Modified molybdenum trioxide electrode material and preparation method thereof

Abstract

The invention relates to the technical field of electrode materials, and discloses a modified molybdenum trioxide electrode material and a preparation method thereof.The electrode material is of a nanorod-shaped structure, the length-diameter ratio is 25, and the electrode material is formed by compounding a nanorod-shaped molybdenum trioxide primary product, graphene oxide and modified carbon nanotubes; according to the modified molybdenum trioxide electrode material and the preparation method thereof, the unique electrode material with the nanorod-shaped structure is constructed, and the special structure can effectively increase electron transmission paths, improve electron conduction efficiency and improve electrode reaction kinetics. The electrode material is mainly realized by compounding a nanorod-shaped molybdenum trioxide primary product with the graphene oxide and the modified carbon nanotube, and the graphene oxide uniformly coats the surface of the molybdenum trioxide nanorod, so that not only can the electron conduction capability of the material be improved, but also the volume change of the molybdenum trioxide in the charge-discharge process can be buffered, and the charge-discharge performance of the electrode material is improved. The stability of the material structure is enhanced.

Description

Technical Field

[0001] The invention relates to the technical field of electrode materials, and in particular to a modified molybdenum trioxide electrode material and a preparation method thereof. Background Art

[0002] In today's energy field, energy storage devices such as lithium-ion batteries and supercapacitors have attracted much attention due to their importance. As a highly promising electrode material, molybdenum trioxide has a unique layered structure and a high theoretical specific capacity, showing certain application prospects in the fields of batteries and supercapacitors. However, some of its own defects seriously limit its practical application.

[0003] From the perspective of structural characteristics, the electronic conductivity of traditional molybdenum trioxide materials is relatively low, which greatly hinders the rapid transmission of electrons within the material, resulting in sluggish electrode reaction kinetics during charging and discharging, thereby affecting the charging and discharging rate and power density of the energy storage device.

[0004] Therefore, developing a simple and efficient molybdenum trioxide electrode material and improving its comprehensive performance have become key issues that need to be urgently addressed in this field. Summary of the invention

[0005] 1. Technical issues to be resolved

[0006] In view of the deficiencies in the prior art, the present invention provides a modified molybdenum trioxide electrode material and a preparation method thereof.

[0007] (II) Technical solution

[0008] To achieve the above-mentioned purpose, the present invention provides the following technical solutions:

[0009] A modified molybdenum trioxide electrode material, which has a nanorod-like structure and an aspect ratio of 25, and is composited from a nanorod-like molybdenum trioxide primary product, graphene oxide, and modified carbon nanotubes; the graphene oxide is uniformly coated on the surface of the molybdenum trioxide nanorods, and the modified carbon nanotubes are interspersed between the molybdenum trioxide nanorods and the graphene oxide.

[0010] The preparation method of modified molybdenum trioxide electrode material comprises the following steps:

[0011] Preparation of solution A: dissolve ammonium molybdate in a 6%-8% by volume diacetone ethanol solution, stir magnetically for 30 minutes, and prepare a solution A with a molybdate ion concentration of 0.01-0.03 mol / L;

[0012] Preparation of reaction precursor solution: According to the mass ratio of solution A to triethyl citrate solution of 1:(1.5 - 2), slowly and dropwise add the triethyl citrate solution with a concentration of 0.01 - 0.03 mol / L into solution A, and at the same time use a hydrochloric acid solution with a concentration of 0.8 - 1.0 mol / L to adjust the pH value to 2.0 - 2.5, and stir evenly to obtain the reaction precursor solution;

[0013] Preparation of nanorod-shaped molybdenum trioxide primary product: Transfer the reaction precursor solution to a stainless steel autoclave with a polytetrafluoroethylene liner, and carry out hydrothermal reaction at a temperature of 150 - 180 °C for 12 - 15 h; after the reaction is completed, naturally cool to room temperature; then centrifuge the product, and wash the precipitate with deionized water and absolute ethanol 3 - 4 times in sequence. Each time when washing, the mass ratio of the usage amount of deionized water and absolute ethanol to the mass of the precipitate is (5 - 7):1; after washing, place the precipitate in a vacuum drying oven for drying treatment to obtain the nanorod-shaped molybdenum trioxide primary product;

[0014] Preparation of modified molybdenum trioxide electrode material: Mix the nanorod-shaped molybdenum trioxide primary product and graphene oxide according to the mass ratio of 1:(0.08 - 0.10), add deionized water with a mass 1 time that of the primary product, and ultrasonically disperse for 40 - 45 min to make the two evenly mixed; then add modified carbon nanotubes accounting for 1.2% - 1.5% of the mass of the nanorod-shaped molybdenum trioxide primary product, and continue to ultrasonically disperse for 20 - 25 min; then transfer to an autoclave and carry out a secondary hydrothermal reaction at 160 - 168 °C for 2.5 - 3 h; after the reaction is completed, cool, centrifuge, wash, and dry to obtain the modified molybdenum trioxide electrode material.

[0015] As a further technical solution: When preparing solution A, the preparation method of the ethanol solution of diacetone is: at a temperature of 35 °C, add diacetone to ethanol, stir and mix evenly to obtain.

[0016] As a further technical solution: The magnetic stirring speed is 350 - 400 r / min.

[0017] As a further technical solution: During the first hydrothermal reaction, the pressure in the autoclave is stabilized at 1.5 MPa through a pressure regulating device.

[0018] As a further technical solution: The preparation method of the modified carbon nanotubes includes: First, put the carbon nanotubes into a mixed acid solution prepared by mixing concentrated sulfuric acid and concentrated nitric acid according to a volume ratio of 4:1, and stir and react at a temperature of 60 °C at a speed of 150-200 revolutions per minute for 4 h; after the reaction is completed, slowly pour the mixture into a large amount of ice water for dilution, then collect the carbon nanotubes by centrifugation, and wash them repeatedly with deionized water until the pH value of the washing liquid reaches 6-7, showing a nearly neutral state. Then, disperse the washed carbon nanotubes in a Tris-HCl buffer solution containing 3%-4% by mass of dopamine, and continuously stir and react at room temperature for 18 h to cause the dopamine to undergo self-polymerization reaction on the surface of the carbon nanotubes to form a polydopamine coating layer; finally, centrifuge the product and dry it at a temperature of 65 °C for 10 h to obtain the modified carbon nanotubes;

[0019] The pH of the Tris-HCl buffer solution of dopamine is 8.0-8.3.

[0020] As a further technical solution: The vacuum drying is: drying at a temperature of 60-80 °C for 3-5 h.

[0021] As a further technical solution: After the secondary hydrothermal reaction is completed, first naturally cool the reaction kettle in the air to 90-100 °C, and then put it into a cooling device with a cooling rate of 10 °C / min to quickly cool it to room temperature.

[0022] As a further technical solution: During the modification treatment of the carbon nanotubes, process ultrasonic treatment is carried out, the ultrasonic power is 200 W, and the ultrasonic time is 20-25 min to promote the uniform progress of the reaction.

[0023] (III) Beneficial effects

[0024] Compared with the prior art, the present invention provides a modified molybdenum trioxide electrode material, which has the following beneficial effects:

[0025] The present invention proposes a modified molybdenum trioxide electrode material and its preparation method. By constructing an electrode material with a unique nanorod-like structure, this special structure can effectively increase the electron transmission path, improve the electron conduction efficiency, and improve the electrode reaction kinetics. The electrode material of the present invention is mainly realized by compounding the nanorod-like molybdenum trioxide primary product with graphene oxide and modified carbon nanotubes. The graphene oxide is uniformly coated on the surface of the molybdenum trioxide nanorods, which can not only improve the electron conduction ability of the material, but also buffer the volume change of molybdenum trioxide during charge and discharge, and enhance the structural stability of the material. The modified carbon nanotubes are interspersed between the molybdenum trioxide nanorods and the graphene oxide, further constructing an efficient electron transmission network and synergistically improving the overall performance of the material.

[0026] In terms of the preparation method, by regulating various parameters, the present invention ensures that the reaction proceeds under optimal conditions, which is conducive to the formation of a uniform and stable reaction precursor solution, laying a foundation for the preparation of primary molybdenum trioxide nanorods with controllable morphology and structure. Ultimately, primary molybdenum trioxide nanorods with regular morphology and uniform size can be obtained, effectively improving the subsequent composite effect of carbon nanotubes with molybdenum trioxide and graphene oxide, and further enhancing the comprehensive performance of the modified molybdenum trioxide electrode material.

[0027] In summary, for the deficiencies in the performance and preparation process of molybdenum trioxide materials in the prior art, the modified molybdenum trioxide electrode material and its preparation method of the present invention effectively solve problems such as low electron conductivity and unstable structure through material structure design and preparation process optimization. Specific Embodiments

[0028] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0029] Example 1

[0030] A preparation method of a modified molybdenum trioxide electrode material, comprising the following steps:

[0031] Preparation of Solution A: At a temperature of 35 °C, diacetone is added to ethanol and stirred and mixed evenly to obtain an ethanol solution with a volume fraction of 6% of diacetone. Ammonium molybdate is dissolved in this solution and stirred at a magnetic stirring speed of 350 r / min for 30 min to prepare Solution A with a molybdate ion concentration of 0.01 mol / L.

[0032] Preparation of the reaction precursor solution: A 0.01 mol / L solution of triethyl citrate is slowly and dropwise added to Solution A, and the mass ratio of Solution A to the triethyl citrate solution is 1:1.5. At the same time, the pH value is adjusted to 2.0 using a 0.8 mol / L hydrochloric acid solution and stirred evenly to obtain the reaction precursor solution.

[0033] Preparation of nanorod-shaped molybdenum trioxide primary product: Transfer the reaction precursor solution to a stainless-steel autoclave with a polytetrafluoroethylene liner, and carry out hydrothermal reaction at 150 °C for 12 h. During the first hydrothermal reaction, the pressure in the autoclave is stabilized at 1.5 MPa through a pressure regulating device. After the reaction is completed, it is naturally cooled to room temperature. Subsequently, the product is centrifuged, and the precipitate is washed 3 times with deionized water and absolute ethanol in sequence. Each time during washing, the mass ratio of deionized water and absolute ethanol to the mass of the precipitate is 5:1. After washing, the precipitate is placed in a vacuum drying oven and dried at 60 °C for 3 h to obtain the nanorod-shaped molybdenum trioxide primary product.

[0034] Preparation of modified molybdenum trioxide electrode material: Mix the nanorod-shaped molybdenum trioxide primary product and graphene oxide at a mass ratio of 1:0.08, add deionized water with a volume 1 time that of the primary product, and ultrasonically disperse for 40 min to make the two evenly mixed. Then add modified carbon nanotubes accounting for 1.2% of the mass of the nanorod-shaped molybdenum trioxide primary product, and continue to ultrasonically disperse for 20 min. Then transfer it to an autoclave and carry out a secondary hydrothermal reaction at 160 °C for 2.5 h. After the reaction is completed, first naturally cool the autoclave to 90 °C in the air, then put it into a cooling device with a cooling rate of 10 °C / min and quickly cool it to room temperature, and then carry out centrifugation, washing, and drying to obtain the modified molybdenum trioxide electrode material. During the modification treatment process of carbon nanotubes, ultrasonic treatment with an ultrasonic power of 200 W and an ultrasonic time of 20 min is carried out; Modification of carbon nanotubes: First, put them into a mixed acid solution prepared by mixing concentrated sulfuric acid and concentrated nitric acid at a volume ratio of 4:1, and stir and react at a speed of 150 revolutions per minute at 60 °C for 4 h. After the reaction is completed, pour it into a large amount of ice water for dilution, centrifuge and collect, wash repeatedly with deionized water until the pH value reaches 6, and then disperse it in a Tris-HCl buffer solution with a mass fraction of 3% dopamine at pH 8.0 and continuously stir and react at room temperature for 18 h. Finally, centrifuge and separate and dry at 65 °C for 10 h.

[0035] Example 2

[0036] A preparation method of a modified molybdenum trioxide electrode material, comprising the following steps:

[0037] Preparation of solution A: At a temperature of 35 °C, add diacetone to ethanol, stir and mix evenly to obtain an ethanol solution with a volume fraction of 7% diacetone. Dissolve ammonium molybdate in this solution and stir at a magnetic stirring speed of 375 r / min for 30 min to prepare solution A with a molybdate ion concentration of 0.02 mol / L.

[0038] Preparation of reaction precursor solution: Slowly and dropwise add a 0.02 mol / L triethyl citrate solution into solution A, with the mass ratio of solution A to the triethyl citrate solution being 1:1.75. At the same time, use a 0.9 mol / L hydrochloric acid solution to adjust the pH value to 2.25, and stir evenly to obtain the reaction precursor solution.

[0039] Preparation of nanorod-shaped molybdenum trioxide primary product: Transfer the reaction precursor solution to a stainless steel autoclave with a polytetrafluoroethylene liner, and carry out a hydrothermal reaction at a temperature of 165 °C for 13.5 h. During the first hydrothermal reaction, the pressure in the autoclave is stabilized at 1.5 MPa through a pressure regulating device. After the reaction is completed, naturally cool it to room temperature. Subsequently, centrifuge the product, and wash the precipitate 3.5 times with deionized water and absolute ethanol in sequence. Each time when washing, the mass ratio of the usage of deionized water and absolute ethanol to the mass of the precipitate is 6:1. After washing, place the precipitate in a vacuum drying oven and dry it at a temperature of 70 °C for 4 h to obtain the nanorod-shaped molybdenum trioxide primary product.

[0040] Preparation of modified molybdenum trioxide electrode material: Mix the nanorod-shaped molybdenum trioxide primary product and graphene oxide in a mass ratio of 1:0.09, add deionized water with a mass 1 time that of the primary product, and ultrasonically disperse for 42.5 min to make the two evenly mixed. Then add modified carbon nanotubes accounting for 1.35% of the mass of the nanorod-shaped molybdenum trioxide primary product, and continue to ultrasonically disperse for 22.5 min. After that, transfer it to an autoclave and carry out a secondary hydrothermal reaction at 164 °C for 2.75 h. After the reaction is completed, first naturally cool the autoclave to 95 °C in the air, then put it into a cooling device with a cooling rate of 10 °C / min to quickly cool it to room temperature, and then carry out centrifugation, washing, and drying to obtain the modified molybdenum trioxide electrode material. During the modification treatment process of the carbon nanotubes, carry out ultrasonic treatment with an ultrasonic power of 200 W and an ultrasonic time of 22.5 min; Modification of carbon nanotubes: First, put them into a mixed acid solution prepared by mixing concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 4:1, and stir and react at a temperature of 60 °C at a speed of 175 revolutions per minute for 4 h. After the reaction is completed, pour it into a large amount of ice water for dilution, centrifuge and collect, wash repeatedly with deionized water until the pH value reaches 6.5, and then disperse it in a Tris-HCl buffer solution with a mass fraction of 3.5% dopamine at pH 8.15, and continuously stir and react at room temperature for 18 h. Finally, centrifuge and separate and dry at a temperature of 65 °C for 10 h.

[0041] Example 3

[0042] A preparation method of a modified molybdenum trioxide electrode material, comprising the following steps:

[0043] Preparation of Solution A: At a temperature of 35 °C, add diacetone to ethanol and stir to mix evenly to obtain an ethanol solution of diacetone with a volume fraction of 8%. Dissolve ammonium molybdate in this solution and stir for 30 min at a magnetic stirring speed of 400 r / min to prepare Solution A with a molybdate ion concentration of 0.03 mol / L.

[0044] Preparation of the reaction precursor solution: Slowly and dropwise add a 0.03 mol / L solution of triethyl citrate into Solution A, with the mass ratio of Solution A to the triethyl citrate solution being 1:2. At the same time, use a 1.0 mol / L hydrochloric acid solution to adjust the pH value to 2.5 and stir evenly to obtain the reaction precursor solution.

[0045] Preparation of the nanorod-shaped molybdenum trioxide primary product: Transfer the reaction precursor solution to a stainless steel reaction kettle lined with polytetrafluoroethylene and carry out a hydrothermal reaction at 180 °C for 15 h. During the first hydrothermal reaction, the pressure in the reaction kettle is stabilized at 1.5 MPa through a pressure regulating device. After the reaction, naturally cool to room temperature. Subsequently, centrifuge the product and wash the precipitate 4 times successively with deionized water and absolute ethanol. Each time during washing, the usage ratio of deionized water and absolute ethanol to the mass of the precipitate is 7:1. After washing, place the precipitate in a vacuum drying oven and dry at 80 °C for 5 h to obtain the nanorod-shaped molybdenum trioxide primary product.

[0046] Preparation of the modified molybdenum trioxide electrode material: Mix the nanorod-shaped molybdenum trioxide primary product and graphene oxide in a mass ratio of 1:0.10, add deionized water with a mass 1 time that of the primary product, and ultrasonically disperse for 45 min to make the two evenly mixed. Then add modified carbon nanotubes accounting for 1.5% of the mass of the nanorod-shaped molybdenum trioxide primary product and continue to ultrasonically disperse for 25 min. Then transfer to a reaction kettle and carry out a secondary hydrothermal reaction at 168 °C for 3 h. After the reaction is completed, first naturally cool the reaction kettle in the air to 100 °C, then place it in a cooling device with a cooling rate of 10 °C / min and quickly cool to room temperature, and then carry out centrifugation, washing, and drying to obtain the modified molybdenum trioxide electrode material. During the modification treatment of the carbon nanotubes, perform ultrasonic treatment with an ultrasonic power of 200 W and an ultrasonic time of 25 min; Modification of carbon nanotubes: First, place them in a mixed acid solution prepared from concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 4:1, stir and react at 60 °C at a speed of 200 revolutions per minute for 4 h. After the reaction, pour into a large amount of ice water for dilution, centrifuge and collect, wash repeatedly with deionized water until the pH value reaches 7, and then disperse in a Tris-HCl buffer solution with a mass fraction of 4% dopamine at pH 8.3 and continuously stir and react at room temperature for 18 h. Finally, centrifuge and separate and dry at 65 °C for 10 h.

[0047] The following are comparative examples:

[0048] Comparative Example 1:

[0049] Based on Example 1, graphene oxide is not added, and the rest of the technical solutions are the same as those of Example 1.

[0050] Comparative Example 2:

[0051] Based on Example 1, modified carbon nanotubes are not added, and the rest of the technical solutions are the same as those of Example 1.

[0052] Comparative Example 3:

[0053] Based on Example 1, the modified carbon nanotubes are replaced with unmodified carbon nanotubes, and the rest of the technical solutions are the same as those of Example 1.

[0054] Experiment:

[0055] The electrodes of the examples and comparative examples are made into electrodes of the same specifications, and a three-electrode system is used to perform cyclic voltammetry tests on an electrochemical workstation. After 80 cycles each, the capacity retention rate is compared.

[0056] Table 1

[0057] Retention rate % Example 1 95.3 Example 2 94.7 Example 3 95.2 Comparative Example 1 90.6 Comparative Example 2 88.1 Comparative Example 3 93.5

[0058] As can be seen from Table 1, the electrode material prepared by the present invention can significantly improve the capacity retention rate of the battery after cyclic charge and discharge.

[0059] AC impedance test:

[0060] The frequency range is set to 0.01 Hz - 100 kHz, and the charge transfer resistance data of the electrode materials of the examples and comparative examples (the same as the above experiment) are tested.

[0061] Table 2

[0062]

[0063]

[0064] As can be seen from Table 2, the electrode material prepared by the present invention has better electrical conductivity.

[0065] Although the embodiments of the present invention have been shown and described, those of ordinary skill in the art can understand that various changes, modifications, substitutions, and variations can be made to these embodiments without departing from the principles and spirit of the present invention. The scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A modified molybdenum trioxide electrode material, characterized in that: The electrode material has a nanorod-like structure with an aspect ratio of 25, and is composited from a nanorod-like primary molybdenum trioxide product, graphene oxide, and modified carbon nanotubes; the graphene oxide is uniformly coated on the surface of the molybdenum trioxide nanorods, and the modified carbon nanotubes are interspersed between the molybdenum trioxide nanorods and the graphene oxide.

2. A method for preparing the modified molybdenum trioxide electrode material according to claim 1, characterized in that: The following steps are involved: Preparation of solution A: dissolve ammonium molybdate in a 6%-8% by volume diacetone ethanol solution, stir magnetically for 30 minutes, and prepare a solution A with a molybdate ion concentration of 0.01-0.03 mol / L; Preparation of reaction precursor solution: according to the mass ratio of solution A to triethyl citrate solution of 1:(1.5-2), slowly drip a 0.01-0.03 mol / L triethyl citrate solution into solution A, and adjust the pH value to 2.0-2.5 with 0.8-1.0 mol / L hydrochloric acid solution, stir evenly, and obtain a reaction precursor solution; Preparation of nanorod-shaped molybdenum trioxide primary product: transfer the reaction precursor solution to a stainless steel reactor lined with polytetrafluoroethylene, and perform a primary hydrothermal reaction at a temperature of 150-180°C for 12-15 hours; after the reaction is completed, cool naturally to room temperature; then centrifuge the product, wash the precipitate with deionized water and anhydrous ethanol for 3-4 times in sequence, and the mass ratio of the amount of deionized water and anhydrous ethanol to the precipitate during each washing is (5-7):1; after washing, place the precipitate in a vacuum drying oven for drying to obtain a nanorod-shaped molybdenum trioxide primary product; Preparation of modified molybdenum trioxide electrode material: Mix the primary product of nanorod-shaped molybdenum trioxide and graphene oxide in a mass ratio of 1:(0.08-0.10), add deionized water with a mass of 1 times that of the primary product, and ultrasonically disperse for 40-45 minutes to make the two evenly mixed; then add modified carbon nanotubes accounting for 1.2%-1.5% of the mass of the primary product of nanorod-shaped molybdenum trioxide, and continue ultrasonically dispersing for 20-25 minutes; then transfer to a reactor and perform a secondary hydrothermal reaction at 160-168°C for 2.5-3 hours; after the reaction is completed, cool, centrifuge, wash and dry to obtain the modified molybdenum trioxide electrode material.

3. The method for preparing the modified molybdenum trioxide electrode material according to claim 2, characterized in that: When preparing solution A, the preparation method of the diacetone ethanol solution is: at a temperature of 35° C., add diacetone to ethanol, stir and mix evenly, to obtain.

4. The method for preparing the modified molybdenum trioxide electrode material according to claim 2, characterized in that: The magnetic stirring speed is 350-400r / min.

5. The method for preparing the modified molybdenum trioxide electrode material according to claim 2, characterized in that: During the initial hydrothermal reaction, the pressure in the reactor was stabilized at 1.5 MPa through a pressure regulating device.

6. The method for preparing the modified molybdenum trioxide electrode material according to claim 2, characterized in that: The preparation method of modified carbon nanotubes comprises: first, placing carbon nanotubes in a mixed acid solution prepared by concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 4:1, stirring the mixture at a temperature of 60°C and a speed of 150-200 rpm for 4 hours; after the reaction is completed, slowly pouring the mixture into a large amount of ice water for dilution, then collecting the carbon nanotubes by centrifugation, and repeatedly washing with deionized water until the pH value of the washing liquid reaches 6-7, then dispersing the washed carbon nanotubes in a Tris-HCl buffer solution containing 3%-4% dopamine by mass, stirring the reaction at room temperature for 18 hours, so that dopamine undergoes self-polymerization reaction on the surface of the carbon nanotube to form a polydopamine coating layer; finally, centrifuging the product and drying it at a temperature of 65°C for 10 hours to obtain the modified carbon nanotubes; The pH of the Tris-HCl buffer solution of dopamine is 8.0-8.

3.

7. The method for preparing the modified molybdenum trioxide electrode material according to claim 2, characterized in that: The vacuum drying is: drying at a temperature of 60-80° C. for 3-5 hours.

8. The method for preparing the modified molybdenum trioxide electrode material according to claim 2, characterized in that: After the secondary hydrothermal reaction is completed, the reactor is first naturally cooled to 90-100°C in the air, and then placed in a cooling device with a cooling rate of 10°C / min to quickly cool to room temperature.

9. The method for preparing the modified molybdenum trioxide electrode material according to claim 2, characterized in that: During the modification process of carbon nanotubes, ultrasonic treatment was performed with an ultrasonic power of 200 W and an ultrasonic time of 20-25 min.

Images