CN115745418A - Quick-response nickel oxide electrochromic film and preparation method and application thereof - Google Patents
Quick-response nickel oxide electrochromic film and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a preparation method of a fast-response nickel oxide electrochromic film, which adopts a magnetron sputtering technology and co-dopes M x T y Ni z And O is used as a cathode target material, a mixed gas of inert gas and oxygen is used as a working gas, a nickel oxide film is deposited on the surface of a transparent glass substrate, and the obtained nickel oxide film is subjected to high-temperature rapid annealing process treatment to obtain the nickel oxide electrochromic film, wherein the coloring response time of the nickel oxide electrochromic film is less than 3.5s, the fading response time of the nickel oxide electrochromic film is less than 1.5s, and the electrochemical cycling stability of the nickel oxide electrochromic film is higher than 3000 circles. The technical scheme of the invention can promote the realization of the nickel oxide film with a crystallized cubic phase structure to form a smooth crack-free structure containing uniformly distributed pores, so that lithium ions can rapidly move in the electrochromic processAnd a large number of channels and reaction sites are provided, so that the electrochromic response speed of the film is improved, and long-time cycling stability is realized.
Description
Technical Field
The invention relates to the technical field of electrochromic devices and application, in particular to a nickel oxide electrochromic film with quick response and a preparation method and application thereof.
Background
The electrochromic material is an intelligent material which can generate stable and reversible color change under external electrical stimulation and has optical modulation capability. Nickel oxide NiO is an anode electrochromic material with a long research history, and can realize reversible change between a transparent reduction state and a dark brown oxidation state in both aqueous electrolytes and organic electrolytes. At present, electrochromic devices which utilize external voltage to adjust double injection of lithium ions and electrons so as to realize rapid and reversible optical switching are applied to the fields of building energy conservation, modern display, automobile awning, VR glasses and the like. The application of the electrochromic device in the fields needs to have the requirements of wide light modulation range, good cycling stability, stable mechanical property, large-area preparation, high response speed and the like.
Conventional electrochromic devices are composed of a transparent electrode layer, an electrochromic layer, an electrolyte layer, and an ion storage layer (counter electrode layer), of which nickel oxide is the most typical material of the ion storage layer. Nickel oxide is an anode electrochromic material, lithium ions and electrons are injected simultaneously under the action of an electric field, the mutual transformation of a colored state and a faded state is realized (formula 1),
NiO x (colored state) + yLi + +ye - ＜＝＞Li y NiO x (faded state) (1)
The process and the fading state of tungsten oxide form a complementary relationship, and the optical modulation amplitude of the electrochromic device is further improved while lithium ions are stored.
The preparation method of the nickel oxide film mainly comprises thermal evaporation, electron beam evaporation, electrochemical deposition, magnetron sputtering and the like, wherein the magnetron sputtering has the advantages of uniform components, strong adhesion between the film and a substrate, room-temperature sputtering, large-area deposition and the like, and is widely used. However for existing applicationsThe nickel oxide film deposited by magnetron sputtering of the electrochromic device has the following defects: the poor optical modulation amplitude, poor ion storage capacity, slow response time, and low fade state transmission limit the commercial application of the product. For example, zhao et al (Coatings, 2022, 12, 118) disclose a method of depositing a nickel oxide thin film on ITO glass by rf magnetron reactive sputtering, and the nickel oxide thin film having a thickness of 140nm prepared by the method has a long fading time of 4.1s, a coloring time of 8.1s, and poor cycle stability; atak et al (solid State Ionics,305 (2017) 43-51) disclose a method for depositing a nickel oxide film on ITO glass by using radio frequency reaction magnetron sputtering, and the modulation amplitude of the prepared nickel oxide film after high-temperature treatment at 300 ℃ is only 4%; lee et al (Journal of Alloys and Compounds,2020 (815): 152399) disclose a method for preparing nickel oxide and tungsten-doped nickel oxide films by direct current reactive magnetron sputtering, and have found that after 1000 CV cycles, the nickel oxide film has a large attenuation and a charge storage capacity of from 12mC cm -2 Reduced to 6mC cm -2 And the optical modulation amplitude is reduced to 8%.
In addition, most of the growth methods adopted by the magnetron sputtering deposition of the nickel oxide film are reactive sputtering of a metallic nickel target, for example, CN109402565a discloses a growth method of a nickel oxide film, which takes a metallic nickel target as a coating target, argon as a sputtering gas, and oxygen as a reaction gas to realize the preparation of the nickel oxide film. However, the reactive sputtering of nickel oxide targets still faces the following problems for uniform and rapid deposition of large-area films in industry: the film is sputtered under high oxygen atmosphere, the target surface is easy to be poisoned, the sputtering voltage and power are difficult to be improved, the sputtering rate is also serious to be reduced, and the high-efficiency film deposition is difficult to be realized. Chinese patent CN112456813A discloses a nickel oxide electrochromic film, a preparation method and application thereof, and co-doped M x T y Ni z O is a target material, wherein M is at least one of lithium, sodium, potassium, rubidium and cesium, and T is at least one of aluminum, silicon and zirconiumThe method comprises the steps of depositing a film on the surface of a transparent conductive substrate by magnetron sputtering, and finally carrying out rapid thermal annealing treatment under the air condition to obtain the co-doped nickel oxide electrochromic film, wherein the obtained film has high preferred orientation growth of nickel oxide and a smooth and compact structure with uniformly distributed pinholes, has good charge capacity and optical modulation amplitude, has fading response time of 9s and 3s respectively, and has an optimized space for cycle stability. Therefore, the invention optimizes the process based on the technology, and based on the application defects of the nickel oxide material in the prior art, the invention further optimizes the components of the doping elements of the target, the process conditions of film coating, the treatment of the film annealing process and the like based on the nickel oxide ceramic target, and utilizes the coupling effect among the process conditions to improve the performances of the nickel oxide electrochromic film, such as the cycling stability, the fading response time and the like, and meet the application requirements of high-performance electrochromic devices.
Disclosure of Invention
The invention discloses a nickel oxide electrochromic film capable of quickly responding, a preparation method and application thereof, which can promote the realization of crystallizing a nickel oxide film with a cubic phase structure to form a smooth crack-free structure containing uniformly distributed micropores, provide a large number of channels and reaction sites for the quick movement of lithium ions in an electrochromic process, contribute to the improvement of the electrochromic response speed of the film, and effectively improve the ion scouring resistance of the film, thereby realizing long-time cycle stability.
In order to achieve the above object, the present invention provides the following technical solutions,
a method for preparing the quickly responding electrochromic Ni oxide film features use of magnetically controlled sputtering technique and co-doping M x T y Ni z O is used as a cathode target material, mixed gas of inert gas and oxygen is used as working gas, and a nickel oxide film is formed on the surface of the transparent glass substrate in a deposition mode, wherein the first doping element M comprises at least one of zinc, tin and silicon, the second doping element T comprises at least one of aluminum, tungsten and niobium, and x: y: z = (0.01-0.2): (0.4-0.7): 1; and a pair ofAnd carrying out high-temperature rapid thermal annealing treatment on the obtained nickel oxide film to obtain the nickel oxide electrochromic film. The nickel oxide electrochromic film prepared by the technical scheme is of a standard cubic phase structure, the surface of the nickel oxide electrochromic film is smooth and has uniformly distributed microporous structures, and in the electrochromic process, the microporous structures provide channels and reaction sites for the rapid movement of lithium ions; the coloring response time of the nickel oxide electrochromic film is less than 3.5s, the fading response time is less than 1.5s, and the electrochemical cycling stability is higher than 3000 circles.
As a preferred embodiment, codoping M x T y Ni z O is the cathode target, M is zinc, T is tungsten, and x: y: z = 0.12: 0.5: 1.
In some preferred embodiments, the high-temperature rapid annealing process comprises heating the nickel oxide film to 500-700 ℃ at a heating rate of 20-80 ℃/s in an air atmosphere, and then keeping the temperature for 2-8 min; and then cooling to room temperature at a cooling rate of 40-80 ℃/s to obtain the nickel oxide electrochromic film. Preferably, the cooling rate is not lower than the heating rate.
In some preferred embodiments, the inert gas is argon, and oxygen to argon = (0.01-0.2) = 1.
In some preferred embodiments, the substrate comprises transparent conductive glass, including any one of ITO, FTO, AZO, GZO conductive glass.
In some preferred embodiments, the magnetron sputtering technique employs process conditions including: the sputtering mode is radio frequency sputtering or intermediate frequency sputtering; the working gas is argon and oxygen, wherein, the ratio of oxygen to argon is (0.01-0.2) to 1; the temperature of the matrix is 25-200 ℃; the background vacuum degree of the reaction chamber is 1.0 multiplied by 10 -3 ～1.0×10 -1 Pa, sputtering pressure of 0.4-2.0 Pa, and sputtering power density of 2.2-6.6W/cm 2 The deposition time is 15-40 min.
The thickness of the nickel oxide electrochromic film prepared by the technical scheme is 100-300 nm; and/or, the nickel oxide electrochromic film has the fading state transmittance of more than 92% under the condition of the wavelength of 550nm, and the optical propertyModulation amplitude is more than 22%, and charge capacity is 8.7mC cm -2 The above. In particular, the nickel oxide film has a standard cubic phase structure, a smooth and crack-free surface and a uniformly distributed microporous structure, can provide a large number of channels and reaction sites for rapid movement of lithium ions in an electrochromic process, is favorable for improving the electrochromic response speed of the nickel oxide film, and has high fading state transmittance, optical modulation amplitude, charge capacity and electrochemical cycling stability.
The nickel oxide electrochromic film prepared by the technical scheme is used for preparing the ion storage layer, is applied to an electrochromic device, can provide the characteristics of quick response and cycle stability for the electrochromic device, and has excellent optical and electrical properties.
The technical effect of the technical scheme of the invention is as follows:
1. the preparation method of the nickel oxide electrochromic film can promote the film to form a smooth crack-free structure containing uniformly distributed micropores, provides a large number of channels and reaction sites for the rapid movement of lithium ions in the electrochromic process, is beneficial to improving the electrochromic response speed of the film, and effectively improves the ion scouring resistance of the film, thereby realizing long-time circulation stability; the obtained nickel oxide electrochromic film has the coloring response time of less than 3.5s, the fading response time of less than 1.5s and the electrochemical cycling stability of more than 3000 circles.
2. By adopting the preparation method for preparing the nickel oxide electrochromic film, particularly the high-temperature rapid thermal annealing process, the temperature is rapidly cooled to room temperature, so that the preparation method is compatible with the high-temperature tempering process of the existing safety glass, and the strength of the glass is improved; on the other hand, the electrochromic performance of the film is further improved, the nickel oxide film can be promoted to realize the formation of a crystalline cubic phase structure, the stable proceeding of electrochromic reaction is facilitated, and the production cost can be reduced.
3. The preparation method of the nickel oxide electrochromic film provided by the invention adopts the conductive ceramic target material to replace the traditional ceramic target material radio frequency reactive sputtering, is beneficial to improving the sputtering rate, can reduce nearly half of the sputtering time by the same thickness, effectively reduces the production cost, and is suitable for future large-scale industrial production.
4. The preparation method of the nickel oxide electrochromic film provided by the invention can obviously increase the charge capacity and the higher cycling stability of the nickel oxide electrochromic film.
5. The preparation method of the nickel oxide electrochromic film provided by the invention adopts the conductive ceramic target material to replace the traditional ceramic target material radio frequency reactive sputtering, is beneficial to improving the sputtering rate, reduces the production cost and is suitable for future large-scale industrial production.
Drawings
Fig. 1 is an XRD pattern of the nickel oxide electrochromic films prepared in example 1 of the present invention and comparative examples 1 to 3, with a test angle of 30 to 90 °.
Fig. 2a to 2d are surface SEM images of the nickel oxide electrochromic films prepared in example 1 of the present invention and comparative examples 1 to 3, respectively.
FIGS. 3a to 3d are surface SEM images of the nickel oxide electrochromic films prepared in example 1 of the present invention and comparative examples 1 to 3, respectively, after 3000 cyclic voltammetry tests using a voltage range of-1.2 to 1.2V and a sweep rate of 50mV/s.
FIGS. 4a to 4d are graphs showing coloring and fading transmittances at 550nm of the nickel oxide thin films prepared in example 1 of the present invention and comparative examples 1 to 3, respectively, at different numbers of electrochemical cycles.
FIGS. 5a to 5d are cyclic voltammetry cycling profiles at different electrochemical cycles for the nickel oxide thin films prepared in example 1 of the present invention and comparative examples 1 to 3, respectively, wherein the coloration/discoloration voltages are +1.2V and-1.2V, respectively.
Fig. 6a and 6b are graphs comparing the coloring response time and the fading response time of the nickel oxide thin films prepared in example 1 and comparative example 2 of the present invention after 3000 electrochemical cycles, respectively.
FIG. 7 is EIS graphs of nickel oxide thin films according to example 1 and comparative example 2 after 3000 electrochemical cycles, wherein coloring/discoloring voltages were +1.2V and-1.2V, respectively.
Detailed Description
The purpose, technical solutions and advantages of the embodiments of the present invention are made clearer, and the technical solutions in the embodiments of the present invention are clearly and completely described. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
As one aspect of the technical solution of the present invention, a method for preparing a nickel oxide electrochromic film includes:
adopting magnetron sputtering technology to co-dope nickel oxide M x T y Ni z O is used as a cathode target material, argon and oxygen are used as working gases, wherein the oxygen and the argon are not less than 0.01-0.2: 1, a nickel oxide film is deposited on the surface of the substrate, wherein the first doping element M comprises at least one of zinc, tin and silicon, the second doping element T comprises at least one of aluminum, tungsten and niobium, and x, y and z are not less than 0.01-0.2: 0.4-0.7: 1; and the number of the first and second groups,
and annealing the obtained nickel oxide film to obtain the nickel oxide electrochromic film.
In some preferred embodiments, the magnetron sputtering technique employs process conditions including: the sputtering mode is radio frequency sputtering or intermediate frequency sputtering, the working gas is inert gas and oxygen, the matrix temperature is 25-200 ℃, the background vacuum degree of the reaction chamber is 1 multiplied by 10 -3 pa～1×10 -1 Pa, sputtering pressure of 0.4-2.0 Pa, and sputtering power density of 2.2W/cm 2 ～6.6W/cm 2 The deposition time is 15-40 min.
Further, inert gases include, but are not limited to, argon; preferably, oxygen: argon = (0.01-0.2): 1.
In some preferred embodiments, the preparation method comprises: putting the nickel oxide film into a rapid annealing device, heating to 500-700 ℃ at a heating rate of 20-80 ℃/s in the air atmosphere, preserving the heat for 2-8 min, cooling to room temperature at a cooling rate of 40-80 ℃/s, and taking out to obtain the nickel oxide electrochromic film.
Further, the substrate includes, but is not limited to, any one of ITO, FTO, AZO, GZO transparent conductive glass.
In some more specific embodiments, the preparation method of the nickel oxide electrochromic film adopts magnetron sputtering deposition, and specifically comprises the following steps:
1. magnetron sputtering deposition of nickel oxide films
Placing a co-doped nickel oxide target material in magnetron sputtering coating equipment, and depositing a nickel oxide film on a transparent conductive glass substrate, wherein the main parameters in the sputtering process are as follows:
(1) The sputtering mode is radio frequency sputtering or intermediate frequency sputtering, and the working gas is argon and oxygen, wherein oxygen and argon = (0.01-0.2) to 1 (volume ratio);
(2) The temperature of the substrate is 25-200 ℃;
(3) Background vacuum of 1X 10 -3 Pa～1×10 -1 pa；
(4) The sputtering air pressure value is 0.4-2.0 Pa;
(5) The power density of sputtering is 2.2W/cm 2 ～6.6W/cm 2 ；
(6) The thickness of the film is 100-300 nm;
wherein, the main component of the co-doped nickel oxide target material can be expressed as M x T y Ni z O, wherein the first doping element M is one of zinc, tin and silicon, the second doping element T is at least one of aluminum, tungsten and niobium, and the molar ratio of the components is as follows: x, y, z = (0.01-0.2): (0.4-0.7): 1.
2. High-temperature rapid annealing process treatment of nickel oxide film
And (2) placing the nickel oxide film prepared in the step (1) in a rapid annealing furnace, heating to 500-700 ℃ at the speed of 20-80 ℃/s in the air atmosphere, preserving the heat for 2-8 min, cooling to room temperature at the cooling rate of 40-80 ℃/s, and taking out to obtain the nickel oxide electrochromic film with a cubic phase structure. Preferably, the temperature decrease rate is not lower than the temperature increase rate.
The prepared nickel oxide electrochromic film has a smooth and compact surface, has a uniformly distributed microporous structure, and is at least used for providing a large number of channels for lithium ions to rapidly move in an electrochromic process.
Particularly, the technical scheme can promote the formation of a standard cubic phase structure of the film, particularly can promote the formation of a smooth and compact structure containing uniformly distributed micropore shapes, and the uniformly distributed micropore structures have larger specific surface areas, provide a large number of channels and reaction sites for lithium ions to rapidly move in the electrochromic process, and contribute to improving the electrochromic response speed of the film.
In some embodiments, the nickel oxide electrochromic film has a thickness of 100 to 300nm.
Furthermore, the transmittance of the nickel oxide electrochromic film in a fading state is more than 92.0% (550 nm condition), and the optical modulation amplitude is more than 22.6% (550 nm condition).
Furthermore, the nickel oxide electrochromic film has higher charge capacity which can reach 8.7 mC-cm at most -2 As described above.
Furthermore, the nickel oxide electrochromic film has high cycling stability, and after 3000 CV cycles, the nickel oxide film still keeps stable light modulation amplitude and high charge capacity.
Further, the nickel oxide electrochromic film has a fast coloring response time and a fast fading response time which are respectively less than 3.5s and 1.5s.
Another aspect of an embodiment of the present invention also provides a use of any one of the nickel oxide electrochromic films described above in the preparation of an electrochromic device.
For example, another aspect of the embodiments of the present invention also provides an ion storage layer, which includes the above nickel oxide electrochromic film.
In conclusion, the preparation method of the nickel oxide electrochromic film provided by the invention is favorable for providing sputtering stability, the obtained co-doped nickel oxide electrochromic film is of a standard cubic phase structure, has a smooth and crack-free surface and a uniformly distributed microporous structure, can provide a large number of channels and reaction sites for lithium ions to rapidly move in an electrochromic process, is favorable for improving the electrochromic response speed of the nickel oxide film, and simultaneously has high fading state transmittance, optical modulation amplitude, charge capacity and electrochemical cycle stability.
The technical solutions of the present invention will be described in further detail below with reference to several preferred embodiments and accompanying drawings, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. It is to be noted that the following examples are intended to facilitate the understanding of the present invention, and do not set forth any limitation thereto. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. The test methods in the following examples, which are not specified under specific conditions, are generally carried out under conventional conditions.
Example 1
The preparation method of the nickel oxide electrochromic film in the embodiment specifically comprises the following steps:
step 1, magnetron sputtering deposition of nickel oxide film
Co-doped nickel oxide target material M x T y Ni z Placing O in magnetron sputtering coating equipment, and depositing on an ITO transparent conductive glass substrate to obtain a nickel oxide film, wherein M is zinc, T is tungsten, x: v: z = 0.12: 0.5: 1, and the main parameters in the sputtering process are as follows:
(1) The sputtering mode is radio frequency sputtering, and the working gas is argon and oxygen, wherein the ratio of oxygen to argon is = 0.08: 1;
(2) The substrate temperature is 25 ℃;
(3) Background vacuum of 3X 10 -2 Pa；
(4) The sputtering air pressure value is 1.6Pa;
(5) The power density of sputtering is 3.5W/cm 2 The deposition time is 30min;
(6) The thickness of the film is 140nm;
step 2, rapid annealing treatment of nickel oxide film
And (2) placing the nickel oxide film prepared in the step (1) in a rapid annealing furnace, heating to 640 ℃ at the speed of 50 ℃/s in the air atmosphere, preserving the heat for 4min, cooling to room temperature at the cooling rate of 65 ℃/s, and taking out to obtain the nickel oxide electrochromic film.
Example 2
The preparation method of the nickel oxide electrochromic film in the embodiment specifically comprises the following steps:
step 1, magnetron sputtering deposition of nickel oxide film
Co-doped nickel oxide target material M x T y Ni z Placing O in magnetron sputtering coating equipment, and depositing on an ITO transparent conductive glass substrate to obtain a nickel oxide film, wherein M is silicon, T is tungsten, x: y: z = 0.2: 0.4: 1, and the main parameters in the sputtering process are as follows:
(1) The sputtering mode is radio frequency sputtering, and the working gas is argon and oxygen, wherein the ratio of oxygen to argon is = 0.1: 1;
(2) The substrate temperature is 25 ℃;
(3) Background vacuum of 5X 10 -2 Pa；
(4) The sputtering air pressure value is 2.0Pa;
(5) The power density of sputtering is 4.0W/cm 2 The deposition time is 25min;
(6) The thickness of the film is 120nm;
step 2, rapid annealing treatment of nickel oxide film
And (2) placing the nickel oxide film prepared in the step (1) in a rapid annealing furnace, heating to 400 ℃ at the speed of 80 ℃/s in the air atmosphere, preserving the heat for 3min, cooling to room temperature at the cooling rate of 80 ℃/s, and taking out to obtain the novel nickel oxide electrochromic film.
Comparative example 1
This comparative example is different from example 1 in that the high temperature rapid annealing process of step 2 is not performed.
Comparative example 2
This comparative example is compared to example 1, except that an undoped nickel oxide target was used.
Comparative example 3
Compared with the embodiment 1, the comparison example has the difference that the undoped nickel oxide target material is adopted, and the high-temperature rapid annealing process treatment of the step 2 is not carried out.
The following respectively performs performance characterization on the nickel oxide electrochromic films prepared in the above examples and comparative examples, including phase structure of the film, surface morphology of the film, optical modulation amplitude of the film, electrochromic response time, electrochemical characteristics, and cycle stability. Specifically, an X-ray diffractometer (XRD) is used for observing the phase structure of the film, a Scanning Electron Microscope (SEM) is used for observing the surface morphology of the film, an ultraviolet-visible spectrophotometer is used for measuring the optical modulation amplitude and electrochromic response time of the film, and an electrochemical workstation is used for measuring the electrochemical properties, the cycle stability and other electrochromic performances of the film.
Referring to fig. 1, XRD patterns of the nickel oxide electrochromic films prepared in example 1 and comparative examples 1 to 3, in which the test 2 theta angle is 20 to 80 deg., as seen by the XRD patterns, example 1 using co-doped nickel oxide M x T y Ni z The method of taking O as the cathode target can promote the nickel oxide film to realize the formation of (200) and (220) crystalline cubic phase structures, and is favorable for stable electrochromic reaction.
FIG. 2a is a surface SEM image of the nickel oxide electrochromic film prepared in example 1, wherein the surface of the nickel oxide electrochromic film has a large number of uniformly distributed microporous structures and is smooth and crack-free; fig. 2b and 2d are surface SEM images of the nickel oxide electrochromic thin films prepared in comparative examples 2 and 3, which have a dense surface structure and no significant pores, and fig. 2c is a surface SEM image of the nickel oxide electrochromic thin film prepared in comparative example 2, which has a large number of cracks on the surface thereof. Obviously, by comparison, the microporous and smooth surface crack-free structure of the nickel oxide electrochromic film obtained by the technical scheme of example 1 provides a large number of channels and reaction sites for the rapid movement of lithium ions in the electrochromic process, which is helpful for improving the electrochromic response speed of the film.
FIGS. 3a and 3b are SEM images of the surfaces of the electrochromic nickel oxide films prepared in example 1 and comparative examples 1 to 3, respectively, after 3000 cyclic voltammetry tests, wherein the cyclic voltammetry tests employ a voltage ranging from-1.2 to 1.2V and a sweep rate of 50mV/s. Referring to FIG. 3a, and comparing with FIGS. 3 b-3 d, the surface topography of the film does not change significantly after several thousand cycles of cyclic voltammetry; while the surfaces of the films of comparative examples 1 to 3 were significantly changed, the surface structures of the films of comparative examples 1 and 2 became denser and the ion transport channels were blocked, compared with fig. 2a, and the surfaces of the films of comparative example 3 were cracked.
Fig. 4a and 4b-d are graphs of the coloring and fading transmittances at 550nm of the nickel oxide electrochromic films prepared in example 1 and comparative examples 1-3, respectively, at different numbers of electrochemical cycles.
Referring to fig. 4a, at a wavelength of 550nm, the faded state transmittance of the nickel oxide electrochromic film prepared in example 1 was 92.0% and the optical modulation amplitude was 22.6%. Referring to fig. 4b, the as-faded state transmittances of the films prepared in comparative examples 1-3 were 91.1%,87.4%, and 87.2%, respectively, and the optical modulation amplitudes were 19.1%,14.3%, and 11%, respectively, at a wavelength of 550 nm. Obviously, the technical solution of example 1 can significantly increase the transmittance and the optical modulation amplitude of the faded state of nickel oxide.
Fig. 5a and 5b-d are cyclic voltammetry graphs for different numbers of electrochemical cycles of the nickel oxide electrochromic films prepared in example 1 and comparative examples 1-3 according to the present invention, respectively, in which the coloration/discoloration voltages are +1.2V and-1.2V, respectively.
The cyclic stability and charge capacity of the nickel oxide films of comparative example 1 and comparative examples 1-3, respectively, were determined after 3000 cyclic voltammetry tests. See table 1 for results.
First, charge capacity performance comparison: the charge capacity of the nickel oxide electrochromic film of example 1 after 3000 CV cycles prepared in example 1 was 8.7mC · cm -2 While the charge capacities of the nickel oxide electrochromic films prepared in comparative examples 1 to 3 were 3.5mC · cm, respectively -2 ，4.8mC·cm -2 And 5.0 mC.cm -2 . By way of comparison, the nickel oxide electrochromic film prepared in example 1 had the following characteristics compared with comparative examples 1 to 3Higher charge capacity.
Further, the cycle stability performance was compared: after 3000 CV cycles, the nickel oxide electrochromic films of examples 1 and 2 still maintained stable optical modulation and charge capacity.
By comparing example 1 with comparative examples 1 to 3, the nickel oxide electrochromic film provided in comparative example 1 began to stabilize after the first 100 times started to decay as the number of cycles slowly increased; the nickel oxide electrochromic film prepared in comparative example 2 decayed in the first 100 times; comparative example 3 shows that the initial 10 times of gradual enhancement in CV cycle, the attenuation starts after 10 times of gradual enhancement, the later trend is stable, and the stability fluctuation is large; while 3000 circles of the nickel oxide electrochromic film prepared in example 1 was stable continuously, it is apparent that example 1 exhibited more excellent cycle stability than comparative examples 1 to 3.
It is apparent that the transmittance, response time, charge capacity, and cycle stability of examples 1-2 are all excellent as analyzed by the results of the property measurements in table 1. The charge capacity and cycle stability of comparative examples 1-3 clearly performed poorly.
By comparing the response time of the example with that of the comparative example 2, the response time of the example 1 in the colored state and the faded state is 3.5s and 1.5s respectively, and compared with the comparative example 2 and the prior art (Chinese patent CN 112456813A), the optimization effect is very obvious.
Further, referring to fig. 6a and 6b, which are the response time of the discoloration and fading of the nickel oxide electrochromic films prepared in example 1 and comparative example 2 according to the present invention after 3000 electrochemical cycles, respectively, the time for coloring and fading of the nickel oxide film of example 1 was 3.5s and 1.5s, respectively, while the time for coloring and fading of the nickel oxide electrochromic film prepared in comparative example 2 was 19.8s and 3.5s, respectively. It is apparent that the nickel oxide electrochromic film prepared in example 1 has a fast color-fading response time.
FIG. 7 is EIS graphs of the nickel oxide electrochromic films prepared in example 1 and comparative example 2 of the present invention after 3000 electrochemical cycles, respectively, at coloring/discoloring voltages of +1.2V and-1.2V; among them, the transfer resistances of the colored state and the faded state of the nickel oxide electrochromic film prepared in example 1 were 25.3 Ω and 10.0 Ω, respectively, while the transfer resistances of the nickel oxide electrochromic film prepared in comparative example 2 were 46.2 Ω and 24.6 Ω, respectively. It is apparent that the nickel oxide electrochromic film prepared in example 1 has a much lower transfer resistance than that of the nickel oxide electrochromic film of comparative example 2, and because of this, example 1 has a faster color-fading response time than comparative example 2.
TABLE 1 results of performance testing of examples and comparative examples
Compared with the prior art, the result promotes the nickel oxide electrochromic film to form a standard cubic phase structure by optimizing the doped element types and the film deposition process, and the nickel oxide electrochromic film has uniformly distributed micropores and a structure with a smooth and compact surface, and the uniformly distributed porous structure has a large specific surface area, so that a large number of channels are provided for the lithium ions to rapidly move in the electrochromic process, and the improvement of the electrochromic response speed of the film is facilitated; and simultaneously, a high-temperature rapid annealing process is adopted, so that the electrochemical cycling stability of the nickel oxide electrochromic film is further improved.
In summary, the nickel oxide electrochromic film prepared in the embodiment is used for preparing the ion storage layer, and is applied to the electrochromic device, so that the nickel oxide electrochromic film can provide the characteristics of quick response and stable cycle performance of more than 3000 circles for the electrochromic device, and has excellent optical and electrical properties.
Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the compositions taught by the present invention also consist essentially of, or consist of, the recited components, and that the processes taught by the present invention also consist essentially of, or consist of, the recited process steps.
The use of the terms including, having, etc. are generally to be construed as open-ended and not limiting unless otherwise specifically stated.
It should be understood that the order of steps or order of performing particular actions is not critical, as long as the present teachings remain operable. Further, two or more steps or actions may be performed simultaneously.
In addition, the inventors of the present invention have also made experiments with other raw materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
The above is only a preferred embodiment of the present invention, and it is not therefore intended to limit the scope of the present invention, and various modifications and variations of the present invention are possible to those skilled in the art. Variations, modifications, substitutions, integrations and parameter changes of the embodiments may be made without departing from the principle and spirit of the invention, which may be within the spirit and principle of the invention, by conventional substitution or may realize the same function.
Claims (10)
1. A preparation method of a fast-response nickel oxide electrochromic film is characterized by comprising the following steps:
s1, deposition of nickel oxide film
Co-doping with M by magnetron sputtering x T y Ni z O is used as a cathode target material, and a nickel oxide film is deposited on the surface of the transparent glass substrate, wherein the first doping element M comprises at least one of zinc, tin and silicon, the second doping element T comprises at least one of aluminum, tungsten and niobium, and x: y: z = (0.01-0.2): (0.4-0.7): 1;
s2, annealing process treatment of nickel oxide film
Carrying out high-temperature rapid annealing process treatment on the nickel oxide film prepared in the step S1 to obtain a nickel oxide electrochromic film;
the nickel oxide electrochromic film is of a standard cubic phase structure, the surface of the nickel oxide electrochromic film is smooth and has uniformly distributed microporous structures, and in the electrochromic process, the microporous structures provide channels and reaction sites for the rapid movement of lithium ions.
2. The method for preparing the fast-response nickel oxide electrochromic film according to claim 1, wherein in S2, the high-temperature fast annealing process comprises heating the nickel oxide film to 500-700 ℃ at a heating rate of 20-80 ℃/S in an air atmosphere, and then keeping the temperature for 2-8 min; then cooling to room temperature at a cooling rate of 40-80 ℃/s to obtain the nickel oxide electrochromic film; wherein the cooling rate is not lower than the heating rate.
3. The method for preparing a fast-response nickel oxide electrochromic film according to claim 1, wherein in S1, a mixed gas of an inert gas and oxygen is used as a working gas; the inert gas is argon; the volume ratio of oxygen to argon is (0.01-0.2) to 1.
4. The method for preparing the fast-response nickel oxide electrochromic film according to claim 1, wherein in S1, the magnetron sputtering technique comprises: the sputtering mode is radio frequency sputtering or intermediate frequency sputtering, the temperature of the matrix is 25-200 ℃, the background vacuum degree of the reaction chamber is 1.0 multiplied by 10 -3 ～1.0×10 -1 Pa, sputtering pressure is 0.4-2.0 Pa, and sputtering power density is 2.2-6.6W/cm 2 The deposition time is 15-40 min.
5. The method for preparing a fast-response nickel oxide electrochromic film according to claim 1, characterized in that: the substrate comprises transparent conductive glass, including any one of ITO, FTO, AZO and GZO conductive glass.
6. A fast-response nickel oxide electrochromic film prepared by the preparation method of the fast-response nickel oxide electrochromic film as claimed in any one of claims 1 to 5.
7. The fast-response nickel oxide electrochromic film according to claim 6, wherein the fast-response nickel oxide electrochromic film comprisesThe thickness of the nickel oxide electrochromic film is 100-300 nm; and/or, the nickel oxide electrochromic film has a faded state transmittance of more than 92%, an optical modulation amplitude of more than 22% and a charge capacity of 8.7mC cm under the condition of a wavelength of 550nm -2 The above; and/or the coloring response time of the nickel oxide electrochromic film is as low as 3.5s, the fading response time is as low as 1.5s, and the electrochemical cycling stability is higher than 3000 circles.
8. Use of the nickel oxide electrochromic thin film according to claim 6 or 7 for the preparation of an electrochromic device.
9. An ion storage layer comprising the nickel oxide electrochromic film according to claim 7 or 8.
10. An electrochromic device comprising the ion storage layer according to claim 9.
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