying oven at 60 deg.C for 12h, and heat treating the product at 450 deg.C for 6h under argon atmosphere; to obtain c-Sb @ a-TiPO_xA composite material.

Performance testing

For a-SbTiPO_xPrecursor and c-Sb @ a-TiPO_xThe final product of the composite material is subjected to morphology and composition tests, as shown in fig. 1, the precursor can be seen to be irregular particles with the size of 0.5-1um in fig. 1(a), and the high-resolution transmission electron microscope does not have lattice stripes in fig. 1(b), which indicates that the material is an amorphous structure. The valence state of Sb is trivalent as shown in X-ray photoelectron spectroscopy (XPS) in FIG. 1(c), and a signal of N is detected in FIG. 1(d), which indicates that a certain amount of ammonia molecules are adsorbed during hydrolysis. c-Sb @ a-TiPO_xThe morphology and elemental analysis of the final composite material is shown in FIG. 2, and it can be seen from FIG. 2(a) that Sb is already presentIs reduced to simple substance. As can be seen from fig. 2(b), the morphology of the sample gradually becomes uniform, and as can be seen from fig. 2(c), the lattice fringes of the simple Sb indicate that Sb changes from trivalent to zero valence from another angle. As can be seen from FIG. 2(d), the Sb, Ti, O and P elements are uniformly distributed, and the product is a pudding structure with uniformly distributed elements.

Testing of mechanism of formation of substance

The invention proves the reaction process of substance formation through a series of in-situ/ex-situ test methods, first principle calculation and multiple groups of comparison experiments, namely c-Sb @ a-TiPO_xAnalysis of the formation of the product is shown in FIG. 3, and it can be seen from the XRD diffraction pattern in FIG. 3(a) that the species are different at different calcination temperatures, first we take the precursor a-SbTiPO_xThe calcination is carried out, the diffraction peak of Sb is gradually shown at 350 ℃, when the temperature is increased to 650 ℃, the diffraction peak of Sb gradually disappears, and the diffraction peak of the titanium compound is replaced, only because the melting point of Sb is only 630 ℃, if the temperature is very high, Sb will run out, the crystallinity of the titanium-based compound is improved along with the increase of the temperature, and only the peak of the titanium-based compound is left. The thermogravimetric analysis in FIG. 3(b) has two weight loss processes, the first is the loss of adsorbed species in the compound during heating, the second is the vaporization of Sb, FIG. 3(c) has a gas generation with a relative molecular mass of 28 during heating, presumably N from the starting material₂Or CO, in order to find out exactly what gas is, a series of comparative experiments were carried out, and the XRD diffraction pattern of the comparative experiment in FIG. 3(d) was used to determine that the gas produced was N₂The whole process can be simulated by theoretical calculation, and as can be seen from the crystal structure diagram in FIG. 3(e), SbPO₄In the hydrolysis process, Ti atoms can replace Sb atoms, so that Sb-O bonds are lengthened, and in the later heating process, the Sb-O bonds are broken through the reduction of ammonia gas to generate simple substances Sb.

Electrochemical performance test

To verify c-Sb @ a-TiPO_xElectrical properties of the final composite material, as c-Sb @ a-TiPO_xThe material is a negative electrode material, and the sodium sheet is a referenceAn electrode and a counter electrode are assembled to form a sodium ion half cell, the electrochemical performance is represented, and a negative electrode is prepared: c-Sb @ a-TiPO_xUniformly dispersing the materials, acetylene black and sodium alginate in a proper amount of water, grinding for 30min by hand to prepare paste slurry, then uniformly coating the slurry on a copper foil, and then drying in vacuum at 60 ℃; rolling the dried copper foil to obtain a negative electrode, using sodium sheets as reference electrode and counter electrode, using Whatman GF/F glass microfiber as diaphragm, and using 1.0M NaClO₄Dissolution in Propylene Carbonate (PC) as the electrolyte was carried out in an argon-filled glove box (Mikrouna, Super 1220/750/900). The charging and discharging test of the battery is carried out on a blue electricity (Land CT-2001A) test system, and the working interval of the battery is 0.01-2.0V. FIG. 4(a) is c-Sb @ a-TiPO prepared in example 1_xThe cycling curves of the samples at different current densities, FIG. 4(b) and FIG. 4(c) are for c-Sb @ a-TiPO prepared in example 1_xConstant current batch titration and internal resistance analysis of the samples, FIG. 4(d) at 0.5Ag^-1The current density of (a), cycle 1000 cycles, also has a capacity retention rate of 93%; the test shows that c-Sb @ a-TiPO_xThe composite material as a negative active material applied to the sodium ion battery has good cycle and rate performance.

Example 2

1) 0.2gSb₂O₃Dispersing in 40ml ethanol, adding 0.4ml LNH₃·H₂O, 0.8mL of TBT, and reacting for 5h at 55 ℃;

2) centrifuging the product, washing with ethanol and water, drying in a vacuum drying oven at 60 deg.C for 12h, and reacting at 450 deg.C for 6h under argon atmosphere; to obtain c-Sb @ a-TiO₂A composite material.

Example 3

1) 0.2g of Sb₂S₃Dispersing in 40ml ethanol, adding 0.4ml LNH₃·H₂O, 0.8mL of TBT, and reacting for 5h at 55 ℃;

2) centrifuging the product, and washing with ethanol and waterDrying the mixture in a vacuum drying oven at 60 ℃ for 12h, and reacting the product at 450 ℃ for 6h under the argon atmosphere; to obtain c-Sb @ a-TiO₂A composite material.

Example 4

c-Bi@a-TiPO_xThe preparation method comprises the following steps:

1) 0.2g of BiPO was added₄Dispersing in 40ml ethanol, adding 0.4ml LNH₃·H₂O, 0.8mL of TBT, and reacting for 5h at 55 ℃;

The XRD diffraction patterns and scanning electron micrographs of the products of examples 2, 3 and 4 are shown in FIGS. 5, 6 and 7, from which FIGS. 5, 6 and 7 it can be seen that Sb is Sb₂O₃，Sb₂S₃And BiPO₄c-Sb @ a-TiO with a pudding structure can be obtained by the same reaction conditions as the raw materials₂And c-Bi @ a-TiPO_x(ii) a The universality of the method is proved.

Comparative example 1

SbPO₄The preparation method of the material comprises the following steps:

(1) mixing 1mmol of antimony potassium tartrate and 2mmol of ammonium dihydrogen phosphate, and dissolving at 70 deg.C;

(2) transferring the mixed solution to a stainless steel reaction kettle, placing the stainless steel reaction kettle in an oven, and reacting for 4 hours at 120 ℃;

(3) centrifuging the product, washing with ethanol and water for several times, and drying in a vacuum drying oven at 60 deg.C for 12 hr to obtain SbPO₄And (4) microspheres. SbPO obtained by the method₄The micron balls have the advantages of large and small sizes, uneven dispersion and slight agglomeration.

Comparative example 2

c-Sb@a-TiPO_xThe preparation method comprises the following specific steps:

1) 0.2g of SbPO₄Dispersing in 40mL ethanol, adding 0.4mL NaOH solution (0.53mmol/L) and 0.8mL TBT, reacting at 55 deg.C for 5h to obtain a-SbTiPO_xThe precursor, NaOH solution, although alkaline, can hydrolyze TBT.

2) Centrifuging the product, washing with ethanol and water for several times, drying in a vacuum drying oven at 60 deg.C for 12h, and reacting at 450 deg.C for 6h under argon atmosphere to obtain c-Sb @ a-TiPO_xA material. No reducing agent is used in the post-calcining process, so that no product can be obtained.

Comparative example 3

c-Sb@a-TiPO_xThe preparation method comprises the following specific steps:

1) 0.2g of SbPO₄Dispersed in 40mL of ethanol, 0.4mL of NH was added₄Cl solution and 0.8mL TBT react for 5h at 55 ℃ to obtain a-SbTiPO_xA precursor. NH (NH)₄The Cl solution contained ammonium ions, but the aqueous solution was not alkaline, and Ti could not enter SbPO, which is disadvantageous to hydrolysis of butyl titanate₄In (c), so that SbPO cannot be destroyed₄The crystal structure of (1).

2) Centrifuging the product, washing with ethanol and water for several times, drying in a vacuum drying oven at 60 deg.C for 12h, and reacting at 450 deg.C for 6h under argon atmosphere. c-Sb @ a-TiPO can not be obtained_xA material. a-SbTiPO can not be obtained in the early stage_xThe precursor does not obtain the product in the process of later calcining.

Comparative example 4

c-Sb@a-TiPO_xThe preparation method comprises the following specific steps:

1) 0.2g of SbPO₄Dispersed in 40mL of ethanol, 0.4mL of NH was added₄HCO₃The solution reacts with 0.8mL of TBT at 55 ℃ for 5 hours to obtain a-SbTiPO_xA precursor. NH (NH)₄HCO₃The solution contains ammonium ions, the aqueous solution shows alkalinity, the hydrolysis of butyl titanate is facilitated, and Ti can enter SbPO₄In this way, SbPO can be destroyed₄The crystal structure of (1).

2) Centrifuging the product, washing with ethanol and water for several times, drying in a vacuum drying oven at 60 deg.C for 12h, and reacting at 450 deg.C for 6h under argon atmosphere. To obtain c-Sb @ a-TiPO_xA material. Obtaining a-SbTiPO at the early stage_xThe precursor is added with the reduction of ammonium ions in the later calcining process, so that the product is obtained.

Claims

1. The composite material with antimony or bismuth uniformly distributed in the titanium-based compound is c-Sb @ a-TiPO_x、c-Sb@a-TiO₂Or c-Bi @ a-TiPO_xComposite material, c-Sb @ a-TiPO_xCrystalline Sb is uniformly distributed in amorphous titanium phosphate, c-Sb @ a-TiO₂Crystalline Sb is uniformly distributed in amorphous titanium dioxide, c-Bi @ a-TiPO_xThe crystalline Bi is uniformly distributed in the amorphous titanium phosphate and is in a pudding-shaped structure.

2. The composite material of claim 1, wherein the antimony or bismuth is homogeneously distributed in the titanium-based compound, and wherein c-Sb @ a-TiPO_x、c-Sb@a-TiO₂Or c-Bi @ a-TiPO_xThe lengths of the two layers are all 0.5-1 um.

3. A preparation method of a composite material with antimony or bismuth uniformly distributed in a titanium-based compound comprises the following steps:

4. The preparation method according to claim 3, wherein the solvent is ethanol, and the mass-to-volume ratio of the antimony source or the bismuth source to the solvent is (0.1-0.5): (30-50), unit: g/mL; the volume ratio of the added quantity of The Butyl Titanate (TBT) to the solvent is as follows: 0.6-1:40, wherein the volume ratio of the addition amount of the ammonia water to the solvent is as follows: 0.1-0.5:40.

5. The process according to claim 3, wherein the hydrolysis temperature is 40-70 ℃ and the hydrolysis time is 3-5 hours; the inert gas is argon, the heat treatment temperature is 400-550 ℃, and the heat treatment time is 4-6 h.

6. A method according to claim 3, wherein said antimony sourceIs SbPO₄、Sb₂O₃Or Sb₂S₃When the antimony source is Sb₂O₃Or Sb₂When S is used, the obtained composite material is c-Sb @ a-TiO₂Composite material, when the antimony source is SbPO₄Then the obtained composite material is c-Sb @ a-TiPO_xThe bismuth source is BiPO₄The obtained composite material is c-Bi @ a-TiPO_xA composite material.

7. The method of claim 6, wherein the SbPO is₄Is prepared by the following method: reacting SbCl₃Dispersing in ethylene glycol, adding a phosphorus source, heating for dissolving, and carrying out hydrothermal reaction at 120-200 ℃ for 4-6 h; centrifuging a reaction product after the hydrothermal reaction, and then sequentially washing with ethanol, washing with water and drying in vacuum to obtain SbPO₄。

8. The method of claim 7, wherein the phosphorus source is NH₄H₂PO₄，SbCl₃The molar ratio of the added amount of the SbCl to the phosphorus source is 1 (1-3), the heating and dissolving temperature is 60-70 ℃, and the SbCl is₃Mass to volume ratio to ethylene glycol: (0.1-0.3): (30-50), unit: g/mL, the vacuum drying temperature is 50-70 ℃, and the drying time is 10-14 h.

9. The application of the composite material with antimony or bismuth uniformly distributed in the titanium-based compound is applied to a sodium ion battery and used as a negative active material of the sodium ion battery.

10. The use of a composite material of claim 9 in which antimony or bismuth is homogeneously distributed in a titanium-based compound, in particular by the following method:

(1) mixing a composite material with antimony or bismuth uniformly distributed in a titanium-based compound, a conductive agent and a binder according to a mass ratio of 7:2:1, adding water, grinding into slurry, coating the slurry on a copper foil, drying, rolling and cutting to obtain a negative plate, wherein the mass of the composite material with antimony or bismuth uniformly distributed in the titanium-based compound per unit area is1.0～1.5mg cm^-2；