Inverted electrochromic energy storage device and preparation method and application thereof

Abstract

The invention discloses an inverted electrochromic energy storage device and a preparation method and application thereof. The inverted electrochromic energy storage device comprises a working electrode, a counter electrode and an electrolyte, wherein the working electrode comprises a color changing unit and an energy storage unit; the color changing unit comprises a first substrate, a metal layer and an electrochromic layer which are arranged in a stacked mode. The energy storage unit comprises a second substrate and an ion storage layer which are arranged in a stacked mode. The counter electrode is arranged between the color changing unit and the energy storage unit; the electrolyte is distributed in the porous structure of the first substrate. According to the inverted electrochromic energy storage device, the reflection type structure is constructed, the color changing unit and the energy storage unit are separated, colorful conversion and observation of colors are carried out above the first substrate, energy storage is adjusted through the thickness of the ion storage layer above the second substrate, and the energy storage efficiency is improved. Therefore, the contradiction between the color quality and the energy storage size of the electrochromic energy storage device is solved, and high energy storage is realized while the device is colorful and discolored.

Description

Technical Field

[0001] The invention relates to an energy storage device, in particular to an inverted electrochromic energy storage device and a preparation method and application thereof, belonging to the technical field of batteries. Background Art

[0002] As the current and voltage of electrochromic materials change, the color changes accordingly. The principle is that an internal redox reaction occurs, accompanied by the insertion and extraction of electrons and ions, which causes the refractive index and extinction coefficient of the electrochromic material itself to change, and finally presents the result of color change on the outside. Electrochromic materials are widely studied because of their rich colors, easy regulation, and energy conservation. With the continuous deepening of research, the application of electrochromic devices has also expanded from simple color change to flexible wearables, sensors, and energy storage. Electrochromic energy storage devices (EESDs) combine the two functions of electrochromism and energy storage, and can judge the real-time energy storage situation inside by the color change on the surface of the device.

[0003] Electrochromic materials are also divided into inorganic electrochromic materials, organic electrochromic materials and composite electrochromic materials according to different types of materials. Inorganic electrochromic materials are mainly transition metal oxides, such as tungsten trioxide (WO3), titanium dioxide (TiO2), nickel oxide (NiO), Prussian blue (PB), manganese dioxide (MnO2), etc.; organic electrochromic materials are mainly viologen, polythiophene (PT), polypyrrole (PPy) and polyaniline (PANI), etc.; later, some people have studied simple composite electrochromic materials. Composite electrochromic materials refer to the use of complementary working electrodes and counter electrodes to expand colors and store energy, and to combine different types of materials together, in the hope of obtaining electrochromic devices with better electrochromic performance than single materials through synergistic effects, further improving the performance of electrochromic devices. These materials can be a composite of inorganic materials and inorganic materials (inorganic-inorganic composite), a composite of inorganic materials and organic materials (inorganic-organic composite), or a composite of organic materials (organic-organic composite).

[0004] Electrochromic devices generally adopt a multilayer structure, which generally includes a transparent conductive substrate, an ion storage layer, an electrolyte layer, an electrochromic layer, and a transparent conductive substrate from top to bottom. The conductive deposition serves as the electrode of the electrochromic device and plays the role of electron transmission. The ion storage layer prevents ions from being deposited on the transparent conductive substrate, which affects the color quality of the electrochromic device. The electrolyte layer is divided into liquid, solid, gel, etc., which provides the ions required for the electrochromic material to undergo redox reactions. The electrochemical properties of the electrolyte, including its ion conductivity, cycle durability, thermal stability and safety, play a decisive role in the overall performance of the electrochromic device. Liquid electrolytes have become the first choice since the development of electrochromic technology due to their high ion conductivity. Among them, organic ester electrolytes are the most popular, such as propylene carbonate. The electrochromic layer is the most critical component in the electrochromic device, which determines the overall performance of the device. This layer needs to achieve significant optical changes in the coloring and fading states, and must have high ionic and electronic conductivity to ensure rapid response. In addition, the electrochromic layer must also have excellent electrochemical stability to support long-term cycling. As mentioned earlier, the material selection of the electrochromic layer is critical to its performance.

[0005] However, there has always been a contradiction in electrochromic devices, that is, it is difficult to coordinate the color quality and energy storage per unit area of ​​electrochromic devices. If you want to obtain an electrochromic device with high color saturation and good color change performance, you need to reduce the thickness of the electrochromic layer, but this solution will result in low energy storage of the electrochromic energy storage device. If you want to improve the performance of the electrochromic energy storage device, you need to thicken the ion storage layer, which will produce an overly thick color change layer, resulting in poor color quality of the electrochromic device itself.

[0006] Secondly, most researchers use electrodeposition to prepare inorganic electrochromic material films such as tungsten oxide. This method limits the thickness of the electrochromic layer. Too long an electrodeposition time will lead to poor material bonding performance and unnecessary shedding during the operation of the device. At the same time, the use of electrodeposition for thin film deposition will inevitably lead to poor uniformity of the film as the thickness increases. In addition, the thin film produced by electrodeposition is more dependent on environmental factors, and it is impossible to guarantee that the performance of the prepared film is always good. Summary of the invention

[0007] The main purpose of the present invention is to provide an inverted structure electrochromic energy storage device and a preparation method thereof, so as to overcome the deficiencies in the prior art.

[0008] Another object of the present invention is to provide applications of the inverted structure electrochromic energy storage device.

[0009] In order to achieve the above-mentioned invention object, the technical solution adopted by the present invention includes:

[0010] The embodiment of the present invention provides an inverted structure electrochromic energy storage device, which includes a working electrode, a counter electrode and an electrolyte, wherein the working electrode includes a color changing unit and an energy storage unit;

[0011] The color-changing unit includes a first substrate with a porous structure, and a metal layer and an electrochromic layer sequentially arranged on the surface of the first substrate, wherein the electrochromic layer is arranged on a side away from the energy storage unit, and the electrochromic layer and the metal layer can form an optical resonant cavity;

[0012] The energy storage unit includes a second substrate and an ion storage layer arranged on the surface of the second substrate;

[0013] The counter electrode is arranged between the color changing unit and the energy storage unit;

[0014] The electrolyte is distributed in the porous structure of the first substrate, between the counter electrode and the first substrate of the color-changing unit, and between the counter electrode and the ion storage layer of the energy storage unit.

[0015] In some embodiments, the inverted electrochromic energy storage device includes an electrochromic layer, a metal layer, a first substrate, an electrolyte, a counter electrode, an electrolyte, an ion storage layer, and a second substrate stacked in sequence from top to bottom.

[0016] The embodiment of the present invention further provides a method for preparing the inverted electrochromic energy storage device, which comprises:

[0017] A metal layer and an electrochromic layer are sequentially arranged on the surface of the first substrate to form a color-changing unit;

[0018] An ion storage layer is arranged on the surface of the second substrate to form an energy storage unit, wherein the color changing unit and the energy storage unit together constitute a working electrode;

[0019] The working electrode, the counter electrode and the liquid electrolyte are assembled into a closed structure and subjected to photocuring treatment to obtain the inverted electrochromic energy storage device.

[0020] The embodiment of the present invention also provides the application of the inverted electrochromic energy storage device in the fields of display, camouflage or energy storage.

[0021] Compared with the prior art, the advantages of the present invention are at least:

[0022] The inverted electrochromic energy storage device provided by the present invention separates the color changing unit from the energy storage unit by constructing a reflective structure, performs colorful color transformation and observation on the first substrate, and adjusts the energy storage by adjusting the thickness of the ion storage layer on the second substrate, thereby solving the contradiction between the color quality and the energy storage size of the electrochromic energy storage device, and realizing high energy storage while the device changes color in multiple colors. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0024] Figure 1 It is a structural diagram of an electrochromic device in the prior art;

[0025] Figure 2 It is a schematic structural diagram of an inverted electrochromic energy storage device in a typical embodiment of the present invention;

[0026] Figure 3 This is a schematic diagram of the inverted electrochromic energy storage device of the present invention, which is a color change range controlled by adjusting the electrochromic layer above the first substrate;

[0027] Figure 4 Schematic diagram of the color change of the inverted electrochromic energy storage device of Example 1 of the present invention from yellow to green, purple to green, and cyan to purple as the voltage is controlled;

[0028] Figure 5 is a schematic diagram of the ultraviolet spectrum of the inverted electrochromic energy storage device according to Example 3 of the present invention changing from yellow to green;

[0029] Figure 6 is a schematic diagram of the ultraviolet spectrum of the inverted electrochromic energy storage device according to Example 2 of the present invention changing from purple to green;

[0030] Figure 7 is a schematic diagram of an ultraviolet light image of the inverted electrochromic energy storage device according to Example 1 of the present invention changing from cyan to purple;

[0031] Figure 8 4 is a graph showing the charge and discharge specific capacity of the inverted electrochromic energy storage device of Example 1 of the present invention. DETAILED DESCRIPTION

[0032] In view of the defects of the prior art, the inventor of this case has proposed the technical solution of the present invention after long-term research and extensive practice. It mainly provides a new device structure idea, solves the imbalance between energy storage and colorful color changes of electrochromic devices, and achieves the switching of multiple colors while ensuring the energy storage performance of the electrochromic device itself. The technical solution of the present invention will be described clearly and completely below. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0033] The following terms need to be explained:

[0034] ITO conductive glass: It is made by coating a layer of indium tin oxide (commonly known as ITO) on soda-lime-based or silicon-borosilicate-based substrate glass using magnetron sputtering.

[0035] FTO conductive glass: fluorine-doped SnO2 conductive glass (SnO2:F).

[0036] Specifically, as one aspect of the technical solution of the present invention, the inverted electrochromic energy storage device involved therein comprises a working electrode, a counter electrode and an electrolyte, wherein the working electrode comprises a color changing unit and an energy storage unit;

[0037] The color-changing unit includes a first substrate with a porous structure, and a metal layer and an electrochromic layer sequentially arranged on the surface of the first substrate, wherein the electrochromic layer is arranged on a side away from the energy storage unit, and the electrochromic layer and the metal layer can form an optical resonant cavity;

[0038] The energy storage unit includes a second substrate and an ion storage layer arranged on the surface of the second substrate;

[0039] The counter electrode is arranged between the color changing unit and the energy storage unit;

[0040] The electrolyte is distributed in the porous structure of the first substrate, between the counter electrode and the first substrate of the color-changing unit, and between the counter electrode and the ion storage layer of the energy storage unit.

[0041] like Figure 1 As shown, the existing electrochromic device is mainly composed of a substrate, an electrochromic layer, an electrolyte layer, an ion storage layer, and a substrate arranged in sequence from top to bottom. Therefore, the electrochromic layer will be blocked by the electrolyte layer, the ion storage layer and the substrate and cannot be directly observed. Although the electrolyte layer and the ion storage layer can be prepared with high-transmittance materials, the color of the electrochromic layer will inevitably be disturbed, thereby reducing the color quality of the device, especially in terms of reduced reflectivity and deviation in electrode color.

[0042] In some preferred embodiments, Figure 2 As shown, the inverted electrochromic energy storage device of the present invention comprises an electrochromic layer, a metal layer, a first substrate, an electrolyte, a counter electrode, an electrolyte, an ion storage layer and a second substrate stacked in sequence from top to bottom. The present invention provides an inverted electrochromic energy storage device, which uses a new idea to solve the difficulties in color change and energy storage of electrochromic devices.

[0043] In some preferred embodiments, the inverted electrochromic energy storage device comprises:

[0044] a porous layer, serving as a first substrate;

[0045] an electrolyte filled in the porous layer;

[0046] A metal layer is disposed on the first surface of the porous layer;

[0047] An electrochromic layer is disposed on the metal layer to form a first optical resonant cavity;

[0048] A conductive material, serving as a second substrate;

[0049] An ion storage layer is arranged on the conductive surface of the second substrate;

[0050] The counter electrode is a metal sheet that connects the first substrate and the second substrate.

[0051] By adopting the above-mentioned design, the present invention enables at least one electrochromic layer to be located at the outermost layer of the electrochromic device. When in use, whether powered on or not, the color, brightness, etc. of the electrochromic layer will not be blocked by other structural layers in the electrochromic device and can be directly observed, thereby achieving a very good visual effect.

[0052] In some embodiments, the metal layer and the electrochromic layer form a metal-medium structure, which can produce optical interference and display multiple colors. Further, by adjusting the thickness of the electrochromic layer material, the constructive and destructive interference of light can be adjusted to achieve selective absorption and reflection of light, so that the structural color of the metal-medium structure can be adjusted accordingly.

[0053] In some embodiments, the optical resonant cavity includes a Fabry-Perot resonant cavity. By forming the optical resonant cavity, the electrochromic device can present a gorgeous optical structural color in the non-powered state, and in the powered state, it can achieve an organic fusion of optical structural color and electrochromic, and the types of colors obtained far exceed the sum of the types of electrochromic and optical structural color. The present invention achieves a colorful color transition of a single device by constructing a Fabry-Perot resonant cavity on multiple first substrates, expanding the color change range of the electrochromic energy storage device.

[0054] In some embodiments, the material of the electrochromic layer includes but is not limited to any one or a combination of two or more of inorganic electrochromic materials, organic electrochromic materials, organic / inorganic composite electrochromic materials, etc., and inorganic electrochromic materials are preferably used because of their better cycle stability.

[0055] In some preferred embodiments, the inorganic electrochromic material includes a combination of any one of Co, Rh, Ir, Ni, Cr, Mn, Fe, Ti, V, Nb, Ta, Mo, W, etc., or an oxide of two or more combinations thereof, and is not limited thereto.

[0056] Furthermore, the inorganic electrochromic material may include any one or a combination of two or more of LiNiO2 (lithium nickelate), IrO2, NiO, V2O5, lithium cobaltate, Rh2O3, CrO3, WO3, MoO3, Nb2O5, Ta2O5, TiO2, etc., and is not limited thereto.

[0057] In some preferred embodiments, the organic electrochromic material includes any one or a combination of two or more of organic polymers, organic small molecules, metal supramolecular polymers, metal organic compounds, etc., and is not limited thereto.

[0058] Further, the organic electrochromic material may include any one or a combination of two or more of methyl viologen, viologen, polyaniline, polythiophene, polypyrrole, Prussian blue, metal organic chelates (such as phthalocyanine compounds), polydiyne, etc., and is not limited thereto.

[0059] In some embodiments, the thickness of the electrochromic layer is >0 and ≤1000 nm, preferably 100-500 nm, and particularly preferably 150-300 nm, so that the overall thickness of the inverted electrochromic energy storage device is smaller and thinner.

[0060] In some embodiments, the metal layer has a porous structure, allowing electrolyte ions to freely pass through and make direct contact with the electrochromic layer.

[0061] In some embodiments, the material of the metal layer is an inactive metal, for example, preferably a metal material with high conductivity such as chromium, gold (Au), silver (Ag), copper (Cu), tungsten (W), titanium, or any one or a combination of two or more of their alloys, and is not limited thereto.

[0062] In some embodiments, the thickness of the metal layer is >0 and ≤1000 nm, preferably 100-450 nm, so that the overall conductivity of the inverted electrochromic energy storage device is improved, while the thickness is controlled within a certain range to make the device thinner and lighter.

[0063] In some embodiments, the surface of the first substrate (ie, the porous layer) is relatively flat, and a plurality of holes are evenly or unevenly distributed on the surface.

[0064] Furthermore, the pores contained in the first substrate have a diameter of 100 nm to 1100 nm, so as to ensure that the electrolyte can contact the electrochromic layer through the metal layer while maintaining the color saturation of the colorful electrochromic device.

[0065] In some embodiments, the material of the first substrate (ie, the porous layer) may include any one or a combination of two or more of organic materials, inorganic materials, organic / inorganic composite materials, etc., and is not limited thereto.

[0066] Further, the material of the first substrate can be, for example, nylon (Nylon), polysulfone (PS), polyacrylonitrile (PAN), modified polysulfone (PSF), polyvinylidene fluoride (PVDF), PVC (polyvinyl chloride), PES (polyether sulfone), PP (polypropylene), cellulose, porous metal film, porous metal oxide film, porous non-metal oxide film, porous carbon film, porous carbon paper, etc., preferably a porous nylon film, or one of other porous films, for allowing the electrolyte to penetrate into the surface electrochromic material. The present invention preferentially uses a porous nylon film as a substrate to prepare an inverted structure electrochromic device, converting the transmission type electrochromic energy storage device in most of the work into a reflective electrochromic energy storage device, and isolating the upper half of the color changing layer from the lower half of the energy storage layer, that is, increasing the thickness of the energy storage layer, which will not affect the naked eye's observation of the upper color.

[0067] In some embodiments, the thickness of the first substrate is >0 and ≤1100 μm, preferably >0 and ≤100 μm.

[0068] In some embodiments, the ion storage layer is made of a material having ion storage capability and is disposed above the second substrate.

[0069] Furthermore, the material of the ion storage layer is the same as that of the electrochromic layer, or the material of the ion storage layer and the material of the electrochromic layer are complementary electrochromic materials.

[0070] In some preferred embodiments, the material of the electrochromic layer is tungsten oxide, and the material of the ion storage layer is Prussian blue. In other words, in addition to the same type of electrochromic materials, the upper electrochromic layer and the lower energy storage layer can be replaced with complementary electrochromic materials, such as upper tungsten oxide and lower Prussian blue.

[0071] Furthermore, the thickness of the ion storage layer is 1000-8000 nm. The film thickness of the ion storage layer thin film supported on the second substrate can be adjusted at will.

[0072] In some embodiments, the material of the second substrate can be at least any one of ITO (indium tin oxide), FTO (fluorine-doped tin oxide), AZO (aluminum-doped zinc oxide), GZO (gallium-doped zinc oxide), ATO (antimony-doped tin oxide), IZO (indium-doped zinc oxide), NTO (niobium-doped titanium oxide), ZnO, OMO (oxide / metal / oxide), silver (Ag) nanowires, metal mesh, PET-ITO and other conductive materials, which plays a role in electron conduction, but is not limited to this.

[0073] Furthermore, the thickness of the second substrate is 0.1-2 cm.

[0074] In some embodiments, the counter electrode includes various metal sheets, and its material includes but is not limited to at least any one of Zn, W, Ag, Pt, Au, Al, Cu, Ti, Mo, Ni, etc., and the counter electrode is located between the second substrate and the second substrate. By adopting this design, the electrochromic layer of the electrochromic device is isolated from the ion storage layer, and a very good visual effect can be obtained.

[0075] Furthermore, the thickness of the counter electrode is 0.2-1 mm.

[0076] In some embodiments, the electrolyte is in direct contact with the metal layer, the electrochromic layer, the counter electrode, and the ion storage layer.

[0077] In some embodiments, the electrolyte includes a UV-curable electrolyte, which can fully fill the pore structure in the porous layer, increase the electrolyte content ratio in the electrochromic device, and after curing, can also strengthen the bonding strength between the first substrate, the counter electrode and the second substrate.

[0078] Furthermore, the electrolyte may include one or more compounds, for example, + , Li+ 、Al 3+ 、Na + , K + Mg 2+ 、Zn 2+ , Rb + or Cs + Compounds containing at least any one of the ions listed above, but not limited to these.

[0079] Furthermore, the anions contained in the electrolyte include ClO4 - TFSI - 、NO3 - and SO4 2- At least one of the above, preferably ClO4 - .

[0080] Furthermore, the cations contained in the electrolyte include Al 3+ and Li + , that is, the electrolyte includes an aluminum salt compound and a zinc salt compound.

[0081] In a preferred embodiment, the electrolyte layer may contain aluminum salt compounds and zinc salt compounds, such as Al(ClO4)3, Al(TFSI)3, Zn(ClO4)2, Zn(TFSI)2, etc. The ions contained in the electrolyte may be embedded in or removed from the electrochromic layer according to the polarity of the applied voltage to affect the color change or light transmittance change thereof.

[0082] Furthermore, the electrolyte may be aluminum perchlorate and zinc perchlorate, aluminum chloride and zinc nitrate, aluminum chloride and zinc sulfate, lithium chloride and zinc chloride, or at least any one of lithium sulfate and zinc chloride, preferably aluminum perchlorate and zinc perchlorate.

[0083] In some preferred embodiments, the raw materials for preparing the UV-curable electrolyte include a polymer, an ionic salt, a photoinitiator and a solvent.

[0084] Furthermore, the raw materials for preparing the ultraviolet light-cured electrolyte include 30-50 wt% of polymer, 10-25 wt% of ion salt, 0.1-1.0 wt% of photoinitiator and 35-45 wt% of solvent.

[0085] Furthermore, the polymer may be selected from but not limited to at least any one of polyacrylate, polyurethane and the like.

[0086] Furthermore, the ionic salt may be selected from but is not limited to H + , Li + 、Al 3+ 、Na + , K+ Mg 2+ 、Zn 2+ , Rb + , Cs + An ionic salt of at least any one of the ions mentioned above.

[0087] Furthermore, the photoinitiator may be 1-hydroxy-cyclohexyl phenyl ketone or the like.

[0088] Further, the solvent can be selected from but not limited to any one or a combination of two or more of a low eutectic solvent, propylene carbonate (PC), ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), etc., preferably propylene carbonate (PC). The solvent of the present invention is an organic solvent. The electrolyte of the present invention is an organic system electrode liquid, and the overall system is relatively stable.

[0089] In some preferred embodiments, the inverted electrochromic energy storage device further includes: a sealing material, which is circumferentially arranged between the peripheral regions of the working electrode and the counter electrode, at least for combining the working electrode and the counter electrode, and leaving a sealed cavity for injecting raw materials for preparing the ultraviolet light-cured electrolyte. The working electrode and the counter electrode are combined, and a sealed cavity is left, into which the electrolyte is subsequently injected and subjected to light curing.

[0090] Furthermore, the sealing material may be epoxy resin or at least any one of 3M glue and the like, but is not limited thereto.

[0091] In a more preferred embodiment, the structure of the inverted electrochromic energy storage device of the present invention comprises:

[0092] Working electrode: The working electrode comprises an upper nylon membrane and a metal layer and an electrochromic layer film loaded thereon, as well as a second substrate below and an ion storage layer film loaded thereon. The electrochromic layer and ion storage layer used in the present invention are both tungsten oxide;

[0093] Counter electrode: The counter electrode is a metal sheet; the metal sheet is used as a connection in the middle of the device;

[0094] Electrolyte: The electrolyte is a photocurable electrolyte, which can fully fill the pore structure in the porous layer, increase the electrolyte content ratio in the electrochromic device, and after curing, it can also strengthen the bonding strength between the first substrate, the counter electrode and the second substrate.

[0095] The inverted electrochromic energy storage device of the present invention is composed of a working electrode, a counter electrode and an electrolyte. Since the tungsten oxide film is loaded on the upper and lower surfaces simultaneously, there is no need to worry about the problem that the discharge window cannot be aligned.

[0096] The inverted electrochromic energy storage device of the present invention separates the electrochromic layer from the ion energy storage layer by constructing a reflective structure, performs colorful color changes and observations on the first substrate, and adjusts the energy storage by adjusting the thickness of the ion storage layer on the second substrate, thereby solving the contradiction between the color quality and the energy storage size of the electrochromic energy storage device, and realizing high energy storage while the device changes color in multiple colors.

[0097] In summary, the present invention provides a new device structure idea, which solves the imbalance between energy storage and colorful color changes of electrochromic devices, while ensuring the energy storage performance of the electrochromic device itself and achieving switching of multiple colors.

[0098] Another aspect of the embodiments of the present invention further provides a method for preparing the aforementioned inverted electrochromic energy storage device, which comprises:

[0099] A metal layer and an electrochromic layer are sequentially arranged on the surface of the first substrate to form a color-changing unit;

[0100] An ion storage layer is arranged on the surface of the second substrate to form an energy storage unit, wherein the color changing unit and the energy storage unit together constitute a working electrode;

[0101] The working electrode, the counter electrode and the liquid electrolyte are assembled into a closed structure and subjected to photocuring treatment to obtain the inverted electrochromic energy storage device.

[0102] In some preferred embodiments, the preparation method comprises: forming a metal layer and an electrochromic layer on a first substrate by physical and / or chemical deposition, or forming an ion storage layer on a second substrate.

[0103] Furthermore, the metal layer and the electrochromic layer are sequentially deposited on the first substrate by physical and / or chemical deposition.

[0104] In one embodiment, the ion storage layer is deposited on the second substrate by physical and / or chemical deposition.

[0105] In some preferred embodiments, the preparation method includes: forming a metal layer on the first substrate, or forming an electrochromic layer on the metal layer, or forming an ion storage layer on the second substrate by at least one of magnetron sputtering, electron beam evaporation, thermal evaporation, ion plating, etc.

[0106] Furthermore, the physical and / or chemical deposition method performed on the first substrate includes any one or more combinations of magnetron sputtering, electron beam evaporation, thermal evaporation, and ion plating, but is not limited thereto.

[0107] Furthermore, the physical and / or chemical deposition method performed on the second substrate includes any one or more combinations of magnetron sputtering, electron beam evaporation, thermal evaporation, and ion plating, but is not limited thereto.

[0108] The present invention preferentially adopts a magnetron sputtering method to construct an electrochromic layer (such as tungsten oxide) on a first substrate and an energy storage layer (such as tungsten oxide) loaded on a second substrate, thereby avoiding the potential negative impact of complex environmental factors such as external temperature and humidity on the performance of the electrochromic device when electrodepositing tungsten oxide. The present invention can accurately control the thickness of tungsten oxide, avoid film unevenness, and film peeling caused by thickening the energy storage layer, thereby making the overall performance of the electrochromic device more stable and greatly shortening the time for mass production of devices.

[0109] The preparation method of the present invention can effectively avoid the influence of too thick ion storage layer on the color quality of the electrochromic device by depositing the electrochromic layer in the inverted electrochromic energy storage device on the first substrate and separating the ion storage layer from top to bottom.

[0110] In some preferred embodiments, some embodiments of the present invention provide a method for preparing an inverted electrochromic energy storage device, comprising:

[0111] Providing a porous film substrate (i.e., a first substrate);

[0112] A metal layer and an electrochromic layer are sequentially arranged on the porous film substrate to form a first optical resonant cavity;

[0113] The porous film substrate is filled with electrolyte.

[0114] In one embodiment, the preparation method specifically includes: forming the metal layer and the electrochromic layer in sequence on the first surface of the first substrate by physical and / or chemical deposition, and forming an ion storage layer thin film on the second substrate by physical and / or chemical deposition.

[0115] In one embodiment, the liquid electrolyte includes a polymer, an ionic salt, a photoinitiator, and a solvent, and the specific types are as defined above and will not be repeated here. By adopting this curable liquid electrolyte, a UV-curable electrolyte can be formed, which not only has the aforementioned advantages, but also can significantly improve the surface color quality of the inverted electrochromic energy storage device and greatly increase its color switching speed.

[0116] Furthermore, the concentration of ionic salts (such as zinc peraluminate and aluminum perchlorate) in the liquid electrolyte is 0.2-1 mol / L.

[0117] Furthermore, the preparation method includes: physically sealing the color-changing unit, the counter electrode, and the energy storage unit from top to bottom, leaving holes for injecting liquid electrolyte, and allowing the liquid electrolyte to stand after injecting the liquid electrolyte, so that the liquid electrolyte fully infiltrates the first substrate and fully contacts the metal layer, the electrochromic layer, and the ion storage layer. Then, the electrolyte is cured by light, and the cured electrolyte is used to further strengthen the connection between the first substrate of the device, the metal counter electrode, and the second substrate.

[0118] Among them, in some more specific embodiments, the preparation method of the inverted electrochromic energy storage device comprises the following steps:

[0119] 1) Preparation of working electrode and counter electrode

[0120] A metal film and an electrochromic layer film are loaded on a first substrate; an ion storage layer film is loaded on a second substrate; the two together form a working electrode; a zinc sheet is used as a counter electrode of an inverted electrochromic energy storage device.

[0121] 2) Assembly

[0122] The working electrode, the counter electrode and the electrolyte are assembled into a closed structure to obtain the inverted electrochromic energy storage device.

[0123] The inverted electrochromic energy storage device of the present invention is composed of a working electrode, a counter electrode and an electrolyte. Since the tungsten oxide film is loaded on the upper and lower surfaces simultaneously, there is no need to worry about the problem that the discharge window cannot be aligned.

[0124] Furthermore, the preparation method includes: arranging a metal layer and an electrochromic layer on the first surface of the first substrate, connecting it to the counter electrode and the energy storage unit, and then filling the first substrate with a photocurable liquid electrolyte by at least one method including but not limited to scraping, spraying, dipping, and pouring, and then performing the photocuring treatment to cure the liquid electrolyte to form a solid electrolyte. This method can efficiently fill the pore structure of the first substrate with electrolyte, increase the content of electrolyte in the electrochromic device, and enable the electrolyte to be more uniformly and fully in contact with the metal layer, the counter electrode, and the ion storage layer, thereby ensuring the electrical performance of the electrochromic device. At the same time, after the electrolyte is photocured to form a solid electrolyte, it can also strengthen the bonding strength of the second substrate, the counter electrode and the first substrate, and improve the mechanical properties of the electrochromic device.

[0125] Furthermore, the preparation method specifically includes: allowing the first substrate to absorb a photocurable electrolyte, and then irradiating the first substrate with light to perform a photocuring treatment to cure the electrolyte to form a solid electrolyte.

[0126] In some preferred embodiments, the light used in the photocuring process includes ultraviolet light, but is not limited thereto, and the photocuring time is 5 to 10 minutes.

[0127] In summary, the preparation method of the present invention does not use most of the transmission-type electrochromic energy storage devices, but constructs a reflective electrochromic energy storage device, and uses the Fabry-Perot resonant cavity to construct the switching of colorful colors. By combining the electrochromic inversion structure with the energy storage device, a stable inverted electrochromic energy storage device is prepared; at the same time, the thin film sputtering using a magnetron sputtering coating instrument has universality of method, high preparation efficiency, and broad application prospects.

[0128] Another aspect of the embodiments of the present invention further provides applications of the aforementioned inverted electrochromic energy storage device, specifically applications in the fields of display, camouflage or energy storage.

[0129] The technical scheme of the present invention is further described in detail below in conjunction with several preferred embodiments and the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. It should be pointed out that the embodiments described below are intended to facilitate the understanding of the present invention, and do not have any limiting effect on it. Based on the embodiments in the present invention, all other embodiments obtained by ordinary technicians in the field without making creative work belong to the scope of protection of the present invention. The experimental methods for which specific conditions are not specified in the following embodiments are usually carried out under conventional conditions or under the conditions recommended by the manufacturer.

[0130] Example 1

[0131] The structure of an inverted electrochromic energy storage device provided in this embodiment is as follows Figure 2 As shown, it includes an electrochromic layer, a metal layer, a first substrate (i.e., a porous layer), a metal counter electrode, an electrolyte, an ion storage layer, and a second substrate arranged in sequence from top to bottom. The porous layer uses a nylon membrane with a thickness of about 50 μm, and a plurality of holes are distributed on the nylon membrane. The pore size of each hole is about 800 nm to 1000 nm. These holes are filled with ultraviolet light-cured electrolytes, which are in direct contact with the electrochromic layer, the metal layer, and the ion storage layer, respectively.

[0132] The ion storage layer is made of tungsten oxide with a thickness of 1800 nm, and the second substrate is made of an ITO layer with a thickness of about 200 nm.

[0133] The metal layer is a metal W layer with a thickness of about 450 nm, which is in-situ deposited on the porous layer and also has a porous structure. The electrochromic layer is a WO3 layer with a thickness of about 225 nm.

[0134] The precursor of the UV-curable electrolyte, namely the UV-curable electrolyte, comprises 40 wt % of polyacrylate, 20 wt % of zinc perchlorate and aluminum perchlorate, 0.4 wt % of a photoinitiator and the remainder of PC solvent, and the sum of the contents of all components is 100 wt %.

[0135] The electrochromic layer and the metal layer above the first substrate form a Fabry-Perot resonant cavity.

[0136] The inverted electrochromic energy storage device can achieve single-sided multi-color electrochromism and has good energy storage capacity at 0.2 mA / cm 2 The current is 818.5mAh / m 2 Specific capacitance.

[0137] The method for preparing the inverted electrochromic energy storage device comprises:

[0138] Depositing a metal layer and an electrochromic layer in sequence on the front side of the porous layer by magnetron sputtering, and depositing an ion storage layer on the front side of the second substrate by magnetron sputtering;

[0139] The porous substrate is immersed in an ultraviolet light-curing electrolyte to fully absorb the ultraviolet light-curing electrolyte, and then the ultraviolet light-curing electrolyte absorbed by the porous substrate is fully irradiated to solidify into a solid electrolyte, and then three electrodes are respectively drawn from the formed inverted electrochromic energy storage device and the metal electrode to complete the device manufacturing.

[0140] The color of the inverted electrochromic energy storage device prepared in this embodiment is cyan before power is applied. By adding a corresponding voltage window (0.3V to 1.6V) between the metal sheet and the metal layer and adjusting the voltage value, the color of the device can be reversibly converted between cyan and purple. By gradually applying voltages of 0.8V, 0.5V, and 0.3V, the device can achieve colorful changes of cyan, blue, and purple. Figure 4 , UV spectrum such as Figure 7 shown. Figure 3 The schematic diagram of the color change range of the electrochromic layer above the first substrate is shown in FIG. Figure 8 shown.

[0141] Comparative Example 1

[0142] The structure of an inverted electrochromic energy storage device provided in this comparative example is similar to that of Example 1, but the electrochromic layer therein is prepared by electrodeposition, and the color presented is poor and uneven.

[0143] Comparative Example 2

[0144] The structure of an inverted electrochromic energy storage device provided in this comparative example is similar to that of Example 1, except that the thickness of the metal layer on the first substrate is changed, and a 20nm metal film is prepared on the first substrate by physical and / or chemical deposition, and the rest of the structure remains unchanged. After the device is prepared, the conductivity is poorer than that of the 450nm metal film.

[0145] Comparative Example 3

[0146] The structure of an inverted electrochromic energy storage device provided in this comparative example is similar to that of Example 1, except that the thickness of the metal layer on the first substrate is changed, and a 600nm metal film is prepared on the first substrate by physical and / or chemical deposition, and the rest of the structure remains unchanged. After the device is prepared, the conductivity is poorer than that of the 450nm metal film.

[0147] Comparative Example 4

[0148] The structure of an inverted electrochromic energy storage device provided in this comparative example is similar to that of Example 1, but the UV-curable electrolyte therein is replaced with commonly used electrochromic electrolytes PC-Al(ClO4)3 and PC-Zn(ClO4)2. After being infiltrated with liquid electrolyte, the device exhibits a darker color than the device of Example 1, and the reflectivity decreases by 53.6%, which seriously affects the color quality of the device.

[0149] Example 2

[0150] The structure of an inverted electrochromic energy storage device provided in this embodiment is similar to that of Embodiment 1, and also includes an electrochromic layer, a metal layer, a porous layer, a metal counter electrode, an electrolyte, an ion storage layer, and a second substrate arranged in sequence from top to bottom. The difference between the two is that:

[0151] The porous layer uses a porous PP film with a thickness of about 100μm. The porous PP film has multiple evenly distributed holes with a pore size of about 1000nm. These holes are filled with UV-cured electrolytes, which are in direct contact with the electrochromic layer, the metal layer, and the ion storage layer. The metal layer uses a metal W layer with a thickness of about 450nm, which is in-situ deposited on the porous PP film and also has a porous structure. The first electrochromic layer uses a WO3 layer with a thickness of about 205nm.

[0152] The electrolyte composition of this embodiment is similar to that of Embodiment 1, which is 40 wt % of polyacrylate, 20 wt % of zinc perchlorate and aluminum perchlorate, 0.4 wt % of photoinitiator and the balance of PC solvent, and the sum of the contents of all components is 100 wt %.

[0153] A method for preparing the inverted electrochromic energy storage device comprises:

[0154] Using magnetron sputtering, at 3*10-3 In a Pa vacuum environment, a metal layer and an electrochromic layer are deposited on the front side of the first substrate, and an ion storage layer is deposited on the front side of the second substrate by a magnetron sputtering method;

[0155] The porous substrate is immersed in an ultraviolet light-curing electrolyte to fully absorb the ultraviolet light-curing electrolyte, and then the ultraviolet light-curing electrolyte absorbed by the porous substrate is fully irradiated to solidify into a solid electrolyte, and then three electrodes are respectively drawn from the formed inverted electrochromic energy storage device and the metal electrode to complete the device manufacturing.

[0156] The color of an inverted electrochromic energy storage device prepared in this embodiment is purple before power is applied. By adding a corresponding voltage window (1.6V to 0.3V) between the metal sheet and the metal layer and adjusting the voltage value, the color of the device can be reversibly converted between purple and green. By gradually applying voltages of 0.8V, 0.5V, and 0.3V, the device can achieve colorful changes of purple, red, and green. The ultraviolet spectrum is as follows Figure 6 .

[0157] Example 3

[0158] The structure of an inverted electrochromic energy storage device provided in this embodiment is similar to that of embodiment 1, except that the UV-curable electrolyte in embodiment 1 is replaced by a polyurethane-PC-aluminum perchlorate gel electrolyte. Also, a porous polypropylene film with a pore size of 500nm to 1000nm is used to replace the nylon membrane.

[0159] The inverted electrochromic energy storage device uses a WO3 layer with a thickness of about 205nm. The electrochromic device is similar to Example 1, and also exhibits multi-color changes from orange to green when a voltage of 1.6V to 0.3V is applied. The ultraviolet spectrum is as follows Figure 5 .

[0160] Example 4

[0161] The structure of an inverted electrochromic energy storage device provided in this embodiment is similar to that of embodiment 1, except that a polyaniline layer is used to replace the tungsten oxide layer in embodiment 1 as the electrochromic layer, and the ion storage layer of the second substrate is also replaced by a polyaniline layer.

[0162] The electrochromic device can achieve reversible switching between khaki and green when voltages of 0.3V and 1.6V are applied.

[0163] Example 5

[0164] The structure of an inverted electrochromic energy storage device provided in this embodiment is similar to that of Embodiment 1, except that a Nb2O5 layer is used to replace the WO3 layer for color change operation, and the ion storage layer material of the second substrate is also correspondingly replaced by a Nb2O5 layer.

[0165] The initial color of the inverted electrochromic energy storage device is orange, and the color of the device gradually changes to brown and brown-black when a voltage of 0.3V is applied.

[0166] Example 6

[0167] The structure of an inverted electrochromic energy storage device provided in this embodiment is similar to that of Embodiment 1, except that a porous carbon paper with a thickness of about 100 μm is used, the porous carbon paper has a plurality of evenly distributed holes, and the pore size of each hole is about 300 nm. These holes are filled with ultraviolet light-cured electrolytes, and the photocured electrolytes are in direct contact with the metal sheet counter electrode, the ion storage layer, the metal layer above the first substrate, and the electrochromic layer, and also play a bonding role.

[0168] The precursor of the UV-curable electrolyte, namely the UV-curable electrolyte, comprises 30 wt % of polyvinyl chloride, 25 wt % of zinc perchlorate, 0.1 wt % of photoinitiator OMBB and the balance of dimethyl carbonate, and the total content of all components is 100 wt %.

[0169] Example 7

[0170] The structure of an inverted electrochromic energy storage device provided in this embodiment is similar to that of embodiment 1, except that an aluminum metal sheet is used as a counter electrode to replace the zinc electrode in embodiment 1; and the photocurable electrolyte contains 40wt% polyacrylate, 20wt% aluminum perchlorate, 0.4wt% photoinitiator and the remainder PC solvent, and the sum of the contents of all components is 100wt%. However, the stability of the device is slightly inferior to that of metal zinc.

[0171] Example 8

[0172] The structure of an inverted electrochromic energy storage device provided in this embodiment is similar to that of embodiment 1, except that the tungsten oxide layer in embodiment 1 is replaced by a phthalocyanine compound as the electrochromic layer with a thickness of 150 nm, and the ion storage layer of the second substrate is also replaced by a phthalocyanine compound with a thickness of 1000 nm. The metal layer is replaced by titanium with a thickness of 100 nm.

[0173] Example 9

[0174] The structure of an inverted electrochromic energy storage device provided in this embodiment is similar to that of embodiment 1, except that the tungsten oxide layer in embodiment 1 is replaced by a MoO3 layer as the electrochromic layer, with a thickness of 300nm, and the ion storage layer of the second substrate is also replaced by a MoO3 layer, with a thickness of 8000nm. The metal layer is replaced by copper, with a thickness of 450nm.

[0175] In addition, the inventors of this case also conducted experiments with other raw materials and conditions listed in this specification by referring to the methods of Examples 1 to 9, and also produced an inverted electrochromic energy storage device that achieves switching of multiple colors while ensuring the energy storage performance of the electrochromic device itself.

[0176] It should be noted that the above is only a preferred embodiment of the present application and is not intended to limit the present application. Although the present application has been described in detail with reference to the aforementioned embodiments, it is still possible for those skilled in the art to modify the technical solutions described in the aforementioned embodiments or to make equivalent substitutions for some of the technical features therein. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. An inverted electrochromic energy storage device, characterized in that: It includes a working electrode, a counter electrode and an electrolyte, wherein the working electrode includes a color changing unit and an energy storage unit; The color-changing unit includes a first substrate with a porous structure, and a metal layer and an electrochromic layer sequentially arranged on the surface of the first substrate, wherein the electrochromic layer is arranged on a side away from the energy storage unit, and the electrochromic layer and the metal layer can form an optical resonant cavity; The energy storage unit includes a second substrate and an ion storage layer arranged on the surface of the second substrate; The counter electrode is arranged between the color changing unit and the energy storage unit; The electrolyte is distributed in the porous structure of the first substrate, between the counter electrode and the first substrate of the color-changing unit, and between the counter electrode and the ion storage layer of the energy storage unit.

2. The inverted electrochromic energy storage device according to claim 1, characterized in that: The invention comprises an electrochromic layer, a metal layer, a first substrate, an electrolyte, a counter electrode, an electrolyte, an ion storage layer and a second substrate which are stacked in sequence from top to bottom.

3. The inverted electrochromic energy storage device according to claim 1, characterized in that: The metal layer and the electrochromic layer form a metal-medium structure, which can produce optical interference and display multiple colors; And / or, the optical resonant cavity comprises a Fabry-Perot resonant cavity; And / or, the material of the electrochromic layer includes any one or a combination of two or more of an inorganic electrochromic material, an organic electrochromic material, and an organic / inorganic composite electrochromic material, preferably an inorganic electrochromic material; Preferably, the inorganic electrochromic material includes a combination of any one of Co, Rh, Ir, Ni, Cr, Mn, Fe, Ti, V, Nb, Ta, Mo, and W, or an oxide of two or more thereof. Particularly preferably, the inorganic electrochromic material includes any one of LiNiO2, IrO2, NiO, V2O5, lithium cobalt oxide, Rh2O3, CrO3, WO3, MoO3, Nb2O5, Ta2O5, and TiO2, or a combination of two or more thereof. Preferably, the organic electrochromic material comprises any one or a combination of two or more of an organic polymer, an organic small molecule, a metal supramolecular polymer, and a metal organic compound. Particularly preferably, the organic electrochromic material comprises any one or a combination of two or more of methyl viologen, viologen, polyaniline, polythiophene, polypyrrole, Prussian blue, an organic metal chelate, and polydiyne. Particularly preferably, a phthalocyanine compound is used. And / or, the thickness of the electrochromic layer is >0 and ≤1000 nm, preferably 100-500 nm, and particularly preferably 150-300 nm.

4. The inverted electrochromic energy storage device according to claim 1, characterized in that: The metal layer has a porous structure, so that electrolyte ions can pass freely and come into direct contact with the electrochromic layer; And / or, the material of the metal layer is an inactive metal, preferably including any one or a combination of two or more of chromium, gold, silver, copper, tungsten, titanium or their alloys; And / or, the thickness of the metal layer is 100 to 450 nm; And / or, the surface of the first substrate is relatively flat, and a plurality of holes are evenly or unevenly distributed on the surface; preferably, the hole diameter is 100nm to 1100nm; and / or, the material of the first substrate includes any one of an organic material, an inorganic material, and an organic / inorganic composite material, or a combination of two or more thereof, preferably including at least any one of nylon, polysulfone, polyacrylonitrile, modified polysulfone, polyvinylidene fluoride, polyvinyl chloride, polyether sulfone, polypropylene, cellulose, a porous metal film, a porous metal oxide film, a porous non-metallic oxide film, a porous carbon film, and a porous carbon paper, and is particularly preferably a porous nylon film; And / or, the thickness of the first substrate is >0 and ≤1100 μm, preferably >0 and ≤100 μm.

5. The inverted electrochromic energy storage device according to claim 3, characterized in that: The material of the ion storage layer is a material having ion storage capability; And / or, the material of the ion storage layer is the same as that of the electrochromic layer, or the material of the ion storage layer and the material of the electrochromic layer are complementary electrochromic materials, preferably, the material of the electrochromic layer is tungsten oxide, and the material of the ion storage layer is Prussian blue; And / or, the thickness of the ion storage layer is 1000-8000 nm; And / or, the material of the second substrate includes at least any one of ITO, FTO, AZO, GZO, ATO, IZO, NTO, ZnO, OMO, silver nanowire, metal mesh, and PET-ITO; and / or, the thickness of the second substrate is 0.1 to 2 cm; And / or, the material of the counter electrode includes at least any one of Zn, W, Ag, Pt, Au, Al, Cu, Ti, Mo, and Ni; And / or, the thickness of the counter electrode is 0.2-1 mm.

6. The inverted electrochromic energy storage device according to claim 1, characterized in that: The electrolyte is in direct contact with the metal layer, the electrochromic layer, the counter electrode, and the ion storage layer; And / or, the electrolyte comprises a UV-curable electrolyte, preferably, the electrolyte comprises H + , Li + 、Al 3+ 、Na + , K + Mg 2+ 、Zn 2+ , Rb + or Cs + Preferably, the electrolyte contains anions including ClO4 - TFSI - 、NO3 - and SO4 2- At least one of the following, particularly preferably ClO4 - ; Preferably, the electrolyte comprises an aluminum salt compound and a zinc salt compound, and particularly preferably, the electrolyte comprises at least any one of aluminum perchlorate and zinc perchlorate, aluminum chloride and zinc nitrate, aluminum chloride and zinc sulfate, lithium chloride and zinc chloride, lithium sulfate and zinc chloride, and particularly preferably aluminum perchlorate and zinc perchlorate; Preferably, the raw materials for preparing the UV-curable electrolyte include polymer, ionic salt, photoinitiator and solvent; particularly preferably, the raw materials for preparing the UV-curable electrolyte include 30-50wt% polymer, 10-25wt% ionic salt, 0.1-1.0wt% photoinitiator and 35-45wt% solvent; Particularly preferably, the polymer includes at least any one of polyacrylate and polyurethane; Particularly preferably, the ionic salt comprises H + , Li + 、Al 3+ 、Na + , K + Mg 2+ 、Zn 2+ , Rb + , Cs + An ionic salt of at least one of the ions in Particularly preferably, the photoinitiator comprises 1-hydroxy-cyclohexyl phenyl ketone; Particularly preferably, the solvent comprises any one of a low eutectic solvent, propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate, or a combination of two or more thereof, preferably propylene carbonate.

7. The inverted electrochromic energy storage device according to claim 1, characterized in that: Also includes: A sealing material is circumferentially arranged between the peripheral areas of the working electrode and the counter electrode, and is used at least to combine the working electrode and the counter electrode, and to leave a sealed cavity for injecting raw materials for preparing the UV-curable electrolyte; preferably, the sealing material includes at least any one of epoxy resin and 3M glue.

8. The method for preparing the inverted electrochromic energy storage device according to any one of claims 1 to 7, characterized in that: include: A metal layer and an electrochromic layer are sequentially arranged on the surface of the first substrate to form a color-changing unit; An ion storage layer is arranged on the surface of the second substrate to form an energy storage unit, wherein the color changing unit and the energy storage unit together constitute a working electrode; The working electrode, the counter electrode and the liquid electrolyte are assembled into a closed structure and subjected to photocuring treatment to obtain the inverted electrochromic energy storage device.

9. The preparation method according to claim 8, characterized in that: include: forming a metal layer and an electrochromic layer on a first substrate by physical and / or chemical deposition, or forming an ion storage layer on a second substrate; Preferably, the preparation method comprises: forming a metal layer on the first substrate, or forming an electrochromic layer on the metal layer, or forming an ion storage layer on the second substrate by at least one of magnetron sputtering, electron beam evaporation, thermal evaporation, and ion plating; And / or, the liquid electrolyte comprises a polymer, an ionic salt, a photoinitiator and a solvent; preferably, the concentration of the ionic salt in the liquid electrolyte is 0.2 to 1 mol / L; And / or, the preparation method comprises: sealing the color changing unit, the counter electrode, and the energy storage unit from top to bottom, and leaving holes for injecting liquid electrolyte, and standing after injecting the liquid electrolyte, so that the liquid electrolyte fully infiltrates the first substrate and fully contacts with the metal layer, the electrochromic layer, and the ion storage layer; And / or, the preparation method comprises: arranging a metal layer and an electrochromic layer on a first surface of a first substrate, connecting the first substrate to a counter electrode and an energy storage unit, and then filling the first substrate with a photocurable liquid electrolyte by at least one of scraping, spraying, dipping, and pouring, and then performing the photocuring treatment to cure the liquid electrolyte to form a solid electrolyte; And / or, the light used in the photocuring process includes ultraviolet light, and the photocuring time is 5 to 10 minutes.

10. Application of the inverted electrochromic energy storage device according to any one of claims 1 to 7 in the fields of display, camouflage or energy storage.

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