Nickel oxide nano triangular electrochromic energy storage difunctional material and preparation method thereof

Abstract

The invention provides a nickel oxide nano triangular electrochromic energy storage difunctional material and a preparation method thereof, and belongs to the field of functional films. The multifunctional material has an amorphous porous nanometer triangular island-shaped structure, nickel oxide nanometer triangles have excellent electrochromic performance and energy storage performance at the same time, the energy storage state of the material can be observed in real time through the color change of the material, the nickel oxide nanometer triangular difunctional material takes FTO conductive glass as a substrate, and the nickel oxide nanometer triangular island-shaped structure is prepared through the method. The thin film is of an amorphous porous nanometer triangular island-shaped structure. The nickel oxide nano triangular film with the amorphous porous nano triangular island-shaped structure is prepared by utilizing a unique oxygen partial pressure pulse control technology, the electrochromic performance and the energy storage performance of the material are greatly improved, and the nickel oxide nano triangular film is suitable for being applied to energy-saving / energy-storage dual-function devices or other advanced energy devices.

Description

Technical Field

[0001] The invention relates to the technical field of electrochromic and capacitor functional films, and in particular to a nickel oxide nano-triangle electrochromic energy storage dual-functional material and a preparation method thereof. Background Art

[0002] The development of materials with high energy efficiency is conducive to coping with the current energy crisis and environmental pollution. Electrochromic materials can control the absorption and transmission of sunlight through reversible redox reactions triggered by external voltage. In addition, the material can regulate visible light and thermal radiation, which is conducive to maintaining comfortable temperatures in office buildings and homes in different seasons, thereby achieving energy saving. Supercapacitors are considered to be a promising energy storage device, which uses the reversible insertion / removal of charge to achieve energy storage. Due to the similar working principles of the two, nickel oxide materials simultaneously exhibit electrochromic and electrical energy storage characteristics during rapid charge transfer. Unifying electrochromic and energy storage on a single electrode can greatly improve energy efficiency. Amorphous nickel oxide has a large number of small ion storage sites and multiple ion transport channels, while nanostructured nickel oxide can greatly reduce the ion transport path and expand the contact area between the electrode and the electrolyte. Amorphous nanostructured nickel oxide has excellent optical contrast, fast response speed and high surface capacitance, so it has broad application prospects for advanced nanodevices with dual functions of energy saving and energy storage. Summary of the invention

[0003] In view of this, the purpose of the present invention is to provide a nickel oxide nanotriangle electrochromic energy storage dual-function material and a preparation method thereof. The nickel oxide prepared by the present invention has an ordered nanotriangle array and an amorphous porous hierarchical structure, which can effectively improve the electron transmission speed and ion diffusion rate, accelerate the reaction kinetics process, and has excellent dual-function characteristics.

[0004] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0005] A nickel oxide nano-triangle electrochromic energy storage dual-function material, wherein the film material has a graded amorphous porous nano-triangle island structure.

[0006] Preferably, the size of the amorphous porous nano-triangle island structure in the nickel oxide nano-triangle electrochromic energy storage dual-function material is 100-500nm, and the tissue gap is less than 20nm.

[0007] Preferably, the nickel oxide nano-triangle electrochromic energy storage dual-function material has excellent electrochromic performance and energy storage performance due to its unique amorphous porous nano-triangle island structure, with a visible light modulation amplitude of 60-70%, a near-infrared light modulation amplitude of 20-30%, a complete coloring time of 2-4s, a fading time of 1-2s, and a coloring efficiency of 30-50cm 2 / C, surface capacitance reaches 5-15mf / cm 2 .

[0008] Preferably, the thickness of the nickel oxide nano-triangle electrochromic energy storage dual-function material is less than 500 nm.

[0009] The present invention also provides a method for preparing the nickel oxide nano-triangle electrochromic energy storage dual-function material described in the above technical solution, comprising the following steps:

[0010] Before use, the FTO conductive glass was ultrasonically cleaned in acetone, ethanol and deionized water in turn. The glass surface was treated with a plasma treatment instrument and then placed in a vacuum oven for drying. Before sputtering, the cleaned FTO conductive glass surface was pretreated with NiO electrodeposition to form a thin seed layer. The treated FTO conductive glass was loaded into a magnetron sputtering instrument, and a nickel target with a purity of 99.99% was loaded at the same time. The vacuum degree of the cavity was first pumped to 2*10 -4 Pa, then the sputtering gas argon and the reaction gas oxygen are introduced, and the oxygen partial pressure in the chamber is stably controlled. Then, a pulse power supply is used to complete the thin film sputtering process of nickel oxide nanotriangle electrochromic energy storage dual-functional material under temperature and oxygen control conditions.

[0011] Preferably, during the preparation process, the oxygen partial pressure is between 0.1Pa-0.2Pa, the sputtering power is 30-50W, the sputtering gas pressure is 1-2Pa, the working distance is 5-10cm, the sputtering temperature is 50-70°C, the operating frequency of the pulse power supply is 0.025Hz, and the sputtering time is 100-150 minutes.

[0012] The present invention provides a nickel oxide nano-triangle electrochromic energy storage dual-function material and a preparation method thereof. The multifunctional material of the present invention has an amorphous porous nano-triangle island structure. The nickel oxide nano-triangle has excellent electrochromic performance and energy storage performance at the same time. The energy storage state of the material can be observed in real time through the color change of the material. The nickel oxide nano-triangle dual-function material uses FTO conductive glass as a substrate, and the film presents an amorphous porous nano-triangle island structure. The present invention utilizes a unique oxygen partial pressure pulse control technology to prepare a nickel oxide nano-triangle film with an amorphous porous nano-triangle island structure. The unique amorphous porous nano-triangle island structure increases the specific surface area of ​​the material, significantly enhances the electrochemical reaction kinetics process, and greatly improves the electrochromic performance and energy storage performance of the material. It is suitable for application in energy-saving / energy storage dual-function devices or in other advanced energy devices.

[0013] Compared with the prior art, it has the following beneficial effects:

[0014] 1. The electrochromic material of the present invention has an ordered nano-triangle array and a porous hierarchical structure, which can effectively accelerate the electrochemical reaction kinetics and greatly improve the response speed and contrast of the material;

[0015] 2. Effective control of amorphous structure realizes greater storage capacity for small ions and richer ion transmission channels. The obtained dual-functional materials have the advantages of visible light and near-infrared dual-band modulation, short reaction time, high coloring efficiency, and large energy storage;

[0016] 3. The preparation method of the present invention is stable, and the size, thickness and structure are controllable, which is conducive to large-scale industrial application. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Various other advantages and benefits will become apparent to those of ordinary skill in the art by reading the detailed description of the preferred embodiments below. The accompanying drawings are only for the purpose of illustrating the preferred embodiments and are not to be considered as limiting the present invention. Moreover, the same reference symbols are used throughout the accompanying drawings to represent the same components. In the accompanying drawings:

[0018] Figure 1 This is an electron microscope scanning image of the nickel oxide nanotriangle electrochromic energy storage dual-function material in Example 1 of the present invention;

[0019] Figure 2 The XRD diffraction pattern of the nickel oxide nanotriangular electrochromic energy storage dual-function material of Example 1 of the present invention;

[0020] Figure 3 The transmittance spectra of the nickel oxide nanotriangle electrochromic energy storage dual-function material in the visible light and near infrared bands of Example 1 of the present invention;

[0021] Figure 4 This is a schematic diagram of the kinetic electrochromic performance of the nickel oxide nanotriangular electrochromic energy storage dual-functional material in Example 1 of the present invention (550nm±1V);

[0022] Figure 5 Electrochromic efficiency diagram of nickel oxide nanotriangular electrochromic energy storage dual-function material in Example 1 of the present invention (550nm-1V);

[0023] Figure 6 The charge and discharge curves of the nickel oxide nanotriangular electrochromic energy storage dual-function material under different current densities in Example 2 of the present invention;

[0024] Figure 7 The surface capacitance corresponding to the current density curve of the nickel oxide nanotriangular electrochromic energy storage dual-function material in Example 2 of the present invention;

[0025] Figure 8 The nickel oxide nanotriangular electrochromic energy storage dual-function material in Example 2 of the present invention is 0.14 mA / cm 2 Charging and discharging curves under current density and their corresponding transmittance changes. DETAILED DESCRIPTION

[0026] The specific implementation of the present invention is further described in detail below in conjunction with the accompanying drawings and examples. The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention.

[0027] In order to better understand the purpose, structure and function of the present invention, the present invention is further described in detail below in conjunction with the accompanying drawings.

[0028] The present invention provides a nickel oxide nano-triangle electrochromic energy storage dual-function material and a preparation method thereof. The nickel oxide prepared by the present invention has an ordered nano-triangle array and an amorphous porous hierarchical structure, which can effectively improve the electron transmission speed and ion diffusion rate, accelerate the reaction kinetics process, and has excellent dual-function characteristics.

[0029] Preferably, the size of the amorphous porous nano-triangle island structure in the nickel oxide nano-triangle electrochromic energy storage dual-function material is less than 500nm, preferably between 100-500nm, and the inter-tissue gap is less than 20nm, preferably between 10-20nm.

[0030] Preferably, the nickel oxide nano-triangle electrochromic energy storage dual-function material has excellent electrochromic performance and energy storage performance due to its unique amorphous porous nano-triangle island structure, with a visible light modulation amplitude of 60-70%, a near-infrared light modulation amplitude of 20-30%, a complete coloring time of 2-4s, a fading time of 1-2s, and a coloring efficiency of 30-50cm2 / C, surface capacitance reaches 5-15mf / cm 2 .

[0031] Preferably, the thickness of the nickel oxide nano-triangle electrochromic energy storage dual-function material is less than 500 nm, preferably between 200 and 450 nm.

[0032] The present invention also provides a method for preparing the nickel oxide nano-triangle electrochromic energy storage dual-function material described in the above technical solution, comprising the following steps:

[0033] Before use, the FTO conductive glass was ultrasonically cleaned in acetone, ethanol and deionized water in turn. The glass surface was treated with a plasma treatment instrument and then placed in a vacuum oven for drying. Before sputtering, the cleaned FTO conductive glass surface was pretreated with NiO electrodeposition to form a thin seed layer. The treated FTO conductive glass was loaded into a magnetron sputtering instrument, and a nickel target with a purity of 99.99% was loaded at the same time. The vacuum degree of the cavity was first pumped to 2*10 -4 Pa, then the sputtering gas argon and the reaction gas oxygen are introduced, and the oxygen partial pressure in the chamber is stably controlled. Then, a pulse power supply is used to complete the thin film sputtering process of nickel oxide nanotriangle electrochromic energy storage dual-functional material under temperature and oxygen control conditions.

[0034] Preferably, during the preparation process, the oxygen partial pressure is between 0.1Pa-0.2Pa, the sputtering power is 30-50W, the sputtering gas pressure is 1-2Pa, the working distance is 5-10cm, the sputtering temperature is 50-70°C, the operating frequency of the pulse power supply is 0.025Hz, and the sputtering time is 100-150 minutes.

[0035] Example 1

[0036] Before use, the FTO conductive glass was ultrasonically cleaned in acetone, ethanol and deionized water in turn. The glass surface was treated with a plasma treatment instrument and then placed in a vacuum oven for drying. Before sputtering, the cleaned FTO conductive glass surface was pretreated with NiO electrodeposition to form a thin seed layer. The treated FTO conductive glass was loaded into a magnetron sputtering instrument, and a nickel target with a purity of 99.99% was loaded at the same time. The vacuum degree of the cavity was first pumped to 2*10 -4 Pa, then the sputtering gas argon and the reaction gas oxygen are introduced, and the oxygen partial pressure in the chamber is stably controlled at 0.1Pa. Then, a pulse power supply is used to complete the thin film sputtering process of nickel oxide nanotriangle electrochromic energy storage dual-functional material under temperature and oxygen control conditions. The sputtering power of sputtering deposition is 30W, the sputtering pressure is 1Pa, the working distance is 5cm, the sputtering temperature is 50℃, the working frequency of the pulse power supply is 0.025HZ, and the sputtering time is 100 minutes.

[0037] The nickel oxide nano-triangle electrochromic energy storage dual-function material electrochromic capacitor dual-function thin film material prepared in this embodiment has an amorphous porous nano-triangle island structure, has excellent electrochromic energy storage dual-function characteristics, has a wide range of modulation in the visible and near-infrared light bands (visible light modulation reaches 60.7%, near-infrared light modulation reaches 21.6%), has an extremely short response time (complete coloring time 2.4s, fading time 1s), and has a high coloring efficiency (43.2cm 2 C -1 ), large capacity (7.1mF / cm 2 ), with a high magnification (64.8%). The scanning electron microscope image of the nickel oxide nanotriangular electrochromic energy storage dual-function material prepared in this embodiment is shown in FIG. Figure 1 As shown, the porous hierarchical nanotriangular array structure of the material is characterized; the X-ray diffraction pattern of the amorphous characteristics of the material is shown Figure 2 As shown; the visible light and near infrared band transmittance spectra of Example 1 are as shown Figure 3 As shown, the dual-band large-range modulation performance of the material is characterized; the schematic diagram of the dynamic electrochromic performance (550nm±1V) is shown Figure 4 As shown, the rapid response characteristics of the material are characterized; Figure 5 This is the electrochromic efficiency diagram (550nm-1V) of the nickel oxide nanotriangle electrochromic energy storage dual-functional material in Example 1 of the present invention, which characterizes the high coloring efficiency of the material.

[0038] Example 2

[0039] Before use, the FTO conductive glass was ultrasonically cleaned in acetone, ethanol and deionized water in turn. The glass surface was treated with a plasma treatment instrument and then placed in a vacuum oven for drying. Before sputtering, the cleaned FTO conductive glass surface was pretreated with NiO electrodeposition to form a thin seed layer. The treated FTO conductive glass was loaded into a magnetron sputtering instrument, and a nickel target with a purity of 99.99% was loaded at the same time. The vacuum degree of the cavity was first pumped to 2*10 -4 Pa, then the sputtering gas argon and the reaction gas oxygen are introduced, and the oxygen partial pressure in the chamber is stably controlled at 0.2Pa. Then, a pulse power supply is used to complete the thin film sputtering process of nickel oxide nanotriangle electrochromic energy storage dual-functional material under temperature and oxygen control conditions. The sputtering power of sputtering deposition is 50W, the sputtering pressure is 2Pa, the working distance is 5cm, the sputtering temperature is 70℃, the working frequency of the pulse power supply is 0.025HZ, and the sputtering time is 150 minutes.

[0040] The nickel oxide nano-triangle electrochromic energy storage dual-function material prepared in this embodiment has an amorphous porous nano-triangle island structure and has excellent dual-function properties. Figure 6The charge and discharge curves of the nickel oxide nanotriangular electrochromic energy storage dual-function material under different current densities in Example 2 of the present invention are used to characterize the good charge and discharge symmetry characteristics of the material; Figure 7 The current density curve corresponding to the surface capacitance of the nickel oxide nanotriangular electrochromic energy storage dual-function material in Example 2 of the present invention characterizes the high surface capacitance of the material; Figure 8 The nickel oxide nanotriangular electrochromic energy storage dual-function material in Example 2 of the present invention is 0.14 mA / cm 2 The charge-discharge curves under current density and their corresponding transmittance change diagrams represent the unification of electrochromic performance and energy storage characteristics on a single electrode.

[0041] In the description of the present application, it should be understood that the terms "center", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inside", "outside", etc., indicating orientations or positional relationships, are based on the orientations or positional relationships shown in the accompanying drawings, and are only for the convenience of describing the present application and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be understood as a limitation on the present application.

[0042] The terms "first" and "second" are used for descriptive purposes only and should not be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of the features. In the description of this application, unless otherwise specified, "plurality" means two or more.

[0043] In the description of this application, it should be noted that, unless otherwise clearly specified and limited, the terms "installed", "connected", and "connected" should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection, or it can be indirectly connected through an intermediate medium, or it can be the internal communication of two components. For ordinary technicians in this field, the specific meanings of the above terms in this application can be understood according to specific circumstances.

[0044] In this specification, each embodiment is described in a progressive manner, and each embodiment focuses on the differences from other embodiments. The same or similar parts between the embodiments can be referred to each other. For the device disclosed in the embodiment, since it corresponds to the method disclosed in the embodiment, the description is relatively simple, and the relevant parts can be referred to the method part.

[0045] The above description of the disclosed embodiments enables one skilled in the art to implement or use the present invention. Various modifications to these embodiments will be apparent to one skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but rather to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A nickel oxide nano-triangle electrochromic energy storage dual-function material, characterized in that: The film material has a hierarchical amorphous porous nano triangular island structure.

2. The nickel oxide nano-triangle electrochromic energy storage dual-function material according to claim 1, characterized in that: The film material is composed of uniform and densely packed amorphous porous nano triangular island structures, the size of which is 100-500nm, which are evenly distributed, and there are gaps between adjacent amorphous porous nano triangular island structures.

3. The nickel oxide nano-triangle electrochromic energy storage dual-function material according to claim 1 or 2, characterized in that: The nickel oxide nanotriangle electrochromic energy storage dual-function material has a visible light modulation amplitude of 60-70%, a near infrared light modulation amplitude of 20-30%, a complete coloring time of 2-4 seconds, a fading time of 1-2 seconds, and a coloring efficiency of 30-50 cm 2 / C, surface capacitance reaches 5-15mf / cm 2 .

4. The nickel oxide nano-triangle electrochromic energy storage dual-function material according to claims 1 to 3, characterized in that: The thickness of the nickel oxide nano-triangle electrochromic energy storage dual-function material is 200-450nm, and the gaps between the amorphous porous nano-triangle island-shaped tissues are about 10-20nm.

5. The method for preparing the nickel oxide nanotriangle electrochromic energy storage dual-function material according to any one of claims 1 to 3, characterized in that: The following steps are involved: Before use, the FTO conductive glass is ultrasonically cleaned in acetone, ethanol and deionized water in turn, and then a plasma treatment instrument is used to decompose high-speed moving atoms and molecules, and plasma is generated through dissociation and collision. The generated plasma acts on the surface of the FTO glass to improve the wettability and work function of the FTO glass surface. After completion, it is placed in a vacuum oven for drying. Before sputtering, the NiO electrodeposition method is used to pre-treat the surface of the washed FTO conductive glass to form a thin seed layer, and then it is loaded into a magnetron sputtering instrument, and a nickel target with a purity of 99.99% is loaded at the same time. The vacuum degree of the cavity is first pumped to 2*10 by a magnetic suspension molecular pump. -4 Pa, then sputtering gas argon and reaction gas oxygen are introduced, and the oxygen partial pressure in the chamber is stably controlled between 0.1Pa-0.2Pa. Then, a pulse power supply is used to complete the thin film sputtering process of nickel oxide nano-triangle electrochromic energy storage dual-functional material under temperature and oxygen control conditions.

6. The preparation method according to claim 5, characterized in that: The sputtering power of the sputtering deposition is 30-50W, the sputtering gas pressure is 1-2Pa, the working distance is 5-10cm, the sputtering temperature is 50-70°C, the working frequency of the pulse power supply is 0.025Hz, and the sputtering time is 100-150 minutes.

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