Titanium dioxide-coated molybdenum trioxide material containing oxygen defects, and preparation method and application thereof

Abstract

This invention discloses a titanium dioxide-coated oxygen-defect-containing molybdenum trioxide material, its preparation method, and its applications. The titanium dioxide-coated oxygen-defect-containing molybdenum trioxide material (MoO) 3‑x The preparation method of TiO2 is as follows: First, TiO2 is coated onto the surface of MoO3 using tetrabutyl titanate as the titanium source. Then, low-carbon fatty alcohols such as methanol and ethanol are used as reducing agents to introduce oxygen vacancies. The TiO2 coating layer avoids the formation of oxygen vacancies on the surface of MoO3. 3‑x Contact with the electrolyte inhibits dissolution and confines MoO₂. 3‑x This allows it to maintain structural stability during repeated proton insertion / extraction processes. The introduction of oxygen vacancies can increase the interlayer spacing of MoO3 and improve the MoO2 content. 3‑x The conductivity of TiO2 promotes proton transport dynamics. Therefore, MoO 3‑x @TiO2, as a proton storage electrode material, combines high capacity, high rate capability, and good cycling stability.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of nanofunctional materials and aqueous ion batteries, and particularly relates to a titanium dioxide coated oxygen defect-containing molybdenum trioxide material as well as a preparation method and application thereof. BACKGROUND

[0002] In recent years, with the deepening of industrialization process, mobile electronic devices or large-scale power grid energy storage devices are further developed, and the demand for excellent electric energy storage systems is increasingly urgent. Lithium ion batteries with organic electrolyte have high energy density characteristics since the 1990s, and have occupied most of the energy storage market. However, the pollution and flammability of organic electrolyte to the environment will cause safety hazards; at the same time, the uneven distribution, scarcity and rising prices of lithium resources will further increase the cost of future energy storage devices. Therefore, in order to solve the current predicament, people urgently need to develop safe and low-cost energy storage systems.

[0003] Compared with organic electrolyte, aqueous electrolyte has faster ionic conductivity, lower cost, non-toxicity and environmental friendliness; at the same time, it has non-flammability, which means higher safety factor. In addition, compared with Li + , Na + , Zn 2 + , etc. metal ions, protons have the smallest ion radius, which is transmitted in aqueous solution by Grotthuss mechanism, showing faster diffusion dynamics. Among the candidates of proton storage materials, orthorhombic molybdenum trioxide (α-MoO3) has a layer structure conducive to ion intercalation / deintercalation and a theoretical capacity as high as 372mA h g -1 . However, α-MoO3 is a semiconductor, and the electron / ion conduction rate is low, and it is seriously dissolved in acidic electrolyte, and the repeated deintercalation of protons between the layers can easily lead to structural collapse. For example, Liu et al. reported that α-MoO3 exhibited a low 120mA h g -1discharge specific capacity and the too low amount of protons in the electrolyte is not conducive to the electrochemical reaction of a-Mo03. The redox peak platform of a-Mo03 disappears after the fifth cycle, showing poor reversibility (Liu WB, Hao JW, Xu CJ, et al. Investigation of zinc ion storage of transition metal oxides, sulfides, and borides in zinc ion battery systems [J]. Chem. Commun. 2017, 53, 6872). Although Wang et al. used 1 M H2S04as electrolyte to ensure sufficient amount of protons, a-Mo03 only shows 10 A g -1 The discharge specific capacity of 125 mA h g -1 is shown below at 125 mA h g 3-x However, the too high amount of protons in the electrolyte makes a-Mo03 dissolve seriously, only retaining 67% of the discharge specific capacity after 100 cycles (Wang XF, Xie YM, Tang K, et al. Redox Chemistry of Molybdenum Trioxide for Ultrafast Hydrogen-Ion Storage [J]. Angew. Chem. Int. Ed. 2018, 57, 11569-11573). Recently, Shi et al. reported that MoO 3-x / MXene composite containing oxygen defects supported by MXene shows a high discharge specific capacity of 369.8 mA h g -1 at 0.2 A g -1 current density in 2 M Zn(OTf)2aqueous electrolyte. Although the introduction of oxygen defects can expand the interlayer spacing of a-Mo03, promote proton diffusion, and reduce the band gap, improving electronic conductivity, which is conducive to the capacity and rate performance. However, the introduction of defects increases the surface energy of a-Mo03, which will exacerbate its own dissolution and water decomposition. MoO 3-x / MXene only retains 46.7% of the discharge specific capacity after 1600 cycles at 4 A g -1 current density (Shi JJ, Hou YX, Liu ZY, et al. The high-performance MoO 3-x / MXene cathodes for zinc-ion batteries based on oxygen vacancies and electrolyte engineering[J]. Nano Energy. 2022, 91, 106651). Therefore, it is an urgent need to further develop high-performance α-MoO3 for proton storage electrode materials. Summary of the Invention

[0004] To solve the problems of poor conductivity and poor cycle stability of molybdenum trioxide mentioned above, the purpose of the present invention is to provide a titanium dioxide-coated molybdenum trioxide material with oxygen defects, its preparation method and application. The preparation method of the present invention has the advantages of simplicity, non-toxicity and low cost. The prepared material, as a proton storage electrode material, has excellent rate performance and cycle stability.

[0005] The present invention combines surface coating and defect introduction to synthesize a titanium dioxide-coated molybdenum trioxide material with oxygen defects, and applies it to a proton storage electrode material, which improves the proton transport kinetics while enhancing the structural stability of MoO3, reducing side reactions, and greatly improving the rate performance and cycle stability.

[0006] The purpose of the present invention is achieved through the following technical solutions:

[0007] The present invention provides a preparation method of a titanium dioxide-coated molybdenum trioxide material with oxygen defects (i.e., MoO 3-x @TiO2, 0 < x < 1), including the following steps:

[0008] (1) After dispersing molybdenum trioxide in an anhydrous ethanol solution, tetrabutyl titanate is added dropwise, and then an ethanol aqueous solution is slowly dropped in, and stirred continuously at a specific temperature for several hours. After suction filtration, it is washed with anhydrous ethanol to obtain a white precipitate, which is dried to obtain a powder. The powder obtained from the reaction is calcined at a high temperature to obtain a titanium dioxide-coated molybdenum trioxide powder;

[0009] ((2) Disperse the titanium dioxide-coated molybdenum trioxide powder obtained in step (1) in deionized water, add a reducing agent, and transfer it to a high-pressure reaction kettle for hydrothermal reaction for several hours. The obtained product is the titanium dioxide-coated molybdenum trioxide material with oxygen defects MoO 3-x @TiO2 (0 < x < 1).

[0010] Further, the mass ratio of tetrabutyl titanate to molybdenum trioxide in step (1) ranges from 1:(0.54 - 2.1).

[0011] Further, in step (1), the range of the specific temperature is 40 - 50 °C, and the range of the continuous stirring time is 24 - 48 hours.

[0012] Further, in step (1), the temperature range of the high-temperature calcination is 500-600 DEG C, and the time range of the high-temperature calcination is 2-4 hours.

[0013] Further, in step (2), the reducing agent is a low-carbon fatty alcohol, and the number of carbon atoms of the low-carbon fatty alcohol is ≤2.

[0014] Further, the low-carbon fatty alcohol is one or more of methanol, ethanol or ethylene glycol.

[0015] Further, in step (2), the temperature of the hydrothermal reaction is 150-190 DEG C, and the time range of the hydrothermal reaction is 4-8 hours.

[0016] The application provides a titanium dioxide-coated oxygen-defect-containing molybdenum trioxide material prepared by the preparation method. 3-x @TiO2, 0 < x < 1. 3-x @TiO2, 0 < x < 1.

[0017] The application also provides application of the titanium dioxide-coated oxygen-defect-containing molybdenum trioxide material as a proton storage electrode material in a battery.

[0018] Further, the application of the titanium dioxide-coated oxygen-defect-containing molybdenum trioxide material as a proton storage electrode material (MoO 3-x @TiO2, 0 < x < 1) in a battery. When used as a positive electrode active material of the battery, protons are released from MoO 3-x @TiO2 during charging, and protons are inserted into MoO 3-x @TiO2 during discharging; when used as a negative electrode active material of the battery, protons are inserted into MoO 3-x @TiO2 during charging, and protons are released from MoO 3-x @TiO2 during discharging.

[0019] Compared with the prior art, the application has the following beneficial effects:

[0020] 1. The application is advantageous for maintaining oxygen defects in MoO3 by first performing surface coating and then introducing oxygen defects. The preparation method of the application is safe, non-toxic and low in cost, and is advantageous for large-scale production and application.

[0021] 2. MoO 3-x @TiO2 (0 < x < 1) prepared by the application combines surface coating and oxygen defects. Introducing oxygen defects into MoO3 can significantly increase the layer spacing of MoO 3-xThe conductivity of TiO2 promotes the proton transmission kinetics, reduces the band gap, and improves the electron transfer rate, thereby significantly improving the rate performance. The TiO2 coating layer avoids the dissolution of MoO 3-x in contact with the electrolyte, inhibits dissolution, and restricts MoO 3-x , so that it remains structurally stable during repeated proton intercalation / deintercalation processes. Therefore, the MoO 3-x (0 < x < 1) with TiO2 has better cycle stability; the MoO 3-x @TiO2(0 < x < 1) has higher capacity and rate performance. Therefore, the MoO 3-x @TiO2 of the present application has high capacity, large rate, and good cycle stability as a proton storage electrode material. 3-x @TiO2 of the present application has high capacity, large rate, and good cycle stability as a proton storage electrode material.

[0022] 3. The MoO 3-x @TiO2 as a proton storage electrode material for aqueous ion batteries has the advantages of environmental friendliness, low price, and high safety compared to organic electrolyte batteries; and has higher rate performance compared to other aqueous metal ion batteries. Therefore, the aqueous ion battery with MoO 3-x @TiO2 as a proton storage electrode material can be used in large-scale energy storage power grids and other fields. BRIEF DESCRIPTION OF DRAWINGS

[0023] Figure 1 The XRD (X-ray diffraction) patterns of the MoO 3-x @TiO2 prepared in Example 1 and the MoO3@TiO2 prepared in Comparative Example 1.

[0024] Figure 2 The EPR (electron paramagnetic resonance) patterns of the MoO 3-x @TiO2 prepared in Example 1 and the MoO3@TiO2 prepared in Comparative Example 1.

[0025] Figure 3 The XPS (X-ray photoelectron spectroscopy) patterns of the MoO 3-x @TiO2 prepared in Example 1 before and after etching.

[0026] Figure 4 The TGA (thermogravimetric analysis) pattern of the MoO 3-x @TiO2 prepared in Example 1.

[0027] Figure 5 The TEM (transmission electron microscope) pattern of the MoO 3-x @TiO2 prepared in Example 1.

[0028] Figure 6 MoO3@TiO2prepared in Example 1 3-x @TiO2, MoO3@TiO2prepared in Comparative Example 1, and MoO3@TiO2prepared in Comparative Example 2 3-x Rate capability of MoO3@TiO2prepared in Example 1 as a battery cathode active material at 1 A g -1 Cycle performance of MoO3@TiO2prepared in Example 1 as a battery cathode active material at 1 A g

[0029] Figure 7 MoO3@TiO2prepared in Example 1 3-x Rate capability of MoO3@TiO2prepared in Example 1 and MoO3@TiO2prepared in Comparative Example 1 as a battery cathode active material.

[0030] Figure 8 MoO3@TiO2prepared in Example 1 3-x Cycle performance of MoO3@TiO2prepared in Example 1 as a battery cathode active material at 10 A g -1 Cycle performance of MoO3@TiO2prepared in Example 1 as a battery cathode active material at 10 A g

[0031] Figure 9 MoO3@TiO2prepared in Example 1 3-x In-situ XRD of MoO3@TiO2prepared in Example 1 as a proton storage electrode material.

[0032] Figure 10 MoO3@TiO2prepared in Example 1 3-x Cycle performance of MoO3@TiO2prepared in Example 1 as a battery anode active material at 5 A g -1 Cycle performance of MoO3@TiO2prepared in Example 1 as a battery anode active material at 5 A g DETAILED DESCRIPTION

[0033] The method for preparing the molybdenum trioxide nanoribbons is as follows:

[0034] Dissolve 1.52 g of ammonium molybdate tetrahydrate into 50 mL of deionized water, then add 9.1 mL of concentrated nitric acid (68 wt%) and continue stirring for 30 min. Transfer the solution into a 100 mL polytetrafluoroethylene-lined stainless steel reaction kettle, and then perform hydrothermal reaction at 180 °C for 24 h. After the reaction kettle is cooled to room temperature, wash the off-white precipitate with deionized water for 3 times, and then dry the collected off-white precipitate at 80 °C for 12 h to obtain the molybdenum trioxide nanoribbons.

[0035] Example 1

[0036] (1) 280 mg of molybdenum trioxide nanoribbons were dispersed in 80 mL of anhydrous ethanol, and 0.3 mL of tetrabutyl titanate was added dropwise. Then, 21 mL of 95 wt% ethanol aqueous solution was added dropwise at a rate of 5 drops / min. The mixture was stirred continuously at 45 °C for 48 hours. After filtration, the mixture was washed three times with anhydrous ethanol to obtain a white precipitate, which was then dried at 80 °C for 12 hours to obtain a powder. The powder obtained from the reaction was calcined at 550 °C for 3 hours in an air atmosphere to obtain titanium dioxide-coated molybdenum trioxide (MoO3@TiO2) powder.

[0037] (2) Disperse 100 mg of titanium dioxide-coated molybdenum trioxide (MoO3@TiO2) powder obtained in step (1) into 15 mL of deionized water, add 15 mL of anhydrous ethanol, transfer to a high-pressure reactor, and hydrothermally react at 170 °C for 6 hours. The resulting product is titanium dioxide-coated oxygen-defective molybdenum trioxide material MoO2. 3-x @TiO2.

[0038] Figure 1 The MoO prepared in Example 1 3-x XRD patterns of MoO3@TiO2 prepared in Comparative Example 1 and @TiO2. Figure 1 It can be seen that the (020) crystal plane of MoO3 is shifted at a low angle. According to Bragg's equation, the interplanar spacing of the (020) crystal planes is... Increase to

[0039] Figure 2 The MoO prepared in Example 1 3-x EPR spectra of @TiO2 and MoO3@TiO2 prepared in Comparative Example 1. Figure 2 It can be seen from MoO 3-x @TiO2 has a significant spike at g=2.003, proving that hydrothermal reduction successfully introduced oxygen defects.

[0040] Figure 3 The MoO prepared in Example 1 3-x XPS (X-ray photoelectron spectroscopy) images of TiO2 before and after etching. Figure 3 Mo was observed both before and after etching. 5+ The presence of peaks further confirms the existence of oxygen vacancies, which are distributed throughout the MoO₂. 3-x In addition, the MoO prepared in Example 1 was also used. 3-x @TiO2 etching before and after XPS Mo 5+ content and Figure 4 MoO 3-x @TiO2 TGA (thermogravimetric analysis) results under different atmospheres, MoO 3-xThe chemical formula of TiO2can be quantified as MoO 2.93 @TiO2.

[0041] Figure 5 MoO 3-x @TiO2prepared in Example 1. The TEM (Transmission Electron Microscope) image of TiO2is shown in Figure 1. Figure 5 MoO 3-x The surface-coated TiO2layer is 15-20 nm.

[0042] When assembling the battery, 160 mg of MoO 3-x @TiO2prepared in Example 1 was mixed with 30 mg of Super-P and 10 mg of polyvinylidene fluoride binder in a mass ratio of 8:1.5:0.5, and then dropped into 1.5 mL of N-methylpyrrolidone to form a uniform slurry. The slurry was then coated on a graphite paper and dried in a vacuum drying oven at 80°C for 12 h to obtain a positive electrode sheet. The positive electrode sheet, a negative zinc sheet, and a glass fiber separator were placed in a button cell, and 180 μL of a mixed electrolyte (solvent: deionized water) of ZnSO4(2 M) and Al2(SO4)3(0.5 M) was added, and then the cell was sealed. The cell was subjected to constant current charge and discharge tests, and the specific capacity of the cell was calculated based on the mass of the positive electrode active material.

[0043] Figure 6 MoO 3-x @TiO2prepared in Example 1, MoO3@TiO2prepared in Comparative Example 1, and MoO 3-x @TiO2prepared in Comparative Example 2. -1 As a positive electrode active material of a battery, the cycle performance at a current density of 1 A g Figure 6 It can be seen that MoO 3-x @TiO2prepared in Example 1 has excellent cycle stability as a positive electrode active material of a water-based ion battery at a current density of 1 A g -1 , and retains a specific capacity of 166.9 mA h g -1 after 1000 cycles, which is significantly better than MoO3@TiO2prepared in Comparative Example 1 (80.7 mA h g -1 ) and MoO 3-x @TiO2prepared in Comparative Example 2 (129.0 mA h g -1 ) as a positive electrode active material of a battery.

[0044] Figure 7 MoO 3-xRate performance test charts of aqueous ion batteries using @TiO2 and MoO3@TiO2 prepared in Comparative Example 1 as positive electrode active materials. Benefiting from the introduction of oxygen defects, the MoO3@TiO2 prepared in Example 1... 3-x Aqueous ion batteries using TiO2 as the positive electrode active material exhibit excellent rate performance, even at 30 A g. -1 Even at extremely high current densities, it can still provide 93.2 mA hg. -1 Specific capacity. In contrast, the aqueous ion battery prepared in Comparative Example 1, using MoO3@TiO2 as the positive electrode active material, exhibited a current density exceeding 10 A g. -1 It cannot store charge at that time.

[0045] Figure 8 The MoO prepared in Example 1 3-x @TiO2 as a positive electrode active material in batteries at 10A g -1 Cyclic performance graph at current density. (Example) Figure 8 As shown, the MoO prepared in Example 1 3-x Aqueous ion batteries using TiO2 as the positive electrode active material at 10A g -1 It exhibits an ultra-long cycle life at high current densities, maintaining 117.7 mA hg after 5000 cycles. -1 It has a high specific capacity and a coulomb efficiency close to 100%.

[0046] Figure 9 The MoO prepared in Example 1 3-x In-situ XRD pattern of TiO2 as a proton storage electrode material. Figure 9 It can be seen that during the first negative scan, as protons are embedded, the H containing protons... 0.34 MoO3 and H 1.68 The MoO3 phase can be observed. After the first negative scan, the α-MoO3 phase transforms into the H2MoO3 phase. During the subsequent positive scan, as protons are extracted, the H2MoO3 phase transforms into H... 0.6 MoO3 phase. In the subsequent second CV lap, H... 0.6 MoO3 participates in electrochemical reactions as an active substance.

[0047] The MoO prepared by this invention 3-x TiO2, due to its moderate potential, can be used not only as a proton storage electrode material for positive electrode activity in batteries, but also as a negative electrode active material when paired with a redox couple at a higher potential. Here, the present invention also provides a MoO2... 3-x @TiO2 is used as the negative electrode active material in aqueous ion batteries. MoO 3-xThe preparation process of the TiO2 negative electrode sheet is the same as that of the positive electrode sheet. When assembling the battery, the negative electrode sheet, the carbon nanotube coated titanium mesh, and the glass fiber separator are placed in a soft package, 0.2 mL of a mixed electrolyte (solvent is deionized water) of AlCl3 (1 M) and KBr (50 mM) is added, and the battery is obtained by sealing. The battery is subjected to constant current charge and discharge test, and the specific capacity of the battery is calculated according to the mass of the positive and negative active materials.

[0048] Figure 10 MoO3@TiO2 prepared in Example 1 is shown. 3-x @TiO2 as the negative active material of the water-based ionic battery is cycled at a current density of 5 A g -1 @TiO2 as the negative active material of the water-based ionic battery is cycled at a current density of 5 A g -1 @TiO2 as the negative active material of the water-based ionic battery is cycled at a current density of 5 A g -1 @TiO2 as the negative active material of the water-based ionic battery is cycled at a current density of 5 A g -1 @TiO2 as the negative active material of the water-based ionic battery is cycled at a current density of 5 A g

[0049] Example 2

[0050] (1) 163 mg of molybdenum trioxide nanobelt was dispersed in 80 mL of anhydrous ethanol, then 0.3 mL of tetrabutyl titanate was added dropwise, followed by 21 mL of 95 wt% ethanol aqueous solution at a rate of 5 drops / min, and stirring at 40℃ for 48 hours. After filtration, the white precipitate was washed with anhydrous ethanol for 3 times, and dried at 80℃ for 12 hours to obtain a powder. The powder obtained by the reaction was calcined at 500℃ for 4 hours in air atmosphere to obtain a titanium dioxide coated molybdenum trioxide (MoO3@TiO2) powder;

[0051] (2) 200 mg of the titanium dioxide coated molybdenum trioxide (MoO3@TiO2) powder obtained in step (1) was dispersed in 10 mL of deionized water, and then transferred to a high-pressure reaction kettle after adding 20 mL of ethylene glycol. The obtained product is a titanium dioxide coated oxygen defect molybdenum trioxide material MoO 3-x @TiO2.

[0052] Example 3

[0053] (1) 630 mg of molybdenum trioxide nanobelt was dispersed in 80 mL of anhydrous ethanol, 0.3 mL of tetrabutyl titanate was added dropwise, then 21 mL of 95 wt% ethanol aqueous solution was added dropwise at a rate of 5 drops / min, stirring at 50°C for 24 hours, white precipitate was obtained after filtration and washing with anhydrous ethanol for 3 times, and the powder was dried at 80°C for 12 hours. The powder obtained by reaction was calcined at 600°C for 2 hours in air atmosphere to obtain a molybdenum trioxide coated with titanium dioxide (MoO3@TiO2) powder;

[0054] (2) 100 mg of the molybdenum trioxide coated with titanium dioxide (MoO3@TiO2) powder obtained in step (1) was dispersed in 10 mL of deionized water, then transferred into a high-pressure reaction kettle after adding 20 mL of methanol, and hydrothermal reaction was carried out at 190°C for 4 hours. The obtained product was a molybdenum trioxide coated with oxygen defect material MoO 3-x @TiO2.

[0055] Example 4

[0056] (1) 500 mg of molybdenum trioxide nanobelt was dispersed in 80 mL of anhydrous ethanol, 0.3 mL of tetrabutyl titanate was added dropwise, then 21 mL of 95 wt% ethanol aqueous solution was added dropwise at a rate of 5 drops / min, stirring at 45°C for 24 hours, white precipitate was obtained after filtration and washing with anhydrous ethanol for 3 times, and the powder was dried at 80°C for 12 hours. The powder obtained by reaction was calcined at 550°C for 4 hours in air atmosphere to obtain a molybdenum trioxide coated with titanium dioxide (MoO3@TiO2) powder;

[0057] (2) 100 mg of the molybdenum trioxide coated with titanium dioxide (MoO3@TiO2) powder obtained in step (1) was dispersed in 15 mL of deionized water, then transferred into a high-pressure reaction kettle after adding 15 mL of methanol, and hydrothermal reaction was carried out at 160°C for 8 hours. The obtained product was a molybdenum trioxide coated with oxygen defect material MoO 3-x @TiO2.

[0058] Example 5

[0059] (1) 300 mg of molybdenum trioxide nanobelt was dispersed in 80 mL of anhydrous ethanol, 0.3 mL of tetrabutyl titanate was added dropwise, then 21 mL of 95 wt% ethanol aqueous solution was added dropwise at a rate of 5 drops / min, stirring at 40°C for 32 hours, white precipitate was obtained after filtration and washing with anhydrous ethanol for 3 times, and the powder was dried at 80°C for 12 hours. The powder obtained by reaction was calcined at 600°C for 3 hours in air atmosphere to obtain a molybdenum trioxide coated with titanium dioxide (MoO3@TiO2) powder;

[0060] (2) 150 mg of the molybdenum trioxide coated with titanium dioxide (MoO3@TiO2) powder obtained in step (1) was dispersed into 15 mL of deionized water, and then transferred into a high-pressure reaction kettle after adding 15 mL of methanol. The obtained product was a molybdenum trioxide coated with oxygen defect molybdenum trioxide material MoO3@TiO2 after hydrothermal reaction at 170°C for 6 hours. 3-x @TiO2.

[0061] Comparative Example 1

[0062] The specific preparation method and battery assembly process were the same as those of Example 1, except that step (2) was not performed, and a molybdenum trioxide coated with titanium dioxide material MoO3@TiO2 was obtained.

[0063] Comparative Example 2

[0064] The specific preparation method and battery assembly process were the same as those of Example 1, except that step (1) was not performed, and a molybdenum trioxide coated with oxygen defect molybdenum trioxide material MoO3@TiO2 was obtained. 3-x .

[0065] The embodiments of the present application are not limited to the above examples, and any changes, combinations, modifications, replacements, simplifications, etc. made under the scope of the claims of the present application should be equivalent replacement manners, and are all included in the protection scope of the present application.

Claims

1. A method for producing a titanium dioxide-coated molybdenum trioxide material containing oxygen defects, characterized in that The method comprises the following steps: (1) dispersing molybdenum trioxide into anhydrous ethanol solution, dropwise adding tetrabutyl titanate, then dropwise adding an ethanol aqueous solution, continuously stirring at 40-50℃ for 24-48 hours, performing suction filtration, washing and drying to obtain a powder, and calcining the obtained powder at 500-600℃ for 2-4 hours to obtain a titanium dioxide coated molybdenum trioxide powder; the mass ratio of the tetrabutyl titanate to the molybdenum trioxide is 1:(0.54-2.1); (2) The powder obtained in step (1) is dispersed into water, a low-carbon-number fatty alcohol with carbon atom number ≤2 is added as a reducing agent, and a hydrothermal reaction is carried out at 160-190°C for 4-8 hours. The obtained product is a titanium dioxide-coated oxygen-defect-containing molybdenum trioxide material MoO 3-x @TiO2, and the obtained product is used as a proton storage electrode material. In the MoO 3-x @TiO2, 0 < x < 1.

2. The method of claim 1, wherein the method is characterized by: In step (2), the reducing agent is at least one of methanol, ethanol or ethylene glycol.

3. The titanium dioxide-coated molybdenum trioxide material prepared by the method of any one of claims 1-2, characterized in that, The general formula of the titanium dioxide coated oxygen-deficient molybdenum trioxide material is MoO 3-x @TiO2, the MoO 3-x @TiO2, 0 < x < 1.

4. Use of the titanium dioxide coated molybdenum trioxide material containing oxygen defects as claimed in claim 3 as a proton storage electrode material in a battery.

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