Multi-band dynamic color matching device of carbon nano-tube film and preparation method of multi-band dynamic color matching device

Abstract

The invention provides a multiband dynamic color matching device of a carbon nanotube film and a preparation method of the multiband dynamic color matching device. The method is realized through an electrochromic device, and the electrochromic device specifically comprises an electrochromic layer, a carbon nano-tube film, an electrolyte layer, an ion storage layer and a carbon nano-tube film. Wherein the carbon nano-tube film, the electrochromic layer and the ion storage layer are all prepared by a chemical method, the advantages of low cost and high efficiency are achieved, meanwhile, the porosity, flexibility and conductivity of the carbon nano-tube film can be reserved, transmission of electrolyte ions and release of ion intercalation / deintercalation stress are facilitated, and the electrochemical performance of the battery is improved. The response speed of the device is increased, the service life of the device is prolonged, the structure of the device is simplified, and the application prospect of the device in the multi-band stealth and flexible wearable fields is expanded.

Description

Technical Field

[0001] The present invention relates to the technical field of electrochromic change, and relates to a multi-band dynamic color adjustment device and a preparation method thereof, and in particular to a multi-band dynamic color adjustment device of a nano carbon tube film and a preparation method thereof. Background Art

[0002] Carbon nanotubes are considered to be candidate materials for the preparation of super-strong fibers, transparent conductive films, next-generation carbon-based chips, etc. However, carbon nanotubes are considered to be the blackest material in the world due to their strong absorption capacity for visible light, and due to their highly crystalline surface and chemical inertness, they cannot be chemically dyed by conventional methods. Although Zhang et al. (Scienceadvances, 8(26)(2022)7789) covered the surface of carbon nanotubes with an amorphous inorganic oxide film using atomic layer deposition technology and realized the structural colorization of carbon nanotubes using the principle of thin film interference, the color is not adjustable. The color of an oxide with a certain thickness is fixed, and the atomic layer deposition process is very slow, which is not conducive to its large-scale use. Wang et al. (ACSPhotonics 11(6)(2024)2335-2341) used magnetron sputtering to deposit WO3 on the carbon nanotube film and used zinc foil as the counter electrode to achieve its multi-color change. However, due to the density of the film deposited by sputtering, the response time of the device is relatively long. In addition, due to the use of metal as the counter electrode, the entire device no longer fully possesses the properties of the carbon nanotube film, such as mechanical properties and infrared camouflage characteristics. Summary of the invention

[0003] The present invention provides a multi-band dynamic color-adjusting device of a nano-carbon tube film and a preparation method thereof, which is intended to address the problems existing in the prior art. The present invention uses one of spraying, spin coating or filtration to prepare a nano-carbon tube film, so that the nano-carbon tube film is a loose porous structure, and one of spraying, spin coating or electrodeposition is used to deposit an electrochromic and ion storage layer on the nano-carbon tube film, so that the nano-carbon tube film and the film thereon can retain a porous structure, which is not only conducive to the penetration of electrolytes and ion migration, reducing the response time, but also conducive to the release of stress during the ion embedding and removal process, and improving the cycle life. More importantly, the flexibility and good light scattering ability of the nano-carbon tube film are maintained, so that the film has uniform color at all angles and can be applied to the field of flexible wearables. In addition, since the upper and lower electrodes of the electrochromic device are both made of nano-carbon tube films, it can not only achieve color adjustment in the visible band, but also take into account the color adjustment ability in the mid- and far-infrared bands, which expands its application potential in military camouflage, infrared anti-counterfeiting and other aspects.

[0004] The purpose of the present invention is achieved by at least one of the following technical solutions.

[0005] The present invention provides a multi-band dynamic color adjustment method for a carbon nanotube film, comprising the following steps:

[0006] (1) using a dispersion of carbon nanotubes to prepare a carbon nanotube film as an electrode layer by spraying, spin coating, or suction filtration;

[0007] (2) taking the carbon nanotube films obtained in the two steps (1), depositing a dispersion of electrochromic particles or a dispersion of ion storage nanoparticles on different carbon nanotube films by spraying, spin coating, or electrodeposition to obtain an electrochromic layer and an ion storage layer;

[0008] (3) Two carbon nanotube films coated with an electrochromic layer and an ion storage layer respectively are assembled into an electrochromic device, an electrolyte solution is injected in the middle and encapsulated to obtain a carbon nanotube film device with multi-band dynamic color adjustment.

[0009] Further preferably, in step (1) of the above method, the concentration of the carbon nanotube dispersion is 1 wt% to 10 wt%; and the thickness of the prepared carbon nanotube film is 1 to 10 μm.

[0010] Further preferably, in step (2) of the above method, the concentration of the dispersion of electrochromic particles is 1 to 10 wt %, and the thickness thereof is 100 to 300 nm.

[0011] Further preferably, the electrochromic particles in the dispersion of the electrochromic particles are selected from one of WO3, TiO2, MoO3, Nb2O5, Ta2O5, and V2O5.

[0012] Further preferably, in step (2) of the above method, the concentration of the dispersion of the ion reservoir nanoparticles is 1 to 10 wt %, and the thickness thereof is 100 to 300 nm.

[0013] Further preferably, the ion reservoir nanoparticles in the dispersion of ion reservoir nanoparticles are selected from one of NiO, Co3O4, V2O5, and Ir2O3.

[0014] Further preferably, the molar concentration of the electrolyte solution is 1-10M, and the solvent in the electrolyte solution is one or more of propylene carbonate and acetonitrile.

[0015] Further preferably, in step (3) of the above method, the electrolyte in the electrolyte solution is selected from one of an inorganic ion conductor, an ionic liquid and an ion conductive polymer; the inorganic ion conductor is selected from one of LiClO4, LiPF6 and LiBF4; the ionic liquid is selected from one of imidazolium salts, piperidinium salts and pyridinium salts; the ion conductive polymer is selected from one of PVDF-based, PEO-based and PAN-based gel polymers.

[0016] A multi-band dynamic color adjustment device of a nano-carbon tube film is composed of five layers, wherein the upper and lower electrode layers are composed of nano-carbon tube films; from top to bottom, they are an electrochromic layer, a first nano-carbon tube film, an electrolyte layer, an ion storage layer, and a second nano-carbon tube film.

[0017] The present invention uses a simple and inexpensive chemical film-making method, fully utilizes the conductivity of carbon nanotubes and the porosity of carbon nanotube films, and relies on the multi-band adjustment characteristics of electrochromic oxides and the reasonable design of electrochromic structures to overcome the difficulties of coloring carbon nanotube films, such as the high cost of coloring and the inability to dynamically adjust colors in multiple bands, thereby improving the color adjustment speed, color adjustment life and multi-band color adjustment capability, and expanding its application field.

[0018] Compared with the prior art, the present invention has the following beneficial effects:

[0019] 1. The preparation method proposed in the present invention has the characteristics of low cost, compact structure and short response time, and can be used in the fields of flexible wearable and military camouflage technology, and has good application prospects.

[0020] 2. The multi-band dynamic color adjustment method of the carbon nanotube film proposed in the present invention adopts cheap chemical film-making technology, which not only retains the original porosity of the carbon nanotube film, but also facilitates the insertion and extraction of ions and the release of stress during the electrochromic process, thereby improving the response speed and cycle life of the device. The upper and lower electrodes are both flexible carbon nanotube films, which not only maintain flexibility but also take into account its visible and mid-infrared color adjustment capabilities, thus expanding its application field. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 It is a schematic diagram of the multi-band dynamic color adjustment device of the carbon nanotube film of the present invention;

[0022] Description of reference numerals: electrochromic layer 1 , first carbon nanotube film 2 , electrolyte layer 3 , ion storage layer 4 , second carbon nanotube film 5 .

[0023] Figure 2 The reflectivity spectrum of the carbon nanotube film prepared by the present invention in the coloring and fading conditions;

[0024] Figure 3 This is a visible light picture of the carbon nanotube film prepared by the present invention in a colored state;

[0025] Figure 4 This is a visible light picture of the carbon nanotube film prepared in the present invention in a faded state. DETAILED DESCRIPTION

[0026] The present invention will be further described in detail below in conjunction with specific embodiments, but the embodiments of the present invention are not limited thereto. For process parameters not particularly noted, conventional techniques may be used.

[0027] like Figure 1 As shown, the carbon nanotube film multi-band dynamic color adjustment device is composed of an electrochromic layer 1, a first carbon nanotube film 2, an electrolyte layer 3, an ion storage layer 4, and a second carbon nanotube film 5 from top to bottom. The thickness of the electrochromic layer and the ion storage layer is 100 to 300 nm, and the thickness of the carbon nanotube film is 1 to 10 um.

[0028] The method for preparing the multi-band dynamic color adjustment device of the carbon nanotube film comprises the following steps:

[0029] (1) using a dispersion of carbon nanotubes to prepare a carbon nanotube film as an electrode layer by spraying, spin coating, or suction filtration;

[0030] (2) taking the carbon nanotube films obtained in the two steps (1), depositing a dispersion of electrochromic particles or a dispersion of ion storage nanoparticles on different carbon nanotube films by spraying, spin coating, or electrodeposition to obtain an electrochromic layer and an ion storage layer;

[0031] (3) Two carbon nanotube films coated with an electrochromic layer and an ion storage layer respectively are assembled into an electrochromic device, an electrolyte solution is injected in the middle and encapsulated to obtain a carbon nanotube film device with multi-band dynamic color adjustment.

[0032] Example 1

[0033] A 1 wt% carbon nanotube dispersion was filtered to obtain a 1 um thick carbon nanotube film. A 5 wt% WO3 dispersion was sprayed on the carbon nanotube film to obtain a 300 nm thick electrochromic layer. A 4 wt% NiO dispersion was sprayed on another carbon nanotube film to obtain a 100 nm thick ion storage layer. The two carbon nanotube films were placed in the same manner. Figure 1 The structure is combined and 1M propylene carbonate LiClO4 solution is injected to obtain a multi-band dynamic color nanotube film device, such as Figure 2 to Figure 4 As shown, its colored state is dark blue under visible light, and its faded state is light blue. In the mid- and far-infrared regions, the faded state is a low-reflection state, i.e., a high-emission state, and the colored state is a high-reflection state, i.e., a low-emission state, showing different color characteristics in different bands.

[0034] Example 2

[0035] A 5 wt% carbon nanotube dispersion was filtered to obtain a 5 um thick carbon nanotube film. An 8 wt% TiO2 dispersion was sprayed on the carbon nanotube film to obtain a 300 nm thick electrochromic layer. A 5 wt% Co3O4 dispersion was sprayed on another carbon nanotube film to obtain a 200 nm thick ion storage layer. The two carbon nanotube films were placed in the same manner. Figure 1 The structure was combined and a 5M LiClO4 solution of propylene carbonate and acetonitrile (v / v=10:1) was injected to obtain a multi-band dynamic color-tuning nanocarbon tube film device.

[0036] Example 3

[0037] A nanotube film with a thickness of 8 μm was obtained by filtration from a nanotube dispersion with a concentration of 8 wt%. A WO3 dispersion with a concentration of 10 wt% was sprayed on the nanotube film to obtain an electrochromic layer with a thickness of 300 nm. A V2O5 dispersion with a concentration of 10 wt% was sprayed on another nanotube film to obtain an ion storage layer with a thickness of 300 nm. The two nanotube films were placed in the same manner as described above. Figure 1 The structure was combined and a 3M LiPF6 solution of propylene carbonate and acetonitrile (v / v=10:2) was injected to obtain a multi-band dynamic color-adjusting nanocarbon tube film device.

[0038] Example 4

[0039] A 10 wt% carbon nanotube dispersion was filtered to obtain a 10 um thick carbon nanotube film. A 5 wt% MoO3 dispersion was sprayed on the carbon nanotube film to obtain a 250 nm thick electrochromic layer. A 5 wt% Ir2O3 dispersion was sprayed on another carbon nanotube film to obtain a 150 nm thick ion storage layer. The two carbon nanotube films were placed in a vacuum filtration process. Figure 1 The structure was combined and a 1M LiBF4 solution of propylene carbonate and acetonitrile (v / v=10:5) was injected to obtain a multi-band dynamic color-tuning nanocarbon tube film device.

[0040] Example 5

[0041] A 5wt% dispersion of carbon nanotubes was filtered to obtain a 10um thick carbon nanotube film. A 5wt% dispersion of Nb2O5 was sprayed on the carbon nanotube film to obtain a 300nm thick electrochromic layer. A 1wt% dispersion of Ir2O3 was sprayed on another carbon nanotube film to obtain a 100nm thick ion storage layer. The two carbon nanotube films were placed in the same manner. Figure 1 The structures were combined and 10 M acetonitrile imidazole salt solution was injected to obtain a multi-band dynamic color-tuning nanocarbon tube film device.

[0042] Example 6

[0043] A 5wt% nanotube dispersion was filtered to obtain a 10um thick nanotube film. A 5wt% Ta2O5 dispersion was sprayed on the nanotube film to obtain a 300nm thick electrochromic layer. A 10wt% V2O5 dispersion was sprayed on another nanotube film to obtain a 100nm thick ion storage layer. The two nanotube films were placed in the same way. Figure 1 The structures were combined and an 8M acetonitrile piperidine salt solution was injected to obtain a multi-band dynamic color-tuning carbon nanotube film device.

[0044] Example 7

[0045] A 5wt% carbon nanotube dispersion was filtered to obtain a 10um thick carbon nanotube film. A 5wt% V2O5 dispersion was sprayed on the carbon nanotube film to obtain a 300nm thick electrochromic layer. A 10wt% V2O5 dispersion was sprayed on another carbon nanotube film to obtain a 100nm thick ion storage layer. The two carbon nanotube films were placed in the same manner. Figure 1 The structures were combined and injected into a 1M acetonitrile PVDF-based ion-conductive polymer solution to obtain a multi-band dynamic color-tuning carbon nanotube film device.

[0046] Example 8

[0047] A 5wt% carbon nanotube dispersion was filtered to obtain a 10um thick carbon nanotube film. A 5wt% WO3 dispersion was sprayed on the carbon nanotube film to obtain a 300nm thick electrochromic layer. A 10wt% V2O5 dispersion was sprayed on another carbon nanotube film to obtain a 100nm thick ion storage layer. The two carbon nanotube films were placed in the same manner. Figure 1 The structures were combined and injected into a 1M acetonitrile PEO-based ion conductive polymer solution to obtain a multi-band dynamic color-tuning carbon nanotube film device.

[0048] Example 9

[0049] A 5wt% carbon nanotube dispersion was filtered to obtain a 10um thick carbon nanotube film. A 5wt% WO3 dispersion was sprayed on the carbon nanotube film to obtain a 300nm thick electrochromic layer. A 10wt% V2O5 dispersion was sprayed on another carbon nanotube film to obtain a 100nm thick ion storage layer. The two carbon nanotube films were placed in the same manner. Figure 1 The structure was combined and injected with 2M propylene carbonate PAN-based ion conductive polymer solution to obtain a multi-band dynamic color-tuning nanotube film device.

[0050] Example 10

[0051] A 5wt% carbon nanotube dispersion was filtered to obtain a 10um thick carbon nanotube film. A 5wt% WO3 dispersion was sprayed on the carbon nanotube film to obtain a 300nm thick electrochromic layer. A 10wt% V2O5 dispersion was sprayed on another carbon nanotube film to obtain a 100nm thick ion storage layer. The two carbon nanotube films were placed in the same manner. Figure 1 The structure was combined and a 2M propylene carbonate pyridinium salt solution was injected to obtain a multi-band dynamic color-adjusting nanocarbon tube film device.

[0052] Embodiment 11

[0053] A 5wt% carbon nanotube dispersion was filtered to obtain a 10um thick carbon nanotube film. A 5wt% WO3 dispersion was sprayed on the carbon nanotube film to obtain a 300nm thick electrochromic layer. A 10wt% V2O5 dispersion was sprayed on another carbon nanotube film to obtain a 100nm thick ion storage layer. The two carbon nanotube films were placed in the same manner. Figure 1 The structure is combined and PVDF-based gel polymer is injected to obtain a nanocarbon tube film device with multi-band dynamic color adjustment.

[0054] It should be understood that the above detailed description of the technical solution of the present invention with the help of optimized embodiments is illustrative rather than restrictive, and it cannot be determined that the specific implementation methods of the present invention are limited to this. For ordinary technicians in the technical field to which the present invention belongs, without departing from the concept of the present invention, modifications to the technical solutions recorded in the embodiments, or equivalent replacement of some of the technical features therein, should be deemed to fall within the scope of patent protection determined by the claims submitted for the present invention.

[0055] The above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the embodiments here. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the claims of the present invention.

Claims

1. A method for preparing a multi-band dynamic color-adjusting device of a carbon nanotube film, characterized in that: The following steps are involved: (1) using a dispersion of carbon nanotubes to prepare a carbon nanotube film as an electrode layer by spraying, spin coating, or suction filtration; (2) taking the carbon nanotube films obtained in the two steps (1), depositing a dispersion of electrochromic particles or a dispersion of ion storage nanoparticles on different carbon nanotube films by spraying, spin coating, or electrodeposition to obtain an electrochromic layer and an ion storage layer; (3) Two carbon nanotube films coated with an electrochromic layer and an ion storage layer respectively are assembled into an electrochromic device, an electrolyte solution is injected in the middle and encapsulated to obtain a carbon nanotube film device with multi-band dynamic color adjustment.

2. The method for preparing a multi-band dynamic color-adjusting device of a carbon nanotube film according to claim 1, characterized in that: In step (1), the concentration of the carbon nanotube dispersion is 1wt% to 10wt%; and the thickness of the prepared carbon nanotube film is 1 to 10 μm.

3. The method for preparing a multi-band dynamic color-adjusting device of a carbon nanotube film according to claim 1, characterized in that: In step (2), the concentration of the electrochromic particle dispersion is 1 to 10 wt %, and the thickness is 100 to 300 nm.

4. The method for preparing a multi-band dynamic color-adjusting device of a carbon nanotube film according to claim 3, characterized in that: The electrochromic particles in the dispersion of the electrochromic particles are selected from one of WO3, TiO2, MoO3, Nb2O5, Ta2O5 and V2O5.

5. The method for preparing a multi-band dynamic color-adjusting device of a carbon nanotube film according to claim 1, characterized in that: In step (2), the concentration of the dispersion of ion reservoir nanoparticles is 1 to 10 wt %, and the thickness thereof is 100 to 300 nm.

6. The method for preparing a multi-band dynamic color-adjusting device of a carbon nanotube film according to claim 5, characterized in that: The ion reservoir nanoparticles in the dispersion of the ion reservoir nanoparticles are selected from one of NiO, Co3O4, V2O5, and Ir2O3.

7. The method for preparing a multi-band dynamic color-adjusting device of a carbon nanotube film according to claim 1, characterized in that: The molar concentration of the electrolyte solution is 1-10M, and the solvent in the electrolyte solution is one or more of propylene carbonate and acetonitrile.

8. The method for preparing a multi-band dynamic color-adjusting device of carbon nanotube film according to claim 1, characterized in that: In step (3), the electrolyte in the electrolyte solution is selected from one of an inorganic ion conductor, an ionic liquid and an ion conductive polymer.

9. The method for preparing a multi-band dynamic color-adjusting device of a carbon nanotube film according to claim 8, characterized in that: The inorganic ion conductor is selected from one of LiClO4, LiPF6 and LiBF4; the ionic liquid is selected from one of imidazolate salts, piperidinium salts and pyridinium salts; the ion conductive polymer is selected from one of PVDF-based, PEO-based and PAN-based gel polymers.

10. A multi-band dynamic color-adjusting device made of a carbon nanotube film by the preparation method according to any one of claims 1 to 9, characterized in that: It consists of five layers, wherein the upper and lower electrode layers are made of carbon nanotube films; from top to bottom, they are respectively an electrochromic layer (1), a first carbon nanotube film (2), an electrolyte layer (3), an ion storage layer (4), and a second carbon nanotube film (5).

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