CN111045268B - All-solid-state electrochromic device with fluoride as electrolyte layer and preparation method thereof - Google Patents
All-solid-state electrochromic device with fluoride as electrolyte layer and preparation method thereof Download PDFInfo
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Abstract
An all-solid-state electrochromic device taking fluoride as an electrolyte layer and a preparation method thereof relate to an all-solid-state electrochromic device and a preparation method thereof. The invention aims to solve the problems of low ionic conductivity, slow deposition rate, poor safety and low transmittance of an electrolyte layer of the existing all-solid-state electrochromic device. An all-solid-state electrochromic device with fluoride as an electrolyte layer comprises a substrate, a bottom transparent conducting layer, an electrochromic layer, a fluoride electrolyte layer, an ion storage layer and a top transparent conducting layer. The method comprises the following steps: 1. sequentially depositing a bottom transparent conductive layer and an electrochromic layer on a substrate; 2. taking fluoride as an evaporation material, and depositing a fluoride electrolyte layer on the electrochromic layer; 3. an ion storage layer and a top transparent conductive layer are sequentially deposited on the fluoride electrolyte layer. The invention can obtain the all-solid-state electrochromic device taking fluoride as the electrolyte layer.
Description
Technical Field
The invention relates to an all-solid-state electrochromic device and a preparation method thereof.
Background
Electrochromism refers to a phenomenon in which the optical properties of a material are reversibly changed by an applied voltage or current. In appearance, the reversible change of the optical transmittance and the reflection color of the material is mainly shown, and in the micro scale, the change of the microstructure and the energy band structure of the material is mainly shown. Materials capable of generating an electrochromic phenomenon are called electrochromic materials.
The electrochromic material mainly comprises a part of transition metal oxide, a part of organic polymer and micromolecules. Among these devices, all-solid-state electrochromic devices, such as anti-glare automobile rearview mirrors, electrochromic smart windows, aircraft windows, etc., have been widely used in various aspects of life due to their long cycle life and good cycle stability. In addition, the electrochromic device also has great application potential in the aspects of display, aerospace thermal control and the like.
At present, the preparation of the electrolyte of the all-solid-state electrochromic device generally comprises three methods: (1) preparation using metallic lithium. However, the storage and preparation of lithium metal is dangerous, and thus, the use of lithium metal is restricted. (2) preparing by using lithium-containing salts. However, because of the poor conductivity of lithium-containing salts, the salts are mainly prepared by a radio frequency sputtering method at present, and the deposition rate is slow, so that the salts are not suitable for industrial production. For example, cao Zhenhu Li is prepared by radio frequency magnetron sputtering methodXSiYRezSmOnAlthough the prepared electrolyte has high ionic conductivity, the electrolyte is not beneficial to industrial production due to long time consumption (patent number: CN 201611244662.9). And (3) preparing by using lithium alloy. Although lithium alloys solve the problem of deposition rate, the problem of safety is not completely solved. For example, yu Xiao uses a method of DC sputtering Li-Mg alloy to prepare LixMgyThe content of Li in N-electrolyte, li-Mg alloy is still high (20 wt%), and the safety problem still remains (Electro-optical performance of inorganic monolithic electronic device with a pulsed DC divided LixMgyN ion conductor[J]Journal of Solid State Electrochemistry,2018, 22. Li-Zn-Mg alloy sputtering preparation of Li by cunning gang et alxMgyN electrolyte and alloy are relatively complex to prepare, and meanwhile, the content of Li is still high, so that the application of the N electrolyte in industry is restricted (patent number: CN 201710333860.0). Linglin Xie adopts a method of DC sputtering Li-Al alloy to prepare LixAlOzThe problems of electrolyte and safety still exist.
In summary, the preparation method of the electrolyte of the existing all-solid-state electrochromic device has the defects, so that the application of the all-solid-state electrochromic device is restricted, and in addition, the transmittance of the existing all-solid-state electrochromic device is poor.
Disclosure of Invention
The invention aims to solve the problems of low ionic conductivity, slow deposition rate, poor safety in the preparation process and low transmittance of an electrolyte layer of the conventional all-solid-state electrochromic device, and provides an all-solid-state electrochromic device taking fluoride as the electrolyte layer and a preparation method thereof.
An all-solid-state electrochromic device with fluoride as an electrolyte layer comprises a substrate, a bottom transparent conducting layer, an electrochromic layer, a fluoride electrolyte layer, an ion storage layer and a top transparent conducting layer; the substrate is sequentially provided with a bottom transparent conducting layer, an electrochromic layer, a fluoride electrolyte layer, an ion storage layer and a top transparent conducting layer from bottom to top.
A preparation method of an all-solid-state electrochromic device taking fluoride as an electrolyte layer is completed according to the following steps:
1. sequentially depositing a bottom transparent conductive layer and an electrochromic layer on a substrate by adopting a vacuum coating method, a magnetron sputtering method, a vacuum thermal evaporation method or an electron beam evaporation method;
the deposition rate of the bottom transparent conductive layer in the first step is 0.1-10 angstrom/s, and the thickness is 50-200 nm; the deposition rate of the electrochromic layer is 0.1-10 angstrom/s, and the thickness is 100-800 nm;
2. fluoride is used as evaporating material, the evaporating material is placed in an evaporating crucible or an evaporating boat in an evaporating chamber, the substrate deposited with the conductive layer and the electrochromic layer is placed on a sample rotating platform of the evaporating chamber, and the evaporating chamber is vacuumized until the degree of vacuum is less than 5.0 x 10-3Pa; evaporating by adopting an electron beam or a resistor, wherein the evaporation rate is 0.1-10 angstrom/s, the evaporation thickness is 50-400 nm, a fluoride electrolyte layer is deposited on the electrochromic layer, and the distance between the sample rotating platform and the evaporation material is 15-50 cm;
the fluoride in the second step is LiF, naF and MgF2、CaF2Or AlF3；
3. Sequentially depositing an ion storage layer and a top transparent conductive layer on the fluoride electrolyte layer by adopting a vacuum coating method, a magnetron sputtering method, a vacuum thermal evaporation method or an electron beam evaporation method;
the deposition rate of the ion storage layer in the third step is 0.1-10 angstrom/s, and the thickness is 100-800 nm; the deposition rate of the top transparent conductive layer is 0.1-10A/s and the thickness is 50-200 nm.
The principle and the advantages of the invention are as follows:
1. the fluoride has excellent stability, a wide electrochemical window, high ionic conductivity and high light transmittance in ultraviolet, visible and near infrared spectrums, and the inorganic electrochromic fluoride electrolyte is prepared by adopting an evaporation method, so that large-scale safe and rapid production of large-size electrochromic devices is possible;
2. the invention adopts a vacuum thermal evaporation mode, and optimizes the performance of the electrolyte layer by adjusting the evaporation rate, the thickness of the deposited film and the type of the evaporation material;
3. the fluoride electrolyte layer of the all-solid-state electrochromic device is prepared by adopting a vacuum thermal evaporation method, so that the safety problem of preparation by using lithium metal and lithium alloy is solved, the deposition rate is high, and the components and properties of the prepared electrolyte are stable, so that the electrochromic device can be quickly, stably and accurately controlled in thickness and can be produced at low production cost;
4. the fluoride electrolyte layer prepared by the invention has a transmittance in the visible near infrared of more than 90%, the all-solid-state electrochromic device taking fluoride as the electrolyte layer has a transmittance in the visible near infrared of more than 70%, and the optical modulation range is more than 40%;
5. the response time of the all-solid-state electrochromic device with fluoride as the electrolyte layer prepared by the invention is less than 20s.
The invention can obtain the all-solid-state electrochromic device taking fluoride as the electrolyte layer.
Drawings
Fig. 1 is an SEM image of the LiF electrolyte layer in the all-solid-state electrochromic device with fluoride as the electrolyte layer prepared in the first example;
FIG. 2 is an SEM image of a cross section of an all-solid-state electrochromic device with a fluoride electrolyte layer prepared in the first example;
FIG. 3 is a graph showing the change of the bleaching transmittance with time of an all-solid electrochromic device prepared in the first example and using fluoride as an electrolyte layer;
FIG. 4 is a graph showing the transmittance spectra of an all-solid electrochromic device prepared in the first example in which a fluoride compound is used as an electrolyte layer in a colored state and a bleached state, wherein 1 is colored and 2 is bleached;
FIG. 5 is MgF of all-solid-state electrochromic device with fluoride as electrolyte prepared in example two2SEM image of electrolyte layer.
Detailed Description
The first embodiment is as follows: the embodiment is an all-solid-state electrochromic device taking fluoride as an electrolyte layer, which comprises a substrate, a bottom transparent conducting layer, an electrochromic layer, a fluoride electrolyte layer, an ion storage layer and a top transparent conducting layer; the substrate is sequentially provided with a bottom transparent conducting layer, an electrochromic layer, a fluoride electrolyte layer, an ion storage layer and a top transparent conducting layer from bottom to top.
The principle and advantages of this embodiment:
1. the fluoride has excellent stability, a wide electrochemical window, high ionic conductivity and high light transmittance in ultraviolet, visible and near infrared spectrums, and the inorganic electrochromic fluoride electrolyte is prepared by adopting an evaporation method in the embodiment, so that large-scale safe and rapid production of large-size electrochromic devices is possible;
2. the performance of the electrolyte layer is optimized by adopting a vacuum thermal evaporation mode and adjusting the evaporation rate, the thickness of a deposited film and the type of an evaporation material;
3. the fluoride electrolyte layer of the all-solid-state electrochromic device is prepared by adopting a vacuum thermal evaporation method, so that the safety problem of preparation by using lithium metal and lithium alloy is solved, meanwhile, the deposition rate is high, and the components and properties of the prepared electrolyte are stable, so that the electrochromic device can be produced quickly, stably and accurately by controlling the thickness and with low production cost;
4. the fluoride electrolyte layer prepared by the embodiment has the transmittance of more than 90% in the visible near infrared, the all-solid-state electrochromic device taking fluoride as the electrolyte layer has the transmittance of more than 70% in the visible near infrared, and the optical modulation range is more than 40%;
5. the response time of the all-solid-state electrochromic device with the fluoride as the electrolyte layer prepared by the embodiment is less than 20s.
This embodiment mode can obtain an all-solid-state electrochromic device using a fluoride as an electrolyte layer.
The second embodiment is as follows: the present embodiment differs from the present embodiment in that: the substrate is a heat-resistant substrate or a flexible substrate; the heat-resistant substrate is glass; the flexible substrate is polyethylene terephthalate or polydimethylsiloxane. Other steps are the same as in the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: the bottom transparent conductive layer is an ITO layer, an FTO layer, an AZO layer or a nano Ag wire layer. The other steps are the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment and one of the first to third embodiments is as follows: the electrochromic layer is WO3Layer, moO3Layer, V2O5Layer or CrO2And (3) a layer. The other steps are the same as those in the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: the fluoride electrolyte layer is a LiF layer, a NaF layer and MgF2Layer, caF2Layer or AlF3And (3) a layer. The other steps are the same as those in the first to fourth embodiments.
The sixth specific implementation mode is as follows: the difference between this embodiment and one of the first to fifth embodiments is as follows: the ion storage layer is NiO layer or TiO layer2Layer or V2O5And (3) a layer. The other steps are the same as those in the first to fifth embodiments.
The seventh concrete implementation mode: the difference between this embodiment and one of the first to sixth embodiments is: the top transparent conducting layer is an ITO layer, an FTO layer, an AZO layer or a nano Ag wire layer. The other steps are the same as those in the first to sixth embodiments.
The specific implementation mode is eight: the difference between this embodiment and one of the first to seventh embodiments is: the thickness of the fluoride electrolyte layer is 50 nm-400 nm. The other steps are the same as those in the first to seventh embodiments.
The specific implementation method nine: the difference between this embodiment and the first to eighth embodiments is: the thickness of the bottom transparent conducting layer is 50 nm-200 nm, the thickness of the electrochromic layer is 100 nm-800 nm, the thickness of the fluoride electrolyte layer is 50 nm-400 nm, the thickness of the ion storage layer is 100 nm-800 nm, and the thickness of the top transparent conducting layer is 50 nm-200 nm. The other steps are the same as those in the first to eighth embodiments.
The detailed implementation mode is ten: the embodiment is a preparation method of an all-solid-state electrochromic device taking fluoride as an electrolyte layer, and the preparation method is completed according to the following steps:
1. sequentially depositing a bottom transparent conductive layer and an electrochromic layer on a substrate by adopting a vacuum coating method, a magnetron sputtering method, a vacuum thermal evaporation method or an electron beam evaporation method;
the deposition rate of the bottom transparent conductive layer in the first step is 0.1-10 angstrom/s, and the thickness is 50-200 nm; the deposition rate of the electrochromic layer is 0.1-10 angstrom/s, and the thickness is 100-800 nm;
2. fluoride is used as evaporating material, the evaporating material is placed in an evaporating crucible or an evaporating boat in an evaporating chamber, the substrate deposited with the conductive layer and the electrochromic layer is placed on a sample rotating table of the evaporating chamber, and the evaporating chamber is vacuumized until the degree of vacuum pumping is less than 5.0 multiplied by 10-3Pa; then adopting electron beam or resistance to evaporate, the evaporation rate is 0.1-10 angstrom/s, the evaporation thickness is 50-400 nm, and the fluoride electrolyte is deposited on the electrochromism layerThe distance between the sample rotating platform and the evaporation material is 15 cm-50 cm;
the fluoride in the second step is LiF, naF and MgF2、CaF2Or AlF3；
3. Sequentially depositing an ion storage layer and a top transparent conductive layer on the fluoride electrolyte layer by adopting a vacuum coating method, a magnetron sputtering method, a vacuum thermal evaporation method or an electron beam evaporation method;
the deposition rate of the ion storage layer in the third step is 0.1-10 angstrom/s, and the thickness is 100-800 nm; the deposition rate of the top transparent conductive layer is 0.1-10A/s and the thickness is 50-200 nm.
The concrete implementation mode eleven: the present embodiment is different from the fifth embodiment in that: in the second step, fluoride is used as an evaporation material, the evaporation material and the substrate deposited with the conductive layer and the electrochromic layer are placed on a sample rotating table of an evaporation chamber, and then the evaporation chamber is vacuumized until the degree of vacuum pumping is less than 5.0 multiplied by 10-3Pa; evaporating by adopting an electron beam or a resistor, wherein the evaporation rate is 10 angstroms per second, the evaporation thickness is 400nm, a fluoride electrolyte layer is deposited on the electrochromic layer, and the distance between the sample rotating platform and the evaporation material is 50cm; the fluoride is AlF3. The rest is the same as the embodiment.
The detailed implementation mode is twelve: the present embodiment is different from the fifth embodiment in that: in the second step, fluoride is used as an evaporation material, the evaporation material and the substrate deposited with the conductive layer and the electrochromic layer are placed on a sample rotating table of an evaporation chamber, and then the evaporation chamber is vacuumized until the degree of vacuum pumping is less than 5.0 multiplied by 10-3Pa; evaporating by adopting an electron beam or a resistor, wherein the evaporation rate is 5 angm/s, the evaporation thickness is 250nm, a fluoride electrolyte layer is deposited on the electrochromic layer, and the distance between the sample rotating platform and an evaporation material is 30cm; the fluoride is CaF2. The others are the same as the embodiments ten to eleven.
The specific implementation mode is thirteen: the present embodiment is different from the fifth embodiment in that: step twoThe method comprises placing the evaporation material and the substrate with the conductive layer and electrochromic layer on a sample rotary table of an evaporation chamber, and vacuumizing the evaporation chamber to vacuum degree less than 5.0 × 10-3Pa; evaporating by adopting an electron beam or a resistor, wherein the evaporation rate is 0.1 angstrom/second, the evaporation thickness is 50nm, a fluoride electrolyte layer is deposited on the electrochromic layer, and the distance between the sample rotating platform and the evaporation material is 15cm; the fluoride in the second step is NaF. The others are the same as the embodiments ten to twelve.
The following examples were used to demonstrate the beneficial effects of the present invention:
the first embodiment is as follows: a preparation method of an all-solid-state electrochromic device taking fluoride as an electrolyte layer is completed according to the following steps:
1. sequentially depositing a bottom transparent conductive layer and an electrochromic layer on a substrate by adopting a vacuum thermal evaporation method;
the deposition rate of the bottom transparent conductive layer in the first step is 2 angstroms/second, and the thickness is 150nm; the deposition rate of the electrochromic layer was 2 angstrom/sec and the thickness was 450nm;
the bottom transparent conductive layer in the first step is an ITO layer;
the electrochromic layer in the step one is WO3A layer;
2. fluoride is used as evaporating material, the evaporating material is placed in an evaporating crucible or an evaporating boat in an evaporating chamber, the substrate deposited with the conductive layer and the electrochromic layer is placed on a sample rotating table of the evaporating chamber, and the evaporating chamber is vacuumized until the degree of vacuum pumping is less than 5.0 multiplied by 10-3Pa; evaporating by adopting an electron beam or a resistor, wherein the evaporation rate is 0.1 angm/s, the evaporation thickness is 100nm, a fluoride electrolyte layer is deposited on the electrochromic layer, and the distance between the sample rotating platform and an evaporation material is 15cm;
the fluoride in the second step is LiF;
3. sequentially depositing an ion storage layer and a top transparent conductive layer on the fluoride electrolyte layer by adopting a vacuum thermal evaporation method;
the ion storage layer in the step three is a NiO layer;
the top transparent conductive layer in the third step is an ITO layer;
the deposition rate of the ion storage layer in the third step is 2 angstrom/second, and the thickness is 250nm; the top transparent conductive layer was deposited at a rate of 2 angstroms/second and a thickness of 150nm.
Fig. 1 is an SEM image of the LiF electrolyte layer in the all-solid-state electrochromic device with fluoride as the electrolyte layer prepared in the first example;
as can be seen from fig. 1, the surface of the LiF film exhibits particles of uniform size.
FIG. 2 is an SEM image of a cross section of an all-solid-state electrochromic device with a fluoride electrolyte layer prepared in the first example;
as can be seen from fig. 2, the cross-sectional delamination of the all-solid-state electrochromic device prepared in the first example, which uses fluoride as the electrolyte layer, is not very obvious, and is beneficial to ion transport.
The test method of the all-solid-state electrochromic device with fluoride as the electrolyte layer prepared in the first embodiment is as follows: the chronoamperometric curve of the device was measured using an electrochemical workstation (CHI 660E), and the curve of the discolored transmittance of the device with time and the graphs of the transmittance spectra of the colored state and the discolored state of the device were measured using a visible near-infrared spectrophotometer (MAYA 2000-Pro, ocean Optics), and the test results thereof are shown in fig. 3 and 4.
FIG. 3 is a graph showing the change of the bleaching transmittance with time of an all-solid electrochromic device prepared in the first example and using fluoride as an electrolyte layer;
as can be seen from fig. 3, the all-solid-state electrochromic device using fluoride as the electrolyte layer prepared in example one has good cycle stability, and after 300 cycles, the attenuation of the device is less than 3%.
FIG. 4 is a spectrum of transmittance spectra of a colored state and a bleached state of an all-solid-state electrochromic device using fluoride as an electrolyte layer, prepared in example one, wherein 1 is colored and 2 is bleached;
as can be seen from fig. 4, the average transmittance of the all-solid-state electrochromic device using fluoride as the electrolyte layer prepared in the first example is lower than 30% in the colored state, the average transmittance of the faded state is about 70%, and the optical modulation range is greater than 40%.
The response time of the all-solid-state electrochromic device prepared in example one and using fluoride as the electrolyte layer was 9.6s (coloration) and 4.0s (discoloration).
Example two: a preparation method of an all-solid-state electrochromic device taking fluoride as an electrolyte layer is completed according to the following steps:
1. sequentially depositing a bottom transparent conductive layer and an electrochromic layer on a substrate by adopting a vacuum thermal evaporation method;
the deposition rate of the bottom transparent conductive layer in the first step is 5 angstroms/second, and the thickness is 150nm; the deposition rate of the electrochromic layer was 5 angstroms/second and the thickness was 400nm;
the bottom transparent conducting layer in the first step is an FTO layer;
the electrochromic layer in the step one is MoO3A layer;
2. fluoride is used as evaporating material, the evaporating material is placed in an evaporating crucible or an evaporating boat in an evaporating chamber, the substrate deposited with the conductive layer and the electrochromic layer is placed on a sample rotating table of the evaporating chamber, and the evaporating chamber is vacuumized until the degree of vacuum pumping is less than 5.0 multiplied by 10-3Pa; evaporating by adopting an electron beam or a resistor, wherein the evaporation rate is 5 angm/s, the evaporation thickness is 250nm, a fluoride electrolyte layer is deposited on the electrochromic layer, and the distance between the sample rotating platform and an evaporation material is 30cm;
the fluoride in the second step is MgF2；
3. Sequentially depositing an ion storage layer and a top transparent conductive layer on the fluoride electrolyte layer by adopting a vacuum thermal evaporation method;
the deposition rate of the ion storage layer in the third step is 5 angstroms/second, and the thickness is 300nm; the top transparent conductive layer was deposited at a rate of 5 angstroms/second and a thickness of 150nm.
FIG. 5 is MgF of all-solid-state electrochromic device with fluoride as electrolyte prepared in example two2SEM images of the electrolyte layer;
from FIG. 5, it can be seen that，MgF2The surface of the film presents uniformly sized particles.
The response time of the all-solid-state electrochromic device prepared in example two, which uses fluoride as the electrolyte layer, was 17.6s (coloration) and 15.4s (discoloration).
Claims (1)
1. A preparation method of an all-solid-state electrochromic device taking fluoride as an electrolyte layer is characterized by comprising the following steps:
1. sequentially depositing a bottom transparent conductive layer and an electrochromic layer on a substrate by adopting a vacuum thermal evaporation method;
the deposition rate of the bottom transparent conductive layer in the first step is 2 angstroms/second, and the thickness is 150nm; the deposition rate of the electrochromic layer was 2 angstroms/second and the thickness was 450nm;
the bottom transparent conductive layer in the first step is an ITO layer;
the electrochromic layer in the step one is WO3A layer;
2. fluoride is used as evaporating material, the evaporating material is placed in an evaporating crucible or an evaporating boat in an evaporating chamber, the substrate deposited with the conductive layer and the electrochromic layer is placed on a sample rotating table of the evaporating chamber, and the evaporating chamber is vacuumized until the degree of vacuum pumping is less than 5.0 multiplied by 10-3Pa; evaporating by adopting an electron beam or a resistor, wherein the evaporation rate is 0.1 angstrom/second, the evaporation thickness is 100nm, a fluoride electrolyte layer is deposited on the electrochromic layer, and the distance between the sample rotating platform and the evaporation material is 15cm;
the fluoride in the second step is LiF;
3. sequentially depositing an ion storage layer and a top transparent conductive layer on the fluoride electrolyte layer by adopting a vacuum thermal evaporation method;
the ion storage layer in the step three is a NiO layer;
the top transparent conductive layer in the third step is an ITO layer;
the deposition rate of the ion storage layer in the third step is 2 angstrom/second, and the thickness is 250nm; the deposition rate of the top transparent conductive layer was 2 angstroms/second and the thickness was 150nm;
the all-solid-state electrochromic device taking fluoride as the electrolyte layer has good cycling stability, and the attenuation of the device is less than 3% after 300 cycles;
the average transmittance of the all-solid-state electrochromic device taking fluoride as an electrolyte layer in a coloring state is lower than 30%, the average transmittance of a fading state is 70%, and the optical modulation range is larger than 40%;
the coloring response time of the all-solid-state electrochromic device taking fluoride as the electrolyte layer is 9.6s, and the fading response time is 4.0s.
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| CN103777424A (en) * | 2012-10-17 | 2014-05-07 | 珠海兴业绿色建筑科技有限公司 | Photochromic device |
| CN104423114B (en) * | 2013-09-05 | 2018-03-06 | 华为技术有限公司 | A kind of full-solid electrochromic multiple device and preparation method thereof |
| CN104593723A (en) * | 2015-01-21 | 2015-05-06 | 中国科学院光电技术研究所 | Method for increasing timeliness of AlF<3> film prepared by utilizing heat evaporation at deep ultraviolet and vacuum ultraviolet wavebands |
| CN105399343A (en) * | 2015-11-20 | 2016-03-16 | 常熟市光学仪器有限责任公司 | Optical glass composite membrane and coating technology |
| CN206608049U (en) * | 2017-01-06 | 2017-11-03 | 张婷 | A kind of light pollution preventive window |
| CN110161607A (en) * | 2018-02-13 | 2019-08-23 | 张家港康得新光电材料有限公司 | Adjustable optical filter and photographic device |
| CN109901339A (en) * | 2019-04-04 | 2019-06-18 | 林嘉佑 | A kind of electrochemistry light adjusting system and windowpane |
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