CN103885264A - Reversible electrochromic housing and method of making same - Google Patents

Abstract

The present invention provides a method for manufacturing a reversible electrochromic shell, comprising the following steps: providing a substrate layer; forming a tungsten oxide layer on the substrate layer, wherein the tungsten oxide layer includes both a tungsten oxygen single bond and a tungsten oxygen double bond structure; providing an electrolytic cell containing an electrolyte, wherein the electrolyte includes a sodium chloride solution and a sodium bicarbonate solution; allowing the electrolyte to infiltrate the substrate layer and the tungsten oxide layer; and embedding/removing cations into/from the tungsten oxide layer in response to a color-changing electric field, and finally the surface of the tungsten oxide layer presents a bright luster discernible to the naked eye.

Description

Reversible electrochromic housing and manufacturing method thereof

technical field

The present invention relates to an electrochromic object, and in particular to a reversible electrochromic object and its manufacturing method.

Background technique

Electrochrome (Electrochrom) refers to the reversible change of the color or transparency of a material under the action of an applied voltage or electric field. When the applied voltage or electric field disappears, the color or transparency of the material returns to its original state. Because the electrochromic material has a memory function, it can be widely used in the fields of display components, color-changing glass, storage media, and exterior decoration. Generally, the material with color-changing function may include a substrate and an electrochromic film formed on the substrate.

Compared with nickel oxide materials, tungsten oxide is the main coating material at present, mainly because tungsten oxide coating has a higher melting point and better wear resistance, and has significant electrochromic, gasochromic, and photochromic characteristics. It can be used to make flat-panel displays, photoelectric color-changing display windows, optical devices with read-write and erase functions, light modulation devices, gas sensors, temperature and humidity sensors, and so on.

An electrochromic device can generally be classified as a first mode device or a second mode device. The first mode device is an anode device, i.e. the change in color of the material is due to the simultaneous removal of electrons and cations, the material can be selected from iridium, rhodium, nickel and cobalt; the second mode device is a cathode device, i.e. the change in color of the material It is due to the simultaneous injection of electrons and cations, and the material is tungsten trioxide (Tungsten Oxide, WO3) or manganese trioxide (MnO3).

The mechanism of electrochromic change of tungsten trioxide is that, when a negative charge is applied to the electrochromic device, electrons and cations are simultaneously injected to rearrange the structure of tungsten trioxide to generate tungsten oxide compounds containing cations. When a positive charge is applied to the electrochromic device, electrons and cations move out of the device at the same time due to the attraction of the positive and negative phases, which is called the reverse reaction and presents a faded state. If the current is interrupted after a negative potential is applied to make it colored, the color will last for a period of time before gradually fading away, which is called a memory characteristic.

The tungsten trioxide film will be nearly transparent and colorless before it changes color, because the electrons in the valence band cannot be excited to the conduction band under the visible wavelength range, which means that tungsten trioxide needs a shorter wavelength to excite electrons Jumping occurs, so the electrons in the valence band of tungsten trioxide will not absorb any visible light, so the undiscolored film will appear nearly transparent and colorless.

Tungsten trioxide discoloration reaction formula (1) is as follows:

……..……………………(1)

……..……………………(1)

M+ represents cations such as hydrogen, lithium, and sodium. MXWO3 is called tungsten bronze (Tungsten Bronze), and its color is dark blue or bronze.

Conventional decorative coatings can be divided into dry and wet processes. The dry process usually uses two categories: physical vapor deposition (Physical Vapor Deposition, PVD) and chemical vapor deposition (Chemical Vapor Deposition, CVD). For example, use electron beam to evaporate tungsten trioxide film, and try to study the electrochromic effect under the conditions of changing parameters (such as: film thickness, evaporation pressure, evaporation temperature, evaporation rate and annealing treatment, etc.) Impact. Previously, different film compositions and thicknesses have been used to present different colors. However, the color characteristics produced by this method are not reversible and recoverable, and the process time is relatively long. In addition, the wet process adopts the way of mixing dye color to decorate the surface. In addition to not having good reversibility of color characteristics, the other method also has problems in wastewater treatment.

Contents of the invention

To sum up, the conventional electrochromic casing and the coating method need to be improved urgently. In view of this, the inventor of this case made in-depth research and persevered, and finally successfully developed an innovative and effective electrochromic shell and its manufacturing method. After many experiments and improvements, he was able to use novel technical thinking and The approachable implementation method fundamentally solves the known problems, and is expected to provide users with more beautiful and practical shells.

An embodiment of the present invention provides an electrochromic object. The electrochromic object includes a substrate layer and a metal oxide layer. The substrate layer is made of a non-transparent material, and the metal oxide layer is formed on the substrate layer, wherein the metal oxide layer includes metal-oxygen single-bond and metal-oxygen double-bond structures.

One embodiment of the present invention provides a method of manufacturing a reversible electrochromic housing. The method includes the following steps: providing a substrate layer, which is a non-transparent material; and forming a tungsten oxide layer on the substrate layer, wherein the tungsten oxide layer includes tungsten-oxygen single bonds and tungsten-oxygen double bonds knot structure.

One embodiment of the present invention provides a method for changing the color of an electrochromic object. The method includes the steps of: providing the electrochromic object, wherein the electrochromic object has a first color; placing the electrochromic object in a solution containing cations; and applying a voltage to the solution so that the The first color becomes a second color.

The products to which the technology of the present invention can be applied include spectacle frames, casings, watch straps, accessories, 3C electronic products or mobile phone protective cases.

Description of drawings

Fig. 1 is the Raman spectrum measured by placing the tungsten trioxide layer of the present invention on the silicon chip base.

FIG. 2 is a schematic diagram of an electrochromic casing with a single-layer coating according to an embodiment of the present invention.

FIG. 3 is a schematic diagram of an electrochromic casing with double-layer coatings according to an embodiment of the present invention.

FIG. 4 is a schematic diagram of an electrochromic casing with a three-layer coating according to an embodiment of the present invention.

Fig. 5 is a flow chart of the steps of manufacturing an electrochromic object according to an embodiment of the present invention

FIG. 6A is a schematic diagram of a color-changing device according to an embodiment of the present invention, wherein the substrate layer is a conductive material.

FIG. 6B is a schematic diagram of a color-changing device according to an embodiment of the present invention, wherein the substrate layer is a non-conductive material.

Fig. 7 is a method for discoloring an electrochromic casing according to an embodiment of the present invention.

[Description of main component symbols]

01: Electrochromic shell

10: Substrate layer

10A: Covered conductive layer

11: The first metal oxide layer

11A: Tungsten oxide layer

12: Second metal oxide layer

13: The third metal oxide layer

14: Doping substances

21: DC power supply

22: first voltage terminal

23: Second voltage terminal

24: counter electrode

25: tank body

26: Aqueous solution

Detailed ways

The present invention is further described in detail with the following preferred embodiments and accompanying drawings.

Please refer to Fig. 1, Fig. 1 is the Raman spectrum measured when the tungsten trioxide layer of the present invention is placed on the silicon chip base. The horizontal axis represents the Raman shift (Raman Shift), also known as the wave number, and the vertical axis represents the absorption intensity (au). Figure 1, the first peak (Raman shift of 520 cm-1) from left to right is the absorption intensity of the silicon carrier after scattering; the second peak is at the Raman shift of 750 cm-1 , it reflects the absorption intensity of the hexavalent tungsten and oxygen single-bond structure (W+6-O) in the tungsten trioxide layer; the third peak is when the Raman shift is 953 cm-1, the reaction In the tungsten trioxide layer, the absorption intensity of the hexavalent tungsten and oxygen double bonded structure (W+6=O) is shown; the fourth peak is at the Raman shift of 980 cm-1, which is reflected in the three In the tungsten oxide layer, the absorption intensity of the pentavalent tungsten and oxygen single bond structure (W+5-O). It is worth mentioning that the tungsten trioxide layer presents a loose columnar structure image under a scanning electron microscope.

FIG. 2 is a schematic diagram of an electrochromic object with a single-layer coating according to an embodiment of the present invention. The electrochromic objects of the present invention can be 3C product shells, 3C product protective cases, accessories (such as necklaces, rings, earrings, bracelets), accessories (such as watches, belts, glasses frames), etc. Please refer to FIG. 2, the electrochromic object 01 includes a substrate layer 10 and a first metal oxide layer 11 disposed on the substrate layer 10, and the first metal oxide layer 11 is located on a surface layer of the electrochromic object 01 . The substrate layer 10 is a substrate selected from 3C product shells, 3C product protective shells, ornaments or accessories, and its material can be metal, metal compound or polymer structure. In particular, the substrate layer 10 is non- Transparent material. In this embodiment, the substrate layer 10 is a shell substrate of a 3C product, and the material is polished stainless steel.

The material of the first metal oxide layer 11 can generally be selected from oxides of iridium, rhodium, nickel, cobalt, tungsten and manganese, but when considering the requirements of non-toxicity, environmental protection, high hardness, wear resistance and chemical corrosion resistance, tungsten oxide is preferred. In this embodiment, the first metal oxide layer 11 is coated on the substrate layer 10 by a physical vapor deposition sputtering process, and the sputtering target is mainly a tungsten target to form an amorphous tungsten oxide layer.

The tungsten oxide layer may further include a dopant, and the dopant further includes at least one of nitrogen and silicon, which can set the color of the electrochromic object 01 .

In another embodiment, the first metal oxide layer 11 is coated on the substrate layer 10 by a physical vapor deposition sputtering process, and the sputtering target is a combination of a tungsten target and nitrogen and oxygen, thereby forming nitrogen-containing tungsten oxide layer.

In another embodiment, the first metal oxide layer 11 is coated on the substrate layer 10 by a physical vapor deposition sputtering process, and the sputtering target is a combination of a tungsten target, silicon and oxygen, thereby forming silicon-containing tungsten oxide layer.

However, the tungsten oxide layers mentioned in the examples of this case all exhibit the same Raman spectrum characteristics as in FIG. 1 , that is, they have both tungsten-oxygen single-bond and double-bond structures.

In this embodiment, the argon-oxygen ratio of the sputtering equipment is 1.1-1.2, the current is 1-2 amps, and the first metal with a thickness of less than 500 nanometers (nm) and a color of 400-600 nm in the visible spectrum can be formed. Oxide layer 11.

In another embodiment, a first metal oxide layer 11 mainly composed of tungsten oxide and having a thickness of less than 500 nm can be sputtered on the substrate layer 10, wherein the argon-oxygen ratio of the sputtering is 1-1.2, The current is 0.5~1A.

In another embodiment, a first metal oxide layer 11 mainly composed of tungsten oxide and having a thickness of less than 500 nm can be sputtered on the substrate layer 10, wherein the argon-oxygen ratio of the sputtering is 1-1.2, The current is 0.3~0.5A.

FIG. 3 is a schematic diagram of an electrochromic object 02 with double-layer coating according to an embodiment of the present invention. As shown in FIG. 3, the electrochromic object 02 includes a substrate layer 10, a first metal oxide layer 11 disposed on the substrate layer 10, and a second metal oxide layer 12 disposed on the first metal oxide layer 11, And the second metal oxide layer 12 is located on a surface layer of the electrochromic object 02 . In this embodiment, a second metal oxide layer 12 mainly composed of tungsten oxide and having a thickness of less than 500 nm can be sputtered on the first metal oxide layer 11, wherein the argon-oxygen ratio of the sputtering is 1-1.2 , The current is 2A, and its color presents a visible spectrum of 400-500 nanometers.

FIG. 4 is a schematic diagram of an electrochromic object 03 with a three-layer coating according to an embodiment of the present invention. As shown in Figure 4, the electrochromic object 03 includes a substrate layer 10, however, if the material of the substrate layer 10 is a non-conductive material, it needs to be planarized on the substrate layer 10 to form a planarized Layer, such as coating a polymer material, curing by ultraviolet light or heat curing, and then plating a conductive material including at least one of titanium, aluminum, nickel and stainless steel to form a conductive layer 10A on the planarization layer (Please refer to FIG. 6B ), wherein the thickness of the conductive layer 10A is less than 3 micrometers. The process time of the ultraviolet light curing is less than 5 minutes, the heating temperature of the heat curing process is between 80-120° C., and the curing time is less than 30 minutes. The first metal oxide layer 11 disposed on the substrate layer 10 or on the conductive layer 10A, the second metal oxide layer 12 disposed on the first metal oxide layer 11 and the second metal oxide layer disposed on the second metal oxide layer 12 There are three metal oxide layers 13 , and the third metal oxide layer 13 is located on the surface of the electrochromic object 03 . In this embodiment, a third metal oxide layer 13 mainly composed of tungsten oxide and having a thickness of less than 500 nm can be sputtered on the second metal oxide layer 12, wherein the argon-oxygen ratio of the sputtering is 1-1.2 , The current is 2A, and its color presents a visible spectrum of 500-600 nanometers.

Please refer to Figure 5 and Figure 6 at the same time. Figure 5 is a flow chart of the steps of manufacturing an electrochromic object according to an embodiment of the present invention, the electrochromic object includes: a substrate layer 10, a metal oxide layer 11, a dopant 14 (containing nitrogen or silicon) , the metal oxide layer 11 is located on the surface of the electrochromic object.

Figure 5 is a method of manufacturing an electrochromic object according to an embodiment of the present invention, the method includes the following steps:

In step 501 , a substrate layer 10 is provided, which is made of non-transparent material. The substrate layer 10 is a substrate selected from 3C product shells, 3C product protective cases, ornaments or accessories.

In step 502 , for the substrate layer 10 , procedures such as degreasing, cleaning and drying are performed.

In step 503 , a judgment is made on the composition of the material: if the base layer 10 is a non-conductive material, step 504 is performed first.

In step 504, planarization is carried out on the substrate layer 10 to form a planarization layer, such as coating a polymer material, curing by ultraviolet light or heat, and then plating layers including titanium, aluminum, nickel and At least one conductive material of stainless steel is used to form a conductive layer 10A on the planarization layer, wherein the thickness of the conductive layer 10A is less than 3 microns. The process time of the ultraviolet light curing is less than 5 minutes, the heating temperature of the heat curing process is between 80-120° C., and the curing time is less than 30 minutes. On the contrary, if the substrate layer 10 is made of conductive material, step 505 is directly performed. In step 505, a physical vapor deposition sputtering process is performed on the substrate layer 10 or the conductive layer 10A to form a metal oxide layer 11, and the metal oxide layer 11 is located on the surface of the electrochromic object. Preferably, the metal oxide layer 11 is a tungsten oxide layer 11A. Taking the tungsten oxide layer 11A as an example, the argon-oxygen ratio of the physical vapor deposition sputtering process is 1.1-1.2, and the current is 1-2 amperes, so that the tungsten oxide layer 11A has a thickness less than 500 nm and a Raman shift and a bond structure. When the Raman shift of the tungsten oxide layer 11A is 750 cm-1, the bonded structure presents a structure of hexavalent tungsten and oxygen single bond (W+6-O), and when the Raman shift is 953 cm-1, the bonding structure presents a hexavalent tungsten-oxygen double bond structure (W+6=O), and the tungsten oxide layer 11A has a color in the visible spectrum of 400-600 nm. In addition, a dopant 14 can be further added to the tungsten oxide layer 11A, and the dopant further includes at least one of nitrogen and silicon. In this way, the color of the electrochromic object can be set. It should be noted that the metal oxide layer 11 is located on the surface layer of the electrochromic object, and the metal oxide layer 11 formed on the substrate layer 10 is not limited to one layer. In another embodiment, a physical vapor deposition sputtering process is performed on a substrate layer 10 to form a metal oxide layer 11 (such as a first metal oxide layer) on the substrate layer 10, wherein the metal oxide The layer includes both metal-oxygen single-bond and metal-oxygen double-bond structures, and has a first color.

FIG. 6A is a schematic diagram of a color changing device according to an embodiment of the present invention, wherein the substrate layer 10 is a conductive material. FIG. 6B is a schematic diagram of a color changing device according to an embodiment of the present invention, wherein the substrate layer 10 is a non-conductive material. Fig. 7 is a flow chart of the steps of the color changing method according to the embodiment of the present invention. Please refer to Fig. 6A and Fig. 6B simultaneously, this discoloration device comprises: a DC power supply 21, has the first voltage end 22 and the second voltage end 23, the first voltage end 22 power supply is connected an electrochromic object 01 (conductive layer ); a pair of electrodes 24, electrically connected to the second voltage terminal 23, the material of the opposite electrodes 24 is metal, such as stainless steel; a tank 25; and an aqueous solution 26, which is contained in the tank 25, the electrochromic object The metal oxide layer 11 of O1 and the counter electrode 24 are immersed in the aqueous solution 26, the aqueous solution 26 includes sodium chloride solution or sodium bicarbonate solution, and the aqueous solution 26 may also include solutions containing electrolytes such as other cations.

Please refer to Figures 6A, 6B and 7 at the same time. Figure 7 is an embodiment of a method for discoloring an electrochromic object according to the present invention. A metal oxide layer 11, the electrochromic object 01 has a first color, the method for discoloring the electrochromic object 01 includes the following steps: In step 701, a tank body 25 containing an aqueous solution 26 is provided, wherein the aqueous solution 26 includes sodium chloride solution or sodium bicarbonate solution. The aqueous solution 26 may also include solutions containing electrolytes such as other cations. However, if environmental protection and economic issues need to be considered, sodium ion solutions are still the first choice.

In step 702 , the aqueous solution 26 is used to wet the tungsten oxide layer 11A and the pair of electrodes 24 of the electrochromic object 01 .

In step 703, in response to a DC power source 21, its first and second voltage terminals 22, 23 are respectively connected to the conductive layer 10A of the electrochromic object 01 and the pair of electrodes 24 to form a An electric field causes the electrochromic object to change from a first color to a second color. In detail, the electric field applied to the aqueous solution 26 can make the cations in the aqueous solution 26 intercalate into the metal oxide layer 11, or make the cations move out from the metal oxide layer 11 to change the color of the electrochromic object 01, that is, form a colored texture , wherein the colored texture includes at least one of characters and patterns. In other words, the aqueous solution 26 can change the color or pattern of the electrochromic object 01 reversibly within the range of the visible spectrum under the action of the positive or negative DC power supply 21 . In the following chemical equation (2), WOx(N, Si) represents tungsten oxide doped with nitrogen or silicon, and Na+(aq) represents a sodium ion solution. When the first voltage terminal of the DC power supply is negative, it can generate positive The colored product Nax (WOx (N, Si))y; on the contrary, when the first voltage terminal of the DC power supply is positive, it will reversely return to tungsten oxide and sodium ion solution doped with nitrogen or silicon respectively.

Electric field

WOx(N, Si) + Na+(aq) Nax (WOx (N, Si)) y….…(2)

The DC power supply 21 has a voltage signal, which is one of the following states:

A first state: the voltage signal has a first voltage level in a first period, wherein the first voltage level is between 1.2-3 volts, and the first period is greater than or equal to 30 seconds;

A second state: the voltage signal has a second voltage level in a second period, wherein the second voltage level is between 3-5 volts, and the second period is less than or equal to 22 seconds;

A third state: the voltage signal has a third voltage level in a third period, wherein the third voltage level is between 5-7 volts, and the third period is between 10-15 seconds;

A fourth state: the voltage signal has a fourth voltage level in a fourth period, wherein the fourth voltage level is between 7-9 volts, and the fourth period is less than 10 seconds.

All in all, the greater the intensity of the external DC power supply 21 , the shorter the time required for color transformation; conversely, the smaller the intensity of the external DC power supply 21 , the longer the time required for color transformation.

Example:

A method of manufacturing an electrochromic object comprising the steps of:

providing a substrate layer, which is a non-transparent material; and

A tungsten oxide layer is formed on the substrate layer, and the tungsten oxide layer is located on the surface layer of the electrochromic object, wherein the tungsten oxide layer includes tungsten-oxygen single-bond and tungsten-oxygen double-bond structures.

The method described in Embodiment 1, before forming the tungsten oxide layer, further includes the following steps:

Coating a polymer material on a surface of the substrate layer to form a planarization layer on the substrate layer; and

A conductive material including at least one of titanium, aluminum, nickel and stainless steel is plated on the planarization layer to form a conductive layer, wherein the thickness of the conductive layer is less than 3 microns, and the tungsten oxide layer is disposed on the conductive layer.

The method of embodiment 1, wherein the tungsten oxide layer includes a dopant, and the dopant further includes at least one of nitrogen and silicon.

The method of embodiment 1, wherein the tungsten oxide layer has a color texture, and the color texture includes at least one of characters and patterns.

The method as in embodiment 1, wherein the step of forming the tungsten oxide layer on the substrate layer comprises:

Performing a sputtering process on the substrate layer to form the tungsten oxide layer, wherein the argon-oxygen ratio is 1.1-1.2, and the current is 1-2 amperes, so that the tungsten oxide layer has a thickness less than 500 nanometers and a Raman shift and a bonded structure, and the tungsten oxide layer exhibits a color in the visible spectrum of 400-600 nanometers.

An electrochromic object comprising:

a substrate layer, which is a non-transparent material; and

A metal oxide layer is formed on the substrate layer, and the metal oxide layer is located on the surface layer of the electrochromic object, wherein the metal oxide layer includes metal-oxygen single bond and metal-oxygen double bond structure.

The object as described in embodiment 6, further comprising:

A planarization layer is formed on a surface of the substrate layer with a polymer material; and

A conductive layer is plated on the planarization layer with a conductive material;

Wherein, the metal oxide layer is formed on the conductive layer.

The object of embodiment 6 or 7, wherein the metal oxide layer includes a dopant, and the dopant further includes at least one of nitrogen and silicon.

The object as described in embodiment 6, wherein the base material layer is the base material of a 3C product case or a 3C product protective shell.

The object of embodiment 6, wherein the substrate layer is a substrate of an accessory.

A method of discoloring the electrochromic object as described in embodiment 6, the method comprising:

A discoloration device is provided, comprising: a tank body; an aqueous solution containing cations, which is accommodated in the tank body; a DC power supply, having a first voltage terminal and a second voltage terminal; and a pair of electrodes, which are electrically connected to the The first voltage terminal is immersed in the aqueous solution;

electrically connecting the electrochromic object to the second voltage terminal, and immersing the metal oxide layer of the electrochromic object in the aqueous solution; and

Applying a voltage to the aqueous solution causes the electrochromic object to change from a first color to a second color.

As in the method described in Example 11, when a voltage is applied to the aqueous solution

, when the first voltage terminal is a positive electrode and the second voltage terminal is a negative electrode

, the cations of the aqueous solution are embedded in the metal oxide layer of the electrochromic object;

When the first voltage terminal is a negative electrode and the second voltage terminal is a positive electrode,

Cations that were originally intercalated into the metal oxide layer are removed from the metal oxide layer.

To sum up, this case provides a reversible electrochromic shell and its manufacturing method, which can quickly decorate the color-changing shell with novel technical thinking, humanized viewpoint, and proven feasible operation mode. Coloring can save the current tedious and unenvironmental discoloration process, which is a great boon for those who love color-changing shells.

This case can be modified in various ways by the people who are familiar with this technology, but they are all in line with the intended protection of the scope of the patent application.

Claims (12)

1. A method of manufacturing an electrochromic object, comprising the steps of: providing a substrate layer, which is a non-transparent material; and A tungsten oxide layer is formed on the substrate layer, and the tungsten oxide layer is located on the surface layer of the electrochromic object, wherein the tungsten oxide layer includes tungsten-oxygen single-bond and tungsten-oxygen double-bond structures. 2. The method according to claim 1, before forming the tungsten oxide layer, further comprising the following steps: Coating a polymer material on a surface of the substrate layer to form a planarization layer on the substrate layer; and A conductive material including at least one of titanium, aluminum, nickel and stainless steel is plated on the planarization layer to form a conductive layer, wherein the thickness of the conductive layer is less than 3 microns, and the tungsten oxide layer is disposed on the conductive layer. 3. The method of claim 1, wherein the tungsten oxide layer comprises a dopant, and the dopant further comprises at least one of nitrogen and silicon. 4. The method of claim 1, wherein the tungsten oxide layer has a color texture, and the color texture includes at least one of characters and patterns. 5. The method of claim 1, wherein the step of forming the tungsten oxide layer on the substrate layer comprises: Performing a sputtering process on the substrate layer to form the tungsten oxide layer, wherein the argon-oxygen ratio is 1.1-1.2, and the current is 1-2 amperes, so that the tungsten oxide layer has a thickness less than 500 nanometers and a Raman shift and a bonded structure, and the tungsten oxide layer exhibits a color in the visible spectrum of 400-600 nanometers. 6. An electrochromic object comprising: a substrate layer, which is a non-transparent material; and A metal oxide layer is formed on the substrate layer, and the metal oxide layer is located on the surface layer of the electrochromic object, wherein the metal oxide layer includes metal-oxygen single bond and metal-oxygen double bond structure. 7. The subject of claim 6, further comprising: A planarization layer is formed on a surface of the substrate layer with a polymer material; and A conductive layer is plated on the planarization layer with a conductive material; Wherein, the metal oxide layer is formed on the conductive layer. 8. The object of claim 6 or 7, wherein the metal oxide layer comprises a dopant, the dopant further comprising at least one of nitrogen and silicon. 9. The object as claimed in claim 6, wherein the base material layer is a base material of a 3C product shell or a 3C product protective case. 10. The object as claimed in claim 6, wherein the substrate layer is a base material of an accessory. 11. A method of discoloring an electrochromic object as claimed in claim 6, the method comprising: A discoloration device is provided, comprising: a tank body; an aqueous solution containing cations, which is accommodated in the tank body; a DC power supply, having a first voltage terminal and a second voltage terminal; and a pair of electrodes, which are electrically connected to the The first voltage terminal is immersed in the aqueous solution; electrically connecting the electrochromic object to the second voltage terminal, and immersing the metal oxide layer of the electrochromic object in the aqueous solution; and Applying a voltage to the aqueous solution causes the electrochromic object to change from a first color to a second color. 12. The method according to claim 11, when applying a voltage to the aqueous solution, when the first voltage terminal is a positive electrode and the second voltage terminal is a negative electrode, the cations of the aqueous solution are inserted into the electrochromic object Metal oxide layer; when the first voltage terminal is a negative electrode and the second voltage terminal is a positive electrode, cations originally embedded in the metal oxide layer are removed from the metal oxide layer.

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