Ion storage material and preparation method and application thereof

Abstract

The invention provides an ion storage material as well as a preparation method and application thereof. The ion storage material comprises a compound shown as a formula (I): SnxAyMzOmRn, the specific M element is anchored in an ion doping form and is mutually combined with the tin oxide-based material, so that the ion storage material has excellent ion and / or electron conduction performance, has high capacity, excellent stability and high cycle capacity retention rate, is a nano material, and is narrow in particle size distribution and fine in particles. As an ion storage layer material of an electrochromic device, the ion storage material can effectively balance ion and / or electron transmission of the device in the charging and discharging process, so that the device has higher contrast ratio and cycle performance, and better optical performance and weather resistance are given to the device. Moreover, the preparation method of the ion storage material is mild in condition, simple in process route, high in yield and suitable for industrial production.

Description

Technical Field

[0001] The present invention belongs to the technical field of color-changing display, and in particular relates to an ion storage material and a preparation method and application thereof. Background Art

[0002] Electrochromism refers to the phenomenon in which a material's optical properties, such as transmittance and reflectance, undergo a reversible color change in response to a voltage. This phenomenon manifests itself as a reversible shift in appearance between a tinted state (e.g., blue or black) and a transparent state. Electrochromism, a current research hotspot, has a wide range of applications, including energy-saving architectural glass, vehicle windows, anti-glare rearview mirrors, electronic displays, electronic paper, camouflage, eyewear, and electronic device casings.

[0003] Traditional electrochromic products are mainly composed of five thin films, including a first conductive layer and a second conductive layer attached to the front transparent substrate and the rear transparent substrate respectively, as well as an ion storage layer, an ion conduction layer (also known as an "electrolyte layer") and an electrochromic layer arranged between the two conductive layers. When voltage is applied to the first conductive layer and the second conductive layer, the ion storage layer assists the electrochromic layer in achieving an electrochromic reaction. The ion storage layer (IS layer), also known as the counter electrode layer (CE layer), mainly functions to store and provide the ions and / or electrons required for electrochromism, thereby maintaining balance throughout the electrochromic process.

[0004] Currently, mass-produced electrochromic products on the market generally suffer from low contrast and insufficient cycle life, failing to meet user experience and requirements. These shortcomings are largely due to the insufficient capacity and poor stability of the ion storage layer materials. Therefore, developing high-capacity and stable ion storage layer materials to improve the contrast and cycle stability of electrochromic products is an urgent problem to be solved in this field. Summary of the Invention

[0005] In view of the shortcomings of the prior art, the purpose of the present invention is to provide an ion storage material and its preparation method and application. The ion storage material has excellent ion and / or electron conductivity, high capacity and good stability, so that the electrochromic device containing it has better contrast and cycle stability.

[0006] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions:

[0007] In a first aspect, the present invention provides an ion storage material comprising a compound represented by formula (I),

[0008] Sn x A y Mz O m R n (I);

[0009] wherein A is selected from at least one element of Group IIIA, Group VA, Group VIIA, Group IIB, and Group IIIB;

[0010] M is selected from at least one element of Group IA, Group IIA, Group IIIA, Group IIB, Group IIIB, Group IVB, Group VB, Group VIB, Group VIIB and Group VIII; R is selected from at least one element of Group IA, Group IIIA, Group IVA, Group VA, Group VIA and Group VIIA; and the value range of x is 0<x≤1; the value range of y is 0≤y≤0.8; the value range of z is 0<z≤0.5; the value range of m is 0<m≤4; the value range of n is 0≤n≤6.

[0011] After extensive research, the present invention screened out M elements with strong electron correlation, and used the M elements to dope the tin oxide-based materials, so that the M elements were anchored in the form of ion doping and combined with the tin oxide-based materials, so that the Sn-containing x A y M z O m R n The ion storage material has a higher carrier concentration, improving the material's ion and / or electron conductivity, and exhibiting high capacity, excellent stability, and cycling performance. As the ion storage layer of an electrochromic device, the ion storage material has high capacity and excellent cycling stability, enabling it to better balance the transport of ions and electrons during charge and discharge, providing the device with improved optical properties and weather resistance, thereby effectively enhancing the contrast and cycling stability of the electrochromic device.

[0012] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. Through the following preferred technical solutions, the objectives and beneficial effects of the present invention can be better achieved and realized.

[0013] In a preferred technical solution, the precursor of the ion storage material is a solid. Preferably, the precursor of the ion storage material before calcination is a solid. In this case, by making the precursor of the ion storage material a solid, or making the precursor of the ion storage material a solid before calcination, the ion storage material can be dehydrated and dried in advance, so that it is at least solid before calcination. This reduces the release of water vapor and other substances during the subsequent calcination process, shortens the calcination time, improves the calcination efficiency, and allows the ion storage material to fully react during the calcination process, thereby obtaining an ion storage material with excellent performance, that is, an ion storage material with high capacity and excellent cyclic stability.

[0014] In a preferred technical solution, the ion storage material is prepared by using Sn-containing oxide and M-containing dopant. Thus, by using M-containing dopant to dope the tin oxide-based material (i.e., Sn-containing oxide), it is anchored in the form of ion doping and combined with the tin oxide-based material, so that the Sn-containing x A y M z O m R n The ion storage material has a higher carrier concentration, which improves the ion and / or electron conductivity of the material, and has high capacity, excellent stability and cycle performance. In addition, by directly doping the tin oxide-based material without using tin-containing salts as precursors, it makes it easier to dope the M element, and the temperature required for subsequent calcination and other processes is also lower, making the Sn-containing x A y M z O m R n The preparation process for the ion storage material is simpler, more cost-effective, and more conducive to mass production. Furthermore, because the tin oxide-based material is directly doped, the yield is higher than when using tin-containing salts as precursors. This means that a smaller amount of doping can achieve a sufficient capacity increase, further saving raw materials and further reducing manufacturing costs.

[0015] In a preferred technical solution, A is selected from at least one of In, F, Cl, Br, I, Sb, Al, Bi, Ga, Tl, Zn, Cd and Ce; and / or M is selected from at least one of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Al, Ga, In, Zn, Cd, Ce, V, Co, W, Cr, Mo, Ti, Ni, Fe, Mn, Rh and Pd; and / or R is selected from at least one of H, B, C, Si, N, P, O, S, F, Cl, Br and I.

[0016] In a preferred technical solution, A is selected from at least one of In, F, Sb, Zn and Al; and / or M is selected from at least one of Ce, V, Co, W, Ti and Ni; and / or R is selected from at least one of H, C, N, P, O, S, F and Cl.

[0017] In a preferred technical solution, the A is selected from at least one element of Group IIIA, Group VIIA, Group IIB and Group IIIB; or, the A is selected from at least one element of Group IIIA, Group VA, Group VIIA and Group IIB; and / or, the M is selected from at least one element of Group IA, Group IIA, Group IIIA, Group IIB, Group IVB, Group VB, Group VIB, Group VIIB and Group VIII; and / or, the R is selected from at least one element of Group IA, Group VA, Group VIA and Group VIIA.

[0018] In a preferred technical solution, the A is selected from at least one of In, F, Zn and Al; and / or the M is selected from at least one of V, Co, W, Ti and Ni; and / or the R is selected from at least one of H, P, O, S and F.

[0019] In a preferred technical solution, the A is selected from at least one element of Group IIIA, Group VA and Group VIIA; and / or, the M is selected from at least one element of Group IIIB, Group VB, Group VIB and Group VIII; or, the M is selected from at least one element of Group VB, Group VIB and Group VIII; and / or, the R is selected from at least one element of Group VIA.

[0020] In a preferred technical solution, the A is selected from at least one of In, F and Sb; and / or the M is selected from at least one of Ce, V, Co and W; or, the M is selected from at least one of V, Co and W; and / or, the R is selected from at least one of O and S.

[0021] In a preferred technical solution, the ratio of y to x is in the range of 0≤y / x≤0.8.

[0022] In a preferred technical solution, the ratio of y to x is in the range of 0≤y / x≤0.5.

[0023] In a preferred technical solution, the ratio of y to x is in the range of 0.05≤y / x≤0.25.

[0024] In a preferred technical solution, the value range of y is 0≤y≤0.5.

[0025] In a preferred technical solution, the value range of y is 0.05≤y≤0.25.

[0026] In a preferred technical solution, the ratio of z to x is in the range of 0<z / x≤0.5.

[0027] In a preferred technical solution, the ratio of z to x is in the range of 0.001≤z / x≤0.2.

[0028] In a preferred technical solution, the ratio of z to x is in the range of 0<z / x<0.01.

[0029] In a preferred technical solution, the ratio of z to x is in the range of 0.04<z / x<0.5.

[0030] In a preferred technical solution, the value range of z is 0.001≤z≤0.2.

[0031] In a preferred technical solution, the value range of m is 0<m≤3.5.

[0032] In a preferred technical solution, the value range of n is 0≤n≤3.

[0033] In a preferred technical solution, the primary particle size of the ion storage material is 10-50 nm.

[0034] In a preferred technical solution, the primary particle size of the ion storage material is 10-20 nm.

[0035] In a preferred technical solution, the average particle size of the ion storage material is 10-500 nm.

[0036] In a preferred technical solution, the average particle size of the ion storage material is 50-200 nm.

[0037] In a preferred technical solution, the specific surface area of ​​the ion storage material is 10-100m 2 / g.

[0038] In a preferred technical solution, the specific surface area of ​​the ion storage material is 15-80m 2 / g.

[0039] In a preferred technical solution, the capacitance of the ion storage material is ≥37 C / g.

[0040] In a preferred technical solution, the capacitance of the ion storage material is ≥40C / g.

[0041] In a preferred technical solution, the capacitance of the ion storage material is ≥45 C / g.

[0042] In a preferred technical solution, the capacitance retention rate of the ion storage material is ≥56% after 1000 charge and discharge cycles at the operating voltage, wherein the operating voltage is selected from the voltage between the maximum oxidation potential and the maximum reduction potential of the ion storage material.

[0043] In a preferred technical solution, the capacitance retention rate of the ion storage material is ≥60% after 1000 charge and discharge cycles at the operating voltage, wherein the operating voltage is selected from the voltage between the maximum oxidation potential and the maximum reduction potential of the ion storage material.

[0044] In a preferred technical solution, the capacitance retention rate of the ion storage material is ≥70% after 1000 charge and discharge cycles at the operating voltage, wherein the operating voltage is selected from the voltage between the maximum oxidation potential and the maximum reduction potential of the ion storage material.

[0045] In a preferred technical solution, the capacitance retention rate of the ion storage material is ≥80% after 1000 charge and discharge cycles at the operating voltage, wherein the operating voltage is selected from the voltage between the maximum oxidation potential and the maximum reduction potential of the ion storage material.

[0046] In a preferred technical solution, the capacitance retention rate of the ion storage material is ≥85% after 1000 charge and discharge cycles at the operating voltage; wherein the operating voltage is selected from the voltage between the maximum oxidation potential and the maximum reduction potential of the ion storage material.

[0047] In a preferred technical solution, the operating voltage has a value range of: 0<operating voltage≤10V.

[0048] In a preferred technical solution, the operating voltage has a value range of: 0<operating voltage≤3V.

[0049] In a preferred technical solution, the operating voltage has a value range of: 0<operating voltage≤2V.

[0050] In a preferred technical solution, the operating voltage has a value range of: 0.5V≤operating voltage≤1.5V.

[0051] In a second aspect, the present invention provides a method for preparing an ion storage material, the preparation method comprising: providing a dispersion liquid, the dispersion liquid comprising a combination of a Sn oxide and a solvent; uniformly mixing the dispersion liquid with an M dopant to obtain a mixed liquid; performing solid-liquid separation on the mixed liquid to obtain a precursor; calcining the precursor to obtain a Sn-containing x A y M z Om R n ion storage material; wherein, the definitions of A, M, R, x, y, z, m and n are as described in the first aspect.

[0052] Preferably, the preparation method is the preparation method of the ion storage material provided in the first aspect.

[0053] Research has revealed that currently commercially available tin oxide (undoped or A-doped) used in the ion storage layer of electrochromic devices offers limited capacity and low stability, resulting in insufficient device contrast and cycling performance. The preparation method provided herein employs a multi-doping process using an M-containing dopant containing an element M with strong electron correlation and a Sn-containing oxide. Through the design and synergy of raw materials and preparation processes, the resulting ion storage material exhibits a higher carrier concentration, enhanced ion and / or electron conductivity, and possesses higher capacity and superior cycling stability.

[0054] In the second aspect of the present invention, the tin oxide-based material (i.e., containing Sn oxide) is doped with a dopant containing M, so that the dopant is anchored in the form of ion doping and combined with the tin oxide-based material, so that the Sn oxide-based material x A y M z O m R n The ion storage material has a higher carrier concentration, which improves the ion and / or electron conductivity of the material, and has high capacity, excellent stability and cycle performance. In addition, by directly doping the tin oxide-based material without using tin-containing salts as precursors, it makes it easier to dope the M element, and the temperature required for subsequent calcination and other processes is also lower, making the Sn-containing x A y M z O m R n The preparation process for the ion storage material is simpler, more cost-effective, and more conducive to mass production. Furthermore, because the tin oxide-based material is directly doped, the yield is higher than when using tin-containing salts as precursors. This means that a smaller amount of doping can achieve a sufficient capacity increase, further saving raw materials and further reducing manufacturing costs.

[0055] In a preferred technical solution, the Sn-containing oxide is selected from at least one of tin oxide and A-doped tin oxide.

[0056] In a preferred technical solution, the solvent is a polar solvent. Due to the high polarity of the polar solvent, the M-containing dopant can effectively adsorb to the surface of the Sn-containing oxide particles of the main material by utilizing the hydroxyl groups on the surface of the dispersion liquid under the influence of the polarity of the solvent. This allows the M-containing dopant to be evenly and tightly adsorbed on the Sn-containing oxide particles of the main material, thereby ensuring a more complete subsequent calcination (annealing) reaction and yielding an ion storage material with excellent performance.

[0057] In a preferred technical solution, the solvent is selected from one of water, acidic aqueous solution, alkaline aqueous solution or saline solution.

[0058] In a preferred technical solution, the solvent is water or an acidic aqueous solution. In this case, when the solvent is an acidic aqueous solution, it can effectively etch the surface of the Sn-containing oxide particles, increasing the active contact sites, allowing the M-containing dopant to more easily and effectively combine with the Sn-containing oxide, thereby forming an excellent high-capacity ion storage material. When the solvent is water, such as deionized water, it can ensure that the M-containing dopant can more easily and effectively combine with the Sn-containing oxide, while also having the advantages of cost savings and environmental friendliness, making it the preferred choice for mass production.

[0059] In a preferred technical solution, the solvent is selected from one of water, hydrochloric acid, nitric acid, acetic acid, hydrofluoric acid, sulfuric acid, ammonia water, sodium chloride solution, calcium chloride solution, aluminum chloride solution or sodium hydroxide solution.

[0060] In a preferred technical solution, the solvent is selected from one of water, hydrochloric acid, nitric acid, acetic acid, hydrofluoric acid or sulfuric acid.

[0061] In a preferred technical solution, the mass ratio of the Sn-containing oxide to the solvent is 1:(0.1-100).

[0062] In a preferred technical solution, the mass ratio of the Sn-containing oxide to the solvent is 1:(0.2-50).

[0063] In a preferred technical solution, the primary particle size of the Sn-containing oxide is 10-50 nm.

[0064] In a preferred technical solution, the primary particle size of the Sn-containing oxide is 10-20 nm.

[0065] In a preferred technical solution, the primary particle size of the M-containing dopant is 1-500 nm.

[0066] In a preferred technical solution, the primary particle size of the M-containing dopant is 10-300 nm.

[0067] In a preferred technical solution, the primary particle size of the M-containing dopant is 100-200 nm.

[0068] In a preferred technical solution, providing the dispersion includes mixing the Sn-containing oxide with a solvent and then performing wet dispersion grinding to obtain the dispersion. Thus, by using a wet dispersion process to fully disperse the Sn-containing oxide and solvent, a dispersion of narrow-sized particles can be obtained. This increases the specific surface area of ​​the Sn-containing oxide, further facilitating the incorporation of an M-containing dopant in subsequent steps, and improving the adsorption of the M-containing dopant on the surface of the Sn-containing oxide particles. This allows the M-containing dopant to be uniformly and tightly adsorbed on the Sn-containing oxide particles, thereby enabling a more complete subsequent calcination (annealing) reaction and resulting in an ion storage material with superior performance.

[0069] In a preferred technical solution, the step of uniformly mixing the dispersion with the M-containing dopant to obtain a mixed liquid comprises: uniformly mixing the dispersion with the M-containing dopant by wet dispersion and grinding to obtain a mixed liquid. Thus, by adopting a wet dispersion process, the material and the solvent undergo efficient relative motion in the cavity, effectively dispersing and shear-grinding the solid particles of the material, i.e., fully dispersing the Sn-containing oxide and the M-containing dopant, and obtaining a mixed liquid with narrow particle size. This increases the specific surface area of ​​the Sn-containing oxide and the M-containing dopant, which is more conducive to the combination of the two, thereby improving the adsorption force of the M-containing dopant on the surface of the Sn-containing oxide particles of the main material. This allows the M-containing dopant to be uniformly and tightly adsorbed on the Sn-containing oxide of the main material, making the subsequent calcination (annealing) reaction more complete, thereby obtaining an ion storage material with better performance.

[0070] In a preferred technical solution, the M-containing dopant is at least one selected from the group consisting of M elemental substance, M-containing oxide, M-containing acid, M-containing base, M-containing salt and M-containing organic matter.

[0071] In a preferred technical solution, the M-containing dopant is selected from at least one of a simple M substance, an M-containing oxide, and an M-containing salt.

[0072] In a preferred technical solution, the M-containing dopant is an M-containing oxide.

[0073] In a preferred technical solution, the mass ratio of the Sn-containing oxide to the M-containing dopant is 1:(0.001-0.5).

[0074] In a preferred technical solution, the mass ratio of the Sn-containing oxide to the M-containing dopant is 1:(0.001-0.2).

[0075] In a preferred technical solution, the solid-liquid separation of the mixed liquid to obtain the precursor includes: solid-liquid separation of the mixed liquid to obtain a precipitated solid; and drying and crushing the precipitated solid to obtain the precursor.

[0076] In a preferred technical solution, the precursor is calcined to obtain Sn x A y M z O m R n The ion storage material comprises: calcining the precursor to obtain an initial ion storage material; crushing the initial ion storage material to obtain the Sn x A y M z O m R n ion storage materials.

[0077] In a preferred technical solution, the drying temperature is 50-140°C.

[0078] In a preferred technical solution, the drying time is 2-48 hours.

[0079] In a preferred technical solution, the calcination is carried out in a protective atmosphere, which is a vacuum atmosphere or an inert gas atmosphere.

[0080] In a preferred technical solution, the calcination temperature is 100-900°C.

[0081] In a preferred technical solution, the heating rate of the calcination is 1-10°C / min.

[0082] In a preferred technical solution, the calcination time is 1-24 hours.

[0083] In a third aspect, the present invention provides an ion storage membrane, which comprises the ion storage material as described in the first aspect or the ion storage material prepared by the preparation method as described in the second aspect.

[0084] In a fourth aspect, the present invention provides an electrochromic device, comprising a first conductive layer, an electrochromic layer, an electrolyte layer, an ion storage layer, and a second conductive layer stacked in sequence, or comprising a first conductive layer, an electrochromic layer, an electrolyte layer, and an ion storage layer stacked in sequence; wherein the ion storage layer comprises the ion storage material as described in the first aspect, or the ion storage material prepared by the preparation method as described in the second aspect, or the ion storage membrane as described in the third aspect.

[0085] In a fifth aspect, the present invention provides a terminal product, comprising the ion storage membrane as described in the third aspect or the electrochromic device as described in the fourth aspect, wherein the terminal product comprises any one of a rearview mirror, a curtain wall, a car sunroof, a car side window, a car windshield, an electronic product housing, glasses, a vehicle, and a display panel.

[0086] Compared with the prior art, the present invention has the following beneficial effects:

[0087] In the ion storage material provided by the present invention, a specific M element is anchored in the form of ion doping and combined with a tin oxide-based material, so that the ion storage material has excellent ion conductivity and / or electron conductivity, high capacity, excellent stability and high cycle capacity retention rate, and is a transparent nanomaterial with a narrow particle size distribution and fine particles. As the ion storage layer material of the electrochromic device, the ion storage material can effectively balance the anion and cation transport of the device during the charge and discharge process, so that the device has higher contrast and cycle performance, and gives the device better optical properties and weather resistance. Moreover, the preparation method of the ion storage material is mild, the process route is simple, the yield is high, and it is suitable for industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0088] Figure 1 XRD spectra of the ion storage materials provided in Examples 1-5 and Comparative Examples 1-2;

[0089] Figure 2A A transmission electron microscope image of the ion storage material provided in Example 1;

[0090] Figure 2B A transmission electron microscope image of the ion storage material provided in Example 2;

[0091] Figure 2C A transmission electron microscope image of the ion storage material provided in Example 3;

[0092] Figure 2D A transmission electron micrograph of the ion storage material provided in Example 4;

[0093] Figure 2E A transmission electron microscope image of the ion storage material provided in Example 5;

[0094] Figure 3A This is the EDS spectrum of the ion storage material provided in Example 1;

[0095] Figure 3B This is an EDS spectrum of the ion storage material provided in Example 2;

[0096] Figure 3C This is an EDS spectrum of the ion storage material provided in Example 3;

[0097] Figure 3D This is an EDS spectrum of the ion storage material provided in Example 4;

[0098] Figure 3E This is the EDS spectrum of the ion storage material provided in Example 5;

[0099] Figure 3F EDS spectrum of the ion storage material provided in Comparative Example 1;

[0100] Figure 3G EDS spectrum of the ion storage material provided in Comparative Example 2;

[0101] Figure 4 The cyclic voltammetry curves of the ion storage material provided in Example 1 at different scan rates;

[0102] Figure 5A The cyclic voltammetry curve of the ion storage material provided in Example 1 before and after 1000 charge and discharge cycles;

[0103] Figure 5B The cyclic voltammogram of the ion storage material provided in Example 2 before and after 1000 charge and discharge cycles;

[0104] Figure 5C The cyclic voltammetry curve of the ion storage material provided in Example 3 before and after 1000 charge and discharge cycles;

[0105] Figure 5D The cyclic voltammetry curve of the ion storage material provided in Example 4 before and after 1000 charge and discharge cycles;

[0106] Figure 5E The cyclic voltammogram of the ion storage material provided in Example 5 before and after 1000 charge and discharge cycles;

[0107] Figure 5F The cyclic voltammetry curve of the ion storage material provided in Example 6 before and after 1000 charge and discharge cycles;

[0108] Figure 5G Cyclic voltammograms of the ion storage material provided in Comparative Example 1 before and after 1000 charge and discharge cycles;

[0109] Figure 5H Cyclic voltammograms of the ion storage material provided in Comparative Example 2 before and after 1000 charge and discharge cycles;

[0110] Figure 6A A normal temperature cyclic transmittance spectrum of a black-transparent electrochromic automobile sunroof glass device prepared using the ion storage material provided in Example 1;

[0111] Figure 6B A normal temperature cyclic transmittance spectrum of a black-transparent electrochromic automobile sunroof glass device prepared using the ion storage material provided in Comparative Example 1;

[0112] Figure 6C A normal temperature cyclic transmittance spectrum of a black-transparent electrochromic automobile sunroof glass device prepared using the ion storage material provided in Comparative Example 2;

[0113] Figure 7A A room temperature cyclic transmittance spectrum of a high-transmittance consumer electronic electrochromic device prepared from the ion storage material provided in Example 1;

[0114] Figure 7B A normal temperature cyclic transmittance spectrum of a high-transmittance consumer electronic electrochromic device prepared from the ion storage material provided in Comparative Example 1;

[0115] Figure 7C This is a room temperature cyclic transmittance spectrum of a high-transmittance consumer electronic electrochromic device prepared using the ion storage material provided in Comparative Example 2. DETAILED DESCRIPTION

[0116] The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the embodiments are merely to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0117] As used herein, the terms "comprises," "including," "having," "containing" or any other variations thereof, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a listed element is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.

[0118] In the present invention, the features defined as "first" or "second" may explicitly or implicitly include one or more such features, and are used to distinguish and describe the features, without any distinction in order or importance.

[0119] The term "at least one" used herein means ≥1, for example, it can be 1 or multiple, illustratively including but not limited to: 2, 2, 3, 4, 5, etc.

[0120] In the description of the present invention, unless otherwise specified, "multiple" means two or more. "Multiple" means two or more.

[0121] One embodiment of the present invention provides an ion storage material, comprising a compound represented by formula (I), Sn x A y Mz O m R n (I), wherein A is at least one element selected from Group IIIA, Group VA, Group VIIA, Group IIB and Group IIIB; it should be noted that A can be one element from Group IIIA, Group VA, Group VIIA, Group IIB and Group IIIB, or can be multiple (two or more) elements, and the multiple elements can belong to the same group or different groups. One or more elements that meet the requirements of Group IIIA, Group VA, Group VIIA, Group IIB and Group IIIB are all within the scope of A described in the present invention.

[0122] In this embodiment, M is selected from at least one element of Group IA, Group IIA, Group IIIA, Group IIB, Group IIIB, Group IVB, Group VB, Group VIB, Group VIIB and Group VIII. It should be noted that M can be one element of Group IA, Group IIA, Group IIIA, Group IIB, Group IIIB, Group IVB, Group VB, Group VIB, Group VIIB and Group VIII, or it can be multiple (two or more) elements. The multiple elements can belong to the same group or different groups. One or more elements of Group IA, Group IIA, Group IIIA, Group IIB, Group IIIB, Group IVB, Group VB, Group VIB, Group VIIB and Group VIII are all within the scope of M described in the present invention.

[0123] In this embodiment, R is selected from at least one element of Group IA, Group IIIA, Group IVA, Group VA, Group VIA and Group VIIA; it should be noted that R can be one element of Group IA, Group IIIA, Group IVA, Group VA, Group VIA and Group VIIA, or it can be multiple (two or more) elements, and the multiple elements can belong to the same group or different groups. One or more elements of Group IA, Group IIIA, Group IVA, Group VA, Group VIA and Group VIIA are all within the scope of R described in the present invention.

[0124] In this embodiment, x can be understood as the molar ratio of the element Sn in the compound represented by formula (I), and its value range is 0<x≤1. For example, x can be 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, etc.

[0125] In this embodiment, y can be understood as the molar ratio of element A in the compound represented by formula (I), and its value range is 0≤y≤0.8, for example, y can be 0, 0.01, 0.02, 0.05, 0.08, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75 or 0.8, etc.; when y=0, it means that the compound does not contain element A. In addition, it should be understood that when A is multiple (two or more) elements, such as A1, A2, and A3, y is the sum of the molar ratios of the multiple elements as A, that is, the sum of the molar ratios of element A1, element A2, and element A3 in the compound represented by formula (I) is y.

[0126] In this embodiment, z can be understood as the molar ratio of the element M in the compound represented by formula (I), and its value range is 0<z≤0.5, for example, z can be 0.01, 0.02, 0.05, 0.08, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45 or 0.5, etc. It should be understood that when M is a plurality of (two or more) elements, for example, M1 and M2, z is the sum of the molar ratios of the plurality of elements serving as M, that is, the sum of the molar ratios of the element M1 and the element M2 in the compound represented by formula (I) is z.

[0127] In this embodiment, m can be understood as the molar ratio of O in the compound shown in formula (I), and its value range is 0<m≤4, for example, m can be 0.1, 0.3, 0.5, 0.8, 1, 1.2, 1.5, 1.8, 2, 2.2, 2.5, 2.8, 3, 3.2, 3.5, 3.8, 4, etc.; under normal circumstances, the value of m can vary depending on the type and chemical valence state of the doping element A; optionally, the value of m can also vary according to the type and chemical valence state of the doping element A and the doping element M.

[0128] In this embodiment, n can be understood as the molar ratio of R in the compound shown in formula (I), and its value range is 0≤n≤6, for example, n can be 0, 0.1, 0.3, 0.5, 0.8, 1, 1.2, 1.5, 1.8, 2, 2.2, 2.5, 2.8, 3, 3.2, 3.5, 3.8, 4, 4.2, 4.5, 4.8, 5, 5.2, 5.5, 5.8 or 6, etc.; when n=0, it means that the compound does not contain element R. Generally, the value of n can vary depending on the type and chemical valence state of the doping element M. It should be understood that when R is a plurality of (two or more) elements, such as R1 and R2, n is the sum of the molar ratios of the plurality of elements as R, that is, the sum of the molar ratios of element R1 and element R2 in the compound shown in formula (I) is n.

[0129] The present invention adopts the M element with strong electron correlation to dope the tin oxide-based material, so that it is anchored in the form of ion doping and combined with the tin oxide-based material. x A y M z O m R n The ion storage material has a higher carrier concentration, improving the material's ion and / or electron conductivity, resulting in high capacity, excellent stability, and cycling performance. As the ion storage layer of an electrochromic device, the ion storage material has high capacity and excellent cycling stability. It can better balance the ion and electron transport of the electrochromic device during charge and discharge, providing the device with better optical performance and weather resistance, thereby effectively improving the contrast and cycling stability of the electrochromic device.

[0130] In one embodiment, the ion storage material is prepared by using Sn-containing oxide and M-containing dopant. Thus, by doping the tin oxide-based material (i.e., Sn-containing oxide) with the M-containing dopant, the ion storage material is anchored and combined with the tin oxide-based material in the form of ion doping, so that the Sn-containing x A y M z O m R n The ion storage material has a higher carrier concentration, which improves the ion and / or electron conductivity of the material, and has high capacity, excellent stability and cycle performance. In addition, by directly doping the tin oxide-based material without using tin-containing salts as precursors, it makes it easier to dope the M element, and the temperature required for subsequent calcination and other processes is also lower, making the Sn-containing x A y M z O m R n The preparation process for the ion storage material is simpler, more cost-effective, and more conducive to mass production. Furthermore, because the tin oxide-based material is directly doped, the yield is higher than when using tin-containing salts as precursors. This means that a smaller amount of doping can achieve a sufficient capacity increase, further saving raw materials and further reducing manufacturing costs.

[0131] In one embodiment, the precursor of the ion storage material is a solid. In another embodiment, the precursor of the ion storage material before calcination is a solid. In this case, by making the precursor of the ion storage material a solid, or making the precursor of the ion storage material a solid before calcination, the ion storage material can be dehydrated and dried in advance, so that it is at least solid before calcination. This reduces the release of water vapor and other substances during the subsequent calcination process, shortens the calcination time, improves the calcination efficiency, and allows the ion storage material to fully react during the calcination process, thereby obtaining an ion storage material with excellent performance, that is, an ion storage material with high capacity and excellent cyclic stability.

[0132] In a specific embodiment, A is selected from at least one of In, F, Cl, Br, I, Sb, Al, Bi, Ga, Tl, Zn, Cd, and Ce; and / or, M is selected from at least one of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Al, Ga, In, Zn, Cd, Ce, V, Co, W, Cr, Mo, Ti, Ni, Fe, Mn, Rh, and Pd; for example, M is selected from any one of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Al, Ga, In, Zn, Cd, Ce, V, Co, W, Cr, Mo, Ti, Ni, Fe, Mn, Rh, and Pd, or, M is selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Al, Ga, In, Zn, Cd, Ce, V, C o, W, Cr, Mo, Ti, Ni, Fe, Mn, Rh and Pd, wherein the combination is not limited to: a combination of Ce and Co, a combination of V and W, a combination of V and Co, a combination of V and Ti, a combination of V and Ni, a combination of Co and W, etc.; and / or, R is selected from at least one of H, B, C, Si, N, P, O, S, F, Cl, Br and I; for example, R is selected from one of H, B, C, Si, N, P, O, S, F, Cl, Br and I, or a combination of multiple (two or more), and the groups formed by the combination include, but are not limited to, hydroxide, oxalate, carbonate, phosphate, sulfate, nitrate, carboxylate, acetylacetonate, C1-C6 (e.g., C1, C2, C3, C4, C5, C6) alkoxy, etc.

[0133] In a specific embodiment, A is selected from at least one of In, F, Sb, Zn and Al; and / or, M is selected from at least one of Ce, V, Co, W, Ti and Ni; and / or, R is selected from at least one of H, C, N, P, O, S, F and Cl.

[0134] In a specific embodiment, A is selected from at least one element of Group IIIA, Group VIIA, Group IIB and Group IIIB; or, A is selected from at least one element of Group IIIA, Group VA, Group VIIA and Group IIB; and / or, M is selected from at least one element of Group IA, Group IIA, Group IIIA, Group IIB, Group IVB, Group VB, Group VIB, Group VIIB and Group VIII; and / or, R is selected from at least one element of Group IA, Group VA, Group VIA and Group VIIA.

[0135] In a specific embodiment, A is selected from at least one of In, F, Zn and Al; and / or M is selected from at least one of V, Co, W, Ti and Ni; and / or R is selected from at least one of H, P, O, S and F.

[0136] In a specific embodiment, A is selected from at least one element of Group IIIA, Group VA and Group VIIA; and / or, M is selected from at least one element of Group IIIB, Group VB, Group VIB and Group VIII; or, M is selected from at least one element of Group VB, Group VIB and Group VIII; and / or, R is selected from at least one element of Group VIA.

[0137] In a specific embodiment, A is selected from at least one of In, F, and Sb; and / or M is selected from at least one of Ce, V, Co, and W; or M is selected from at least one of V, Co, and W; and / or R is selected from at least one of O and S.

[0138] In one embodiment, the ratio of y to x is in the range of 0≤y / x≤0.8. In one embodiment, the ratio of y to x is in the range of 0≤y / x≤0.5. In one embodiment, the ratio of y to x is in the range of 0.05≤y / x≤0.25. For example, y / x can be 0, 0.01, 0.02, 0.05, 0.08, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75 or 0.8, etc.

[0139] In one embodiment, the value range of y is 0≤y≤0.5. In one embodiment, the value range of y is 0.05≤y≤0.25. For example, y can be 0, 0.01, 0.05, 0.06, 0.08, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45 or 0.5, etc.

[0140] In one embodiment, the ratio of z to x is in the range of 0 < z / x ≤ 0.5. In one embodiment, the ratio of z to x is in the range of 0.001 ≤ z / x ≤ 0.2. For example, z / x can be 0.001, 0.01, 0.02, 0.05, 0.08, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, or 0.5.

[0141] In one embodiment, the ratio of z to x is in the range of 0 < z / x < 0.01. Thus, the ion storage material not only has a high capacity, excellent stability, and a high cycle capacity retention rate, but also has a relatively low doping ratio of the M element, which can save costs and is more conducive to mass production.

[0142] In another specific embodiment, the ratio of z to x is in the range of 0.04 < z / x < 0.5. Thus, by making the amount of doped M element sufficiently large, the ion storage material can have more excellent ion and / or electron conductivity, significantly improve capacity, have better stability and higher cycle capacity retention, and improve the contrast of electrochromic devices using the ion storage material, thereby further broadening its application areas, for example, enabling more effective application in fields such as glasses and architectural glass with high contrast requirements.

[0143] In one embodiment, the value range of z is 0.001≤z≤0.2. For example, z can be 0.001, 0.005, 0.01, 0.05, 0.1, 0.15 or 0.2.

[0144] In one embodiment, the value range of m is 0 < m ≤ 5. In one embodiment, the value range of m is 0 < m ≤ 4. In one embodiment, the value range of m is 0 < m ≤ 3.5. In one embodiment, the value range of m is 0 < m ≤ 2. For example, m can be 0.1, 0.2, 0.5, 0.8, 1, 1.2, 1.5, 1.8, 2, 2.2, 2.5, 2.8, 3, 3.2, 3.5, 3.8, 4, 4.5, or 5.

[0145] In one embodiment, the value range of n is 0≤n≤6. In one embodiment, the value range of n is 0≤n≤3. In one embodiment, the value range of n is 0≤n≤2. For example, n can be 0, 0.1, 0.3, 0.5, 0.8, 1, 1.2, 1.5, 1.8, 2, 2.2, 2.5, 2.8, 3, 3.2, 3.5, 3.8, 4, 4.2, 4.5, 4.8, 5, 5.2, 5.5, 5.8 or 6, etc.

[0146] In one embodiment, the ion storage material comprises Sn x F y M z O m+n 、SnM z O m+n 、Sn x In y M z O m+n 、Sn x Sb y M z O m+n any one or a combination of at least two of; and / or, M is selected from at least one of V, Ce, Co, W, Ti, Ni (for example, 1 type, 2 types, etc.); and / or, 0.5<x≤1, and / or, 0≤y≤0.3, and / or, 0.01≤z≤0.2, and / or, 1≤m≤5, and / or, 0.01≤n≤1.

[0147] In one embodiment, the primary particle size of the ion storage material is less than or equal to 100 nm. In one embodiment, the primary particle size of the ion storage material is 10-50 nm. In one embodiment, the primary particle size of the ion storage material is 10-20 nm. For example, the ion storage material can be 5 nm, 10 nm, 12 nm, 15 nm, 18 nm, 20 nm, 22 nm, 25 nm, 28 nm, 30 nm, 32 nm, 35 nm, 38 nm, 40 nm, 42 nm, 45 nm, 48 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, or 100 nm.

[0148] For example, the primary particle size of the ion storage material can be measured by electron microscopy (scanning electron microscopy and / or transmission electron microscopy).

[0149] In one embodiment, the average particle size of the ion storage material is 10-500 nm. In one embodiment, the average particle size of the ion storage material is 50-200 nm. In one embodiment, the average particle size of the ion storage material is 80-160 nm. For example, the average particle size can be 10 nm, 20 nm, 30 nm, 50 nm, 80 nm, 100 nm, 120 nm, 150 nm, 160 nm, 180 nm, 200 nm, 250 nm, 300 nm, 350 nm, 400 nm, 450 nm, or 500 nm.

[0150] For example, the average particle size of the ion storage material (the particle size corresponding to the cumulative particle size distribution percentage reaching 50%, D 50 Particle size) can be obtained by particle size analyzer testing.

[0151] In one embodiment, the specific surface area of ​​the ion storage material is 10-100 m 2 In one embodiment, the specific surface area of ​​the ion storage material is 15-80 m 2 / g. For example, it can be 10m 2 / g、15m 2 / g, 20m 2 / g、30m 2 / g, 40m 2 / g, 50m 2 / g, 60m 2 / g、70m 2 / g、80m 2 / g、90m 2 / g or 100m 2 / g, etc.

[0152] Exemplarily, the specific surface area of ​​the ion storage material is a BET (an abbreviation of three scientists, Brunauer, Emmett and Teller) specific surface area.

[0153] In one embodiment, the electrical conductivity of the ion storage material is ≥0.1 S / cm. In one embodiment, the electrical conductivity of the ion storage material is ≥0.18 S / cm. In one embodiment, the electrical conductivity of the ion storage material is ≥0.45 S / cm. For example, the electrical conductivity may be 0.1 S / cm, 0.15 S / cm, 0.18 S / cm, 0.2 S / cm, 0.3 S / cm, 0.4 S / cm, 0.45 S / cm, 0.5 S / cm, 0.6 S / cm, 0.7 S / cm, 0.8 S / cm, etc.

[0154] In one embodiment, the capacitance of the ion storage material is ≥37 C / g. In one embodiment, the capacitance of the ion storage material is ≥40 C / g. In one embodiment, the capacitance of the ion storage material is ≥45 C / g.

[0155] In one embodiment, the ion storage material has a capacitance retention rate of ≥56% after 1000 charge-discharge cycles at the operating voltage. In one embodiment, the ion storage material has a capacitance retention rate of ≥60% after 1000 charge-discharge cycles at the operating voltage. In one embodiment, the ion storage material has a capacitance retention rate of ≥70% after 1000 charge-discharge cycles at the operating voltage. In one embodiment, the ion storage material has a capacitance retention rate of ≥80% after 1000 charge-discharge cycles at the operating voltage. In one embodiment, the ion storage material has a capacitance retention rate of ≥85% after 1000 charge-discharge cycles at the operating voltage; wherein the operating voltage is selected from a voltage between the maximum oxidation potential and the maximum reduction potential of the ion storage material.

[0156] It should be noted that the operating voltage is divided into a charging voltage and a discharging voltage. A charge-discharge cycle refers to charging at the charging voltage and discharging at the discharging voltage. This means that one cycle can be charging first and then discharging, or discharging first and then charging. For example, the charging voltage is 1V (relative to an AgCl electrode), and the discharging voltage is -1V (relative to an AgCl electrode). The maximum oxidation potential of the ion storage material is 1.5V, and the maximum reduction potential is -1.5V. Both the (operating voltage) charging voltage and the discharging voltage are within this range (the absolute values ​​are smaller, and the positive and negative signs only represent the direction of charge and discharge, not the magnitude of the voltage).

[0157] In one embodiment, the maximum oxidation potential and maximum reduction potential of the ion storage material can be obtained based on its own CV curve. For example, the maximum potential corresponding to the oxidation peak in the CV curve is the maximum oxidation potential, and the maximum potential corresponding to the reduction peak is the maximum reduction potential. In one embodiment, the maximum oxidation potential and maximum reduction potential of the ion storage material can be obtained based on the CV curve of the electrochromic material used to form an EC device. For example, the maximum potential corresponding to the oxidation peak can be determined as the maximum oxidation potential, and the maximum potential corresponding to the reduction peak can be determined as the minimum reduction potential based on the CV curve of the electrochromic material, thereby determining the maximum oxidation potential and maximum reduction potential of the ion storage material. Of course, the maximum oxidation potential and maximum reduction potential of the ion storage material can also be determined using other methods.

[0158] In one embodiment, the operating voltage has a value range of 0 < operating voltage ≤ 3 V. In one embodiment, the operating voltage has a value range of 0 < operating voltage ≤ 2 V. In one embodiment, the operating voltage has a value range of 0.5 V ≤ operating voltage ≤ 1.5 V.

[0159] For example, the capacitance and cycle capacity retention of the ion storage material are measured using an electrochemical workstation in a three-electrode system.

[0160] A specific embodiment of the present invention provides a method for preparing an ion storage material, the preparation method comprising: providing a dispersion liquid, wherein the dispersion liquid comprises a combination of a Sn oxide and a solvent; uniformly mixing the dispersion liquid with an M dopant to obtain a mixed liquid; performing solid-liquid separation on the mixed liquid to obtain a precursor; calcining the precursor to obtain a Sn-containing x A y M z O m R n Ion storage material; wherein, the definitions of A, M, R, x, y, z, m and n are as described in the above specific embodiments.

[0161] In one embodiment, the preparation method is a method for preparing an ion storage material comprising the compound represented by formula (I).

[0162] The present invention has found that existing commercial tin oxide (undoped or A-doped) used in the ion storage layer of electrochromic devices offers limited capacity and low stability, resulting in insufficient device contrast and cycling performance. The preparation method provided by the present invention employs a multi-doping method using an M-containing dopant with strong electron correlation and a Sn-containing oxide. Through the design and synergy of raw materials and preparation processes, the resulting ion storage material has a higher carrier concentration, significantly enhanced ion and / or electron conductivity, and exhibits high capacity and excellent stability.

[0163] In a specific embodiment of the present invention, the tin oxide-based material (i.e., containing Sn oxide) is doped with a dopant containing M, so that the dopant is anchored in the form of ion doping and combined with the tin oxide-based material. x A y M z O m R n The ion storage material has a higher carrier concentration, which improves the ion and / or electron conductivity of the material, and has high capacity, excellent stability and cycle performance. In addition, by directly doping the tin oxide-based material without using tin-containing salts as precursors, it makes it easier to dope the M element, and the temperature required for subsequent calcination and other processes is also lower, making the Sn-containing x A y M z O m R nThe preparation process for the ion storage material is simpler, more cost-effective, and more conducive to mass production. Furthermore, because the tin oxide-based material is directly doped, the yield is higher than when using tin-containing salts as precursors. This means that a smaller amount of doping can achieve a sufficient capacity increase, further saving raw materials and further reducing manufacturing costs.

[0164] In a specific embodiment, the Sn-containing oxide is selected from at least one of tin oxide and A-doped tin oxide. For example, it can be tin oxide, A-doped tin oxide, or a combination (mixture) of tin oxide and A-doped tin oxide.

[0165] In one embodiment, the solvent is a polar solvent. Due to the high polarity of the polar solvent, the M-containing dopant can effectively adsorb to the surface of the Sn-containing oxide particles of the main material by utilizing the hydroxyl groups on the surface of the dispersion liquid. This allows the M-containing dopant to be evenly and tightly adsorbed on the Sn-containing oxide particles of the main material, thereby ensuring a more complete subsequent calcination (annealing) reaction and yielding an ion storage material with excellent performance.

[0166] In one embodiment, the solvent is selected from water, an acidic aqueous solution, an alkaline aqueous solution or a salt solution.

[0167] In one embodiment, the solvent is water or an acidic aqueous solution. In this case, when the solvent is an acidic aqueous solution, it can effectively etch the surface of the Sn-containing oxide particles, increasing active contact sites, allowing the M-containing dopant to more easily and effectively combine with the Sn-containing oxide, thereby forming an excellent high-capacity ion storage material. When the solvent is water, such as deionized water, it can ensure that the M-containing dopant can more easily and effectively combine with the Sn-containing oxide, while also being cost-effective and environmentally friendly, making it the preferred choice for mass production.

[0168] In a specific embodiment, the acidic aqueous solution includes any one or a combination of at least two of a hydrochloric acid aqueous solution, a nitric acid aqueous solution, an acetic acid aqueous solution, a hydrofluoric acid aqueous solution, and a sulfuric acid aqueous solution.

[0169] In the present invention, the concentration of the acidic substance in the acidic aqueous solution is not particularly limited, and its pH value can be less than 7. For example, the pH value of the acidic aqueous solution is 0, 0.1, 0.5, 0.8, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6 or 6.5.

[0170] In one embodiment, the solvent is selected from one of water, hydrochloric acid, nitric acid, acetic acid, hydrofluoric acid, sulfuric acid, aqueous ammonia, sodium chloride solution, calcium chloride solution, aluminum chloride solution or sodium hydroxide solution. In one embodiment, the solvent is selected from one of water, hydrochloric acid, nitric acid, acetic acid, hydrofluoric acid or sulfuric acid.

[0171] In one embodiment, the mass ratio of the Sn-containing oxide to the solvent is 1:(0.1-100). In one embodiment, the mass ratio of the Sn-containing oxide to the solvent is 1:(0.2-50). For example, the mass ratio can be 1:0.1, 1:0.2, 1:0.5, 1:1, 1:3, 1:5, 1:8, 1:10, 1:15, 1:20, 1:25, 1:30, 1:35, 1:40, 1:45, 1:50, 1:55, 1:60, 1:70, 1:80, 1:90, or 1:100.

[0172] In one embodiment, the Sn-containing oxide is a particle of submicron size or less. In one embodiment, the primary particle size of the Sn-containing oxide is 10-50 nm. In one embodiment, the primary particle size of the Sn-containing oxide is 10-20 nm. For example, it can be 10 nm, 12 nm, 15 nm, 18 nm, 20 nm, 22 nm, 25 nm, 28 nm, 30 nm, 32 nm, 35 nm, 38 nm, 40 nm, 42 nm, 45 nm, 48 nm, or 50 nm.

[0173] In one embodiment, the M-containing dopant is a particle of submicron size or less. In one embodiment, the primary particle size of the M-containing dopant is 1-500 nm. In one embodiment, the primary particle size of the M-containing dopant is 10-300 nm. In one embodiment, the primary particle size of the M-containing dopant is 100-200 nm. Exemplarily, the primary particle size of the M-containing dopant can be 1 nm, 5 nm, 10 nm, 20 nm, 50 nm, 80 nm, 100 nm, 150 nm, 200 nm, 300 nm, 400 nm, 450 nm, or 500 nm.

[0174] In a specific embodiment, the Sn oxide-containing primary particles have a true particle size of 10-50 nm and are blue or light green powder; and / or the M dopant-containing primary particles have a true particle size of 10-300 nm.

[0175] For example, the particle sizes of the Sn-containing oxide and the M-containing dopant can be measured by electron microscopy (scanning electron microscopy and / or transmission electron microscopy).

[0176] In a specific embodiment, providing a dispersion liquid includes: mixing the Sn-containing oxide with a solvent and then performing wet dispersion grinding to obtain a dispersion liquid. Among them, the dispersion grinding method includes ball milling dispersion, air flow milling dispersion, mechanical milling dispersion, sand milling dispersion, etc. The so-called wet dispersion grinding refers to grinding and dispersing the material in the presence of a solvent (wet method). Thus, by adopting a wet dispersion process, the Sn-containing oxide and the solvent are fully dispersed, and a dispersion liquid of narrow particle size particles can be obtained, so that the specific surface area of ​​the Sn-containing oxide is larger, which is more conducive to the combination of the M-containing dopant in the subsequent steps, and the adsorption force of the M-containing dopant on the surface of the particles of the main material containing Sn oxide is improved, that is, the M-containing dopant can be evenly and tightly adsorbed on the main material containing Sn oxide, so that the subsequent calcination (annealing) reaction is more sufficient to obtain an ion storage material with better performance.

[0177] In one embodiment, the wet dispersion grinding can be wet mechanical grinding, i.e., the material is dispersed under stirring conditions, wherein the stirring shaft speed is 500-4000 rpm, for example, 600 rpm, 800 rpm, 1000 rpm, 1500 rpm, 2000 rpm, 2500 rpm, 3000 rpm, or 3500 rpm.

[0178] In one embodiment, the wet dispersion grinding can be wet ball milling, i.e., ball milling beads are added to a solvent and the material is ball milled at a certain rotation speed. The size of the ball milling beads is not particularly limited, and may, for example, be 0-500 g, 10-300 g, 50-250 g, or 100-200 g. The rotation speed during ball milling is not particularly limited, and may, for example, be 100-1000 rpm, 200-800 rpm, 300-700 rpm, or 400-600 rpm.

[0179] In a specific embodiment, the wet dispersion grinding time is 0.1-48h, for example, it can be 0.5h, 1h, 2h, 3h, 4h, 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h, 24h, 26h, 28h, 30h, 32h, 34h, 36h, 38h, 40h, 42h, 44h or 46h, etc.

[0180] In one embodiment, the dynamic light scattering of the dispersion is used to measure the D 50 Particle size (particle size corresponding to 50% of the cumulative particle size distribution percentage) is 0.05-1μm, D 99 The particle size (particle size corresponding to when the cumulative particle size distribution percentage reaches 99%) is 0.1-2 μm, and the true particle size of the primary particles measured by transmission electron microscopy is 5-10 nm.

[0181] In one embodiment, the dispersion liquid is mixed evenly with the M-containing dopant to obtain a mixed liquid, which includes: mixing the dispersion liquid and the M-containing dopant evenly by wet dispersion grinding to obtain a mixed liquid. The so-called wet dispersion grinding here can be the same as the wet dispersion grinding method used when forming the dispersion liquid. Thus, by adopting a wet dispersion process, the material and the solvent are efficiently moved relative to each other in the cavity, and the solid particles of the material are effectively dispersed and sheared and ground, that is, the Sn-containing oxide and the M-containing dopant are fully dispersed, and a mixed liquid of narrow particle size particles can be obtained, so that the specific surface area of ​​the Sn-containing oxide and the M-containing dopant is larger, which is more conducive to the combination of the two, thereby improving the adsorption force of the M-containing dopant on the surface of the particles of the main material containing Sn oxide, that is, the M-containing dopant can be evenly and tightly adsorbed on the main material containing Sn oxide, so that the subsequent calcination (annealing) reaction is more sufficient to obtain an ion storage material with better performance.

[0182] In one embodiment, the M-containing dopant is selected from at least one of an M elemental substance, an M-containing oxide, an M-containing acid, an M-containing base, an M-containing salt, and an M-containing organic matter. In one embodiment, the M-containing dopant is selected from at least one of an M elemental substance, an M-containing oxide, and an M-containing salt. In one embodiment, the M-containing dopant is an M-containing oxide. Thus, the appropriate composition of the M-containing dopant can be selected according to actual needs. In particular, when the M-containing dopant is an M-containing oxide, since the mixed materials are all oxides, their properties are more similar and the preparation process is more simplified, which is more conducive to the use of a single simple solvent for preparation, saving manufacturing costs. Moreover, since the materials are all oxides, the reaction can be more sufficient, so that M can be more conveniently and effectively doped into the main material containing Sn oxide, thereby making it easier to prepare an ion storage material with excellent performance.

[0183] In one embodiment, the mass ratio of the Sn-containing oxide to the M-containing dopant is 1:(0.001-0.5). In one embodiment, the mass ratio of the Sn-containing oxide to the M-containing dopant is 1:(0.001-0.2). Illustratively, the mass ratio of Sn-containing oxide to M-containing dopant can be 1:0.001, 1:0.002, 1:0.005, 1:0.008, 1:0.01, 1:0.02, 1:0.05, 1:0.08, 1:0.1, 1:0.12, 1:0.15, 1:0.18, 1:0.2, 1:0.22, 1:0.25, 1:0.28, 1:0.3, 1:0.32, 1:0.35, 1:0.38, 1:0.4, 1:0.42, 1:0.45, 1:0.48 or 1:0.5, etc.

[0184] In one embodiment, the mixed liquid is subjected to solid-liquid separation to obtain a precursor, comprising: subjecting the mixed liquid to solid-liquid separation to obtain a precipitated solid; and drying and crushing the precipitated solid to obtain the precursor.

[0185] In one embodiment, the solid-liquid separation method includes at least one of centrifugal separation, precipitation separation, evaporation separation and filtration separation.

[0186] In a specific embodiment, the drying method can be to place the precipitated solid in a container (such as an oven) for drying, or to place the precipitated solid in air for air drying.

[0187] In one embodiment, the drying temperature is 40-150° C. In one embodiment, the drying temperature is 50-140° C. In one embodiment, the drying temperature is 60-120° C. For example, the drying temperature can be 40° C., 50° C., 60° C., 70° C., 80° C., 90° C., 100° C., 110° C., 120° C., 130° C., 140° C., or 150° C.

[0188] In one embodiment, the drying time is 2-48 hours. In one embodiment, the drying time is 2-24 hours. In one embodiment, the drying time is 3-12 hours. Exemplarily, the drying time can be 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 8 hours, 9 hours, 10 hours, 12 hours, 15 hours, 18 hours, 20 hours, 22 hours, 25 hours, 28 hours, 30 hours, 32 hours, 35 hours, 38 hours, 40 hours, 42 hours, 45 hours or 48 hours, etc.

[0189] In one embodiment, the pulverization method includes at least one of mortar grinding, ball milling, air flow milling, mechanical milling and roller milling.

[0190] In one embodiment, the precursor is calcined to obtain Sn x A y M z O m R n The ion storage material comprises: calcining a precursor to obtain an initial ion storage material; crushing the initial ion storage material to obtain an ion storage material including Sn x A y M z O m R n Thus, the calcined ion storage material is crushed to obtain the desired Sn x A y M z O m Rn The ion storage material has a smaller particle size and a more uniform particle size distribution. The material can be directly used for subsequent dissolution, coating and other operations, so that the membrane containing the ion storage material can be formed more uniform without agglomeration. The electrochromic device containing the ion storage material thus obtained will have better performance, and the obtained electrochromic device will have better high capacity and cycle stability and other characteristics.

[0191] It should be noted that although the initial ion storage material can be obtained by calcination as described herein, the Sn x A y M z O m R n ion storage materials, but in fact, Sn can also be directly obtained after calcination x A y M z O m R n The ion storage material can be prepared without going through a crushing step, and the specific step selection can be adjusted according to actual requirements.

[0192] In a specific embodiment, the calcining device includes a tubular furnace, a muffle furnace or a roller kiln, and may also include a heating device such as an oven and a reactor.

[0193] In one embodiment, the calcination is carried out in a protective atmosphere, which is a vacuum atmosphere or an inert gas atmosphere. In one embodiment, the protective atmosphere includes a nitrogen atmosphere, an argon atmosphere, a helium atmosphere, a neon atmosphere or a vacuum atmosphere.

[0194] In one embodiment, the calcination temperature is 100-900°C. In one embodiment, the calcination temperature is 100-600°C. In one embodiment, the calcination temperature is 150-500°C. For example, the calcination temperature can be 100°C, 150°C, 200°C, 250°C, 300°C, 350°C, 400°C, 450°C, 500°C, 550°C, 600°C, 650°C, 700°C, 750°C, 800°C, 850°C or 900°C, etc. It should be noted that the calcination temperature here can be one temperature or multiple temperatures, that is, multiple temperatures can be set during the calcination process to achieve the effect of staged calcination.

[0195] In a specific embodiment, the heating rate of calcination is 1-20°C / min. In a specific embodiment, the heating rate of calcination is 1-15°C / min. In a specific embodiment, the heating rate of calcination is 1-10°C / min. For example, the heating rate of calcination can be 1°C / min, 2°C / min, 3°C / min, 4°C / min, 5°C / min, 6°C / min, 7°C / min, 8°C / min, 9°C / min, 10°C / min, 11°C / min, 12°C / min, 15°C / min or 20°C / min, etc. It should be noted that the so-called heating rate of calcination here can be one heating rate or multiple heating rates, that is, multiple heating rates can be set during the calcination process to achieve the effect of staged calcination.

[0196] In one embodiment, the calcination time is 1-48 hours. In one embodiment, the calcination time is 1-24 hours. In one embodiment, the calcination time is 2-12 hours. In one embodiment, the calcination time is 2-6 hours. For example, the calcination time can be 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 8 hours, 10 hours, 12 hours, 15 hours, 18 hours, 20 hours, 22 hours, 24 hours, 30 hours, 40 hours, 45 hours or 48 hours. It should be noted that the so-called calcination time here can be a single calcination time or a plurality of calcination times, that is, during the calcination process, a plurality of calcination times can be set to achieve the effect of staged calcination.

[0197] In one embodiment, calcination can include staged calcination. In some embodiments, the temperature can be raised to a first calcination temperature at a first heating rate, maintained at the first calcination temperature (calcination) for a first calcination time; then, the temperature can be raised to a second calcination temperature at a second heating rate, maintained at the second calcination temperature (calcination) for a second calcination time. In this way, the effect of multi-stage calcination can be achieved.

[0198] In one embodiment, the method of pulverizing the initial ion storage material includes grinding with a sand mill, pulverizing with a high-speed mechanical mixer, pulverizing with a high-speed ball mill, or pulverizing with a jet mill.

[0199] In one embodiment, the preparation method of the ion storage material includes: mixing a Sn-containing oxide with a polar solvent and then performing wet dispersion grinding to obtain a dispersion liquid; the mass ratio of the Sn-containing oxide to the polar solvent is 1: (0.2-50); mixing the dispersion liquid with an M-containing dopant and dispersing them uniformly to obtain a mixed liquid; the mass ratio of the Sn-containing oxide to the M-containing dopant is 1: (0.01-0.2); performing solid-liquid separation on the mixed liquid to obtain a precipitated solid; drying and crushing the precipitated solid to obtain a precursor; calcining the precursor at 100-900° C. in a protective atmosphere for 1-24 hours to obtain an initial state ion storage material; crushing the initial state ion storage material to obtain a Sn-containing ion storage material. x A y M z O m R n ion storage materials.

[0200] One embodiment of the present invention provides an ion storage membrane, comprising the ion storage material provided in the aforementioned embodiments or the ion storage material prepared by the preparation method provided in the aforementioned embodiments. In some embodiments, the ion storage membrane can be formed by coating with a coating solution containing the ion storage material dissolved therein and then drying the coating solution to form the ion storage membrane.

[0201] A specific embodiment of the present invention provides an electrochromic device, which includes a first conductive layer, an electrochromic layer, an electrolyte layer, an ion storage layer, and a second conductive layer stacked in sequence, or the electrochromic device includes a first conductive layer, an electrochromic layer, an electrolyte layer, and an ion storage layer stacked in sequence; wherein the ion storage layer includes the ion storage material provided in the aforementioned embodiment, or the ion storage material prepared by the preparation method provided in the aforementioned embodiment, or the ion storage membrane provided in the aforementioned embodiment.

[0202] In one embodiment, the electrochromic device further comprises a first substrate, wherein the first substrate is located on a side of the first conductive layer away from the electrochromic layer. In one embodiment, the electrochromic device further comprises a second substrate, wherein the second substrate is located on a side of the second conductive layer away from the ion storage layer, or the second substrate is located on a side of the ion storage layer away from the electrolyte layer.

[0203] In one embodiment, the first substrate and / or the second substrate may be a flexible substrate, such as PET (polyethylene terephthalate). In another embodiment, the first substrate and / or the second substrate may be a rigid substrate, such as glass.

[0204] A specific embodiment of the present invention provides a terminal product, which includes the ion storage membrane provided in the above embodiment or the electrochromic device provided in the above embodiment, wherein the terminal product includes any one of a rearview mirror, a curtain wall, a car sunroof, a car side window, a car windshield, an electronic product housing, glasses, a vehicle, and a display panel.

[0205] The ion storage material, the preparation method and the application of the ion storage material of the present invention will be further described in detail below with reference to the examples.

[0206] In the following specific examples and comparative examples of the present invention, the raw materials used are all commercially available materials.

[0207] Example 1

[0208] This embodiment provides an ion storage material and a preparation method thereof, the preparation method comprising the following steps:

[0209] (1) The primary particle size is 10-20nm and the chemical formula is Sn 0.9 F 0.1 O 1.75 100 g of nano-fluorine-doped tin oxide (FTO) particles (atomic ratio Sn:F=9:1) were dispersed in 500 mL of deionized water and dispersed by mechanical stirring at a high speed of 1500 rpm for 1 h to obtain a nano-FTO dispersion.

[0210] (2) Weigh 5.0 g of nano VO2 (vanadium dioxide) and slowly add it to the nano FTO dispersion obtained in step (1), continue stirring at a stirring speed of 1500 rpm for 2 h to obtain a mixed solution;

[0211] (3) The mixed solution of step (2) was transferred to a centrifuge, set at 25°C and 9000 rpm for 10 min, the supernatant was discarded and the bottom precipitate was retained, and the precipitate was transferred to a 60°C oven and dried for 12 h to obtain a block material, which was then ground in a mortar for 2 h to obtain a powdered precursor;

[0212] (4) The precursor obtained in step (3) was placed in a crucible, placed in a tube furnace and calcined for 4 hours at 150° C. under a nitrogen atmosphere, and then ground with a sand mill to obtain the ion storage material, which is Sn 0.9 F 0.1 O 1.75 Ion doping material with VO2 at a molar ratio of 1:0.08, chemical formula is Sn 0.9 F 0.1 V 0.08 O 1.91 .

[0213] Example 2

[0214] This embodiment provides an ion storage material and a preparation method thereof, the preparation method comprising the following steps:

[0215] (1) Disperse 100 g of nano-SnO2 (tin dioxide) particles with a primary particle size of 40-50 nm in 500 mL of dilute hydrochloric acid (the mass concentration of hydrochloric acid is about 10%) and disperse the mixture by mechanical stirring at a high speed of 1000 rpm for 4 h to obtain a nano-SnO2 dispersion.

[0216] (2) Weigh 4.0 g of nano-CeO2 (cerium dioxide) and slowly add it to the SnO2 dispersion obtained in step (1), continue stirring at a stirring speed of 1000 rpm for 5 h to obtain a mixed solution;

[0217] (3) The mixed solution of step (2) was transferred to a centrifuge, set at 25°C and 9000 rpm for 10 min, the supernatant was discarded and the bottom precipitate was retained, and the precipitate was transferred to a 120°C oven and dried for 3 h to obtain a bulk material, which was then ball milled in a ball mill at 600 rpm for 5 h to obtain a powdered precursor;

[0218] (4) The precursor obtained in step (3) was placed in a crucible, placed in a tube furnace and calcined for 6 hours under a nitrogen atmosphere at 200°C, and then ground with a sand mill to obtain the ion storage material, which is an ion doping material of SnO2 and CeO2 with a molar ratio of 1:0.035, and the chemical formula is SnCe 0.035 O 2.07 .

[0219] Example 3

[0220] This embodiment provides an ion storage material and a preparation method thereof, the preparation method comprising the following steps:

[0221] (1) The primary particle size is 10-20nm and the chemical formula is Sn 0.8 In 0.2 O 1.9 100 g of nano-indium tin oxide (ITO) particles (atomic ratio Sn:In = 8:2) were placed in a ball mill, and 120 mL of a hydrofluoric acid aqueous solution (the concentration of the hydrofluoric acid aqueous solution was 0.5 mol / L) and 200 g of ball milling beads were added. The mixture was ball milled at 650 rpm for 4 h to obtain a nano-ITO dispersion.

[0222] (2) Weighing 4.0 g of nano-CeO2 (cerium dioxide) and 3.0 g of nano-Co3O4 (cobalt tetroxide) were added to the nano-ITO dispersion obtained in step (1) and ball milling was continued at a speed of 650 rpm for 2 h to obtain a mixed solution;

[0223] (3) The mixed solution of step (2) was allowed to stand for 2 hours to obtain a precipitate, and the precipitate was transferred to a 90°C oven and dried for 4 hours to obtain a block material, and the block material was dry-ground by a jet mill to obtain a powdered precursor;

[0224] (4) The precursor obtained in step (3) was placed in a sagger, placed in a muffle furnace, calcined for 6 hours in a nitrogen atmosphere at 400 ° C, and then pulverized by air flow milling to obtain the ion storage material, which is Sn 0.8 In 0.2 O 1.9 Ion doping material with CeO2 and Co3O4 at a molar ratio of 1:0.034:0.055, the chemical formula is Sn 0.8 In 0.2 Ce 0.034 Co 0.055 O 2.04 .

[0225] Example 4

[0226] This embodiment provides an ion storage material and a preparation method thereof, the preparation method comprising the following steps:

[0227] (1) The primary particle size is 10-20nm and the chemical formula is Sn 0.9 Sb 0.1 O 1.95 100 g of nano antimony-doped tin oxide (ATO) particles (atomic ratio Sn:Sb = 9:1) were dispersed in 200 mL of deionized water and dispersed by magnetic stirring at a stirring speed of 600 rpm for 6 h to obtain a nano ATO dispersion.

[0228] (2) Weigh 1.0 g of nano-VO2 (vanadium dioxide) and 3.0 g of nano-WO3 (tungsten trioxide) and slowly add them to the nano-ATO dispersion obtained in step (1), continue stirring, the stirring speed is 1000 rpm, the stirring time is 4 h, and obtain a mixed solution;

[0229] (3) The mixed solution of step (2) was transferred to a centrifuge, set at 25°C and 9000 rpm for 10 min, the supernatant was discarded and the bottom precipitate was retained, and the precipitate was transferred to an 80°C oven and dried for 8 h to obtain a block material, which was then passed through a 0.1 mm roller machine for 4 times to obtain a powdered precursor;

[0230] (4) The precursor obtained in step (3) was placed in a crucible, placed in a tube furnace and calcined at 500°C for 2 hours under vacuum conditions, and then ground with a sand mill to obtain the ion storage material, which is Sn 0.9 Sb 0.1 O 1.95 Ion doping material with VO2 and WO3 at a molar ratio of 1:0.018:0.019, the chemical formula is Sn 0.9 Sb 0.1 V 0.018 W 0.019 O 2.04 .

[0231] Example 5

[0232] This embodiment provides an ion storage material and a preparation method thereof, the preparation method comprising the following steps:

[0233] (1) The primary particle size is 10-20nm and the chemical formula is Sn 0.9 Sb 0.1 O 1.95 100 g of nano-ATO particles (atomic ratio Sn:Sb=9:1) were dispersed in 200 mL of deionized water and dispersed by magnetic stirring at a stirring speed of 600 rpm for 6 h to obtain a nano-ATO dispersion.

[0234] (2) Weigh 1.7 g of nano-VOSO4 and 2.5 g of nano-H2WO4 and slowly add them to the nano-ATO dispersion obtained in step (1), continue stirring at a stirring speed of 1000 rpm for 4 h to obtain a mixed solution;

[0235] (3) The mixed solution of step (2) was transferred to a centrifuge, set at 25°C and 9000 rpm for 10 min, the supernatant was discarded and the bottom precipitate was retained, and the precipitate was transferred to an 80°C oven and dried for 8 h to obtain a block material, which was then passed through a 0.1 mm roller machine for 4 times to obtain a powdered precursor;

[0236] (4) The precursor obtained in step (3) was placed in a crucible, placed in a tube furnace and calcined at 500°C for 2 hours under vacuum conditions, and then ground with a sand mill to obtain the ion storage material, which is Sn 0.9 Sb 0.1 O 1.95 Ion doping material with VOSO4 and H2WO4 at a molar ratio of 1:0.01:0.01, the chemical formula is Sn 0.9 Sb 0.1 V 0.01 W 0.01 O 1.98 .

[0237] Example 6

[0238] This embodiment provides an ion storage material and a preparation method thereof, the preparation method comprising the following steps:

[0239] (1) The primary particle size is 10-20nm and the chemical formula is Sn 0.9 F 0.1 O 1.75 100 g of nano-FTO particles (atomic ratio Sn:F=9:1) were dispersed in 500 mL of deionized water and dispersed by mechanical stirring at a high speed of 1500 rpm for 1 h to obtain a nano-FTO dispersion.

[0240] (2) Weigh 2.0 g of nano-TiF4 and slowly add it to the nano-FTO dispersion obtained in step (1), continue stirring at a stirring speed of 1500 rpm for 2 h to obtain a mixed solution;

[0241] (3) The mixed solution of step (2) was transferred to a centrifuge, set at 25°C and 9000 rpm for 10 min, the supernatant was discarded and the bottom precipitate was retained, and the precipitate was transferred to a 60°C oven and dried for 12 h to obtain a block material, which was then ground in a mortar for 2 h to obtain a powdered precursor;

[0242] (4) The precursor obtained in step (3) was placed in a crucible, placed in a tube furnace and calcined for 4 hours at 150° C. under a nitrogen atmosphere, and then ground with a sand mill to obtain the ion storage material, which is Sn 0.9 F 0.1 O 1.75 Ion doping material with TiF4 at a molar ratio of 1:0.02, the chemical formula is Sn 0.9 F 0.1 Ti 0.02 O 1.79 .

[0243] Comparative Example 1

[0244] This comparative example provides an ion storage material and a preparation method thereof, the preparation method comprising the following steps:

[0245] (1) The primary particle size is 10-20nm and the chemical formula is Sn 0.9 F 0.1 O 1.75 100 g of nano-FTO particles (atomic ratio Sn:F=9:1) were dispersed in 500 mL of deionized water and dispersed by mechanical stirring at a high speed of 1500 rpm for 3 h to obtain a nano-FTO dispersion.

[0246] (2) The nano-FTO dispersion of step (1) was transferred to a centrifuge, set at 25°C and 9000 rpm for 10 min, the supernatant was discarded and the bottom precipitate was retained, and the precipitate was transferred to a 60°C oven and dried for 12 h to obtain a block material, which was then ground in a mortar for 2 h to obtain a powdered precursor;

[0247] (4) The precursor obtained in step (3) was placed in a crucible, placed in a tube furnace and calcined for 4 hours at 150° C. under a nitrogen atmosphere, and then ground with a sand mill to obtain the ion storage material having the chemical formula Sn 0.9 F 0.1 O 1.75 .

[0248] Comparative Example 2

[0249] This comparative example provides an ion storage material and a preparation method thereof, the preparation method comprising the following steps:

[0250] (1) The primary particle size is 10-20nm and the chemical formula is Sn 0.9 F 0.1 O 1.75 100 g of nano-FTO particles (atomic ratio Sn:F=9:1) were added to a dry mixer and premixed at a stirring speed of 1500 rpm to obtain a premix;

[0251] (2) Weigh 4.0 g of nano-VO2 and slowly add it to the premix obtained in step (1), set the speed to 2500 rpm, and mix it at high speed for 1 hour to obtain a mixed precursor;

[0252] (3) The mixed precursor obtained in step (2) was placed in a crucible, placed in a tube furnace and calcined for 4 hours at 150° C. under a nitrogen atmosphere, and then ground with a sand mill to obtain the ion storage material, which is Sn 0.9 F 0.1 O 1.75 The modified material was dry-doped with VO2 at a molar ratio of 1:0.08.

[0253] The performance tests of the ion storage materials provided in Examples 1-6 and Comparative Examples 1-2 were conducted as follows:

[0254] 1. X-ray diffraction test

[0255] The above ion storage materials were tested by X-ray diffraction (XRD, Rigaku Ultima IV, Japan). The XRD spectra of the ion storage materials provided in Examples 1-5 and Comparative Examples 1-2 are as follows: Figure 1 As shown, the horizontal axis is the 2θ angle, the unit is degree (°), and the vertical axis is the intensity; analysis Figure 1 It can be seen that the VO that could not be found x 、CeO x 、CoO x , WO x The diffraction peaks show that in the ion storage materials provided by Examples 1-5, the elements V, Ce, Co, and W enter the crystal lattice in the form of ion doping.

[0256] 2. Transmission electron microscopy test

[0257] The microscopic morphology of the aforementioned ion storage materials was tested using a transmission electron microscope (TEM, JEOL JEM-F200, Japan). The TEM images of the ion storage materials provided in Examples 1-5 are shown in FIG. Figure 2A 、 Figure 2B 、 Figure 2C 、 Figure 2D 、 Figure 2E As shown, according to the transmission electron microscopy images, the ion storage materials provided by Examples 1-5 are spherical, with an overall uniform particle size distribution, a primary particle size of approximately 10-20 nm, and no morphology of dopant metal oxide particles is found, proving that the elements V, W, Ce, and Co are combined with the tin oxide main material in the form of ion doping.

[0258] 3. Energy spectrum analysis

[0259] The EDS spectrum of the aforementioned ion storage materials was measured using a scanning electron microscope and an energy dispersive spectrometer (EDS, Japan JEOL JEM-F200).

[0260] The EDS spectrum of the ion storage material provided in Example 1 is as follows: Figure 3A As shown, according to Figure 3A The EDS results show that the ion storage material Sn 0.9 F 0.1 V 0.08 O 1.91 The atomic proportion of Sn is 84.1%, the atomic proportion of F is 8.7%, and the atomic proportion of V is 7.2%. V is combined with the main material and is evenly distributed.

[0261] The EDS spectrum of the ion storage material provided in Example 2 is as follows: Figure 3B As shown, according to Figure 3B The EDS results show that the ion storage material SnCe 0.035 O 2.07 The atomic ratio of Sn is 96.5%, the atomic ratio of Ce is 3.5%, and Ce is combined with the main material and distributed evenly.

[0262] The EDS spectrum of the ion storage material provided in Example 3 is as follows: Figure 3C As shown, according to Figure 3C The EDS results show that the ion storage material Sn 0.8 In 0.2 Ce 0.034 Co 0.055 O 2.04 The atomic proportion of Sn is 73.8%, the atomic proportion of In is 17.6%, the atomic proportion of Ce is 3.4%, and the atomic proportion of Co is 5.2%. Ce and Co are both combined with the main material and are evenly distributed.

[0263] The EDS spectrum of the ion storage material provided in Example 4 is as follows: Figure 3D As shown, according to Figure 3D The EDS results show that the ion storage material Sn 0.9 Sb 0.1 V 0.018 W 0.019 O 2.04 The atomic proportion of Sn is 87.4%, the atomic proportion of Sb is 9.5%, the atomic proportion of V is 1.5%, and the atomic proportion of W is 1.6%. V and W are both combined with the main material and are evenly distributed.

[0264] The EDS spectrum of the ion storage material provided in Example 5 is as follows: Figure 3E As shown, according to Figure 3E The EDS results show that the ion storage material Sn 0.9 Sb 0.1 V 0.01 W 0.01 O 1.98 The atomic proportion of Sn is 86.2%, the atomic proportion of Sb is 9.7%, the atomic proportion of V is 0.8%, and the atomic proportion of W is 0.7%. V and W are both combined with the main material and are evenly distributed.

[0265] The EDS spectrum of the ion storage material provided in Comparative Example 1 is as follows: Figure 3F As shown, according to Figure 3F The EDS results show that the ion storage material Sn 0.9 F 0.1 O 1.75 The atomic ratio of Sn is 90.3%, and the atomic ratio of F is 9.7%. The element ratio test results are consistent with the material design.

[0266] The EDS spectrum of the ion storage material provided in Comparative Example 2 is as follows: Figure 3G As shown, according to Figure 3GFrom the EDS results, it can be seen that the atomic ratio of Sn in the ion storage material is 87.6%, the atomic ratio of F is 9.6%, and the atomic ratio of V is 2.8%; in Comparative Example 2, the same raw materials and proportions as in Example 1 are used to prepare a V-doped FTO nanocomposite material using a dry mixing process. It can be seen that a certain amount of V element exists in the main material, but the content is far lower than the designed value. This is because the primary particle size (100-200nm) of the dopant VO2 is 10-20 times that of the main material FTO, and the true density is 4 times that of the main material. In the dry mixing process, it cannot be tightly adsorbed and wrapped around the main material particles, which is not conducive to the subsequent calcination annealing reaction, resulting in a low actual doping amount and insufficient reaction.

[0267] 4. Particle size test

[0268] The Zeta potential and particle size analyzer Brookhaven 90Plus Zeta were used to test the D of ion storage materials. 10 Particle size, D 50 Particle size, D 90 Particle size and D 99 Particle size, the test results are shown in Table 1:

[0269] Table 1

[0270] <![CDATA[D 10 (μm)]]> <![CDATA[D 50 (μm)]]> <![CDATA[D 90 (μm)]]> <![CDATA[D 99 (μm)]]> Example 1 0.063 0.08 0.163 0.19 Example 2 0.073 0.12 0.175 0.22 Example 3 0.096 0.155 0.223 0.255 Example 4 0.075 0.106 0.179 0.220 Example 5 0.070 0.095 0.180 0.212 Comparative Example 1 0.068 0.092 0.172 0.203 Comparative Example 2 0.070 0.095 0.178 0.210

[0271] It can be seen from the data in Table 1 that the particle size distribution of the ion storage materials provided by Examples 1-5 is relatively narrow, especially Example 1, which has a small particle size and a narrow distribution, which will be beneficial for subsequent coating and feeding; since the preparation method of Example 3 adopts dry airflow crushing and grinding, the particle size distribution of the ion storage material of Example 3 is generally large.

[0272] 5. Impurity content analysis

[0273] The impurity content of the aforementioned ion storage material was tested using an inductively coupled plasma atomic emission spectrometer (ICP-AES, Agilent 5110 (OES), USA). The test results are shown in Table 2:

[0274] Table 2

[0275]

[0276]

[0277] Since there will be a small amount of surfactant (organic matter) on the surface of the Sn oxide main material and the M dopant, the prepared ion storage material may contain trace amounts of C, H, and N elements. As can be seen from the data in Table 2, the impurity content in the ion storage materials provided by Examples 1-5 is extremely low, indicating that the organic matter has been basically removed during the calcination process in the preparation method.

[0278] 6. Test of specific surface area, density and electrical conductivity

[0279] The BET specific surface area of ​​the ion storage material was measured using a Micromeritics ASAP 2460 fully automatic specific surface analyzer; the bulk density of the ion storage material was measured using a Dandong Better BT-302 density meter; and the compacted density, powder resistivity, and powder conductivity of the ion storage material under a pressure of 30 MPa were measured using an ST2742B automated powder resistivity meter. The test data are shown in Table 3:

[0280] Table 3

[0281] <![CDATA[BET(m 2 / g)]]> <![CDATA[Bulk density (g / cm 3 )]]> <![CDATA[Compaction density (g / cm 3 )]]> Powder resistivity (Ω·cm) Powder conductivity (S / cm) Example 1 53.3 0.71 1.45 2.16 0.46 Example 2 54.3 0.68 1.51 1.41 0.71 Example 3 17.5 0.60 1.7 85.5 0.10 Example 4 55.6 0.75 1.25 5.46 0.18 Example 5 55.1 0.74 1.48 2.43 0.39 Comparative Example 1 54.2 0.75 1.41 2.56 0.40 Comparative Example 2 53.5 0.74 1.47 2.66 0.39

[0282] It can be seen from the data in Table 3 that the ion storage materials provided by Examples 1, 2, 4 and 5 have a larger BET specific surface area, a smaller powder resistivity, a larger powder conductivity and excellent conductive performance; the ion storage material of Example 3 has a smaller BET specific surface area, a relatively high powder resistivity and a relatively low powder conductivity. This is because the preparation method of Example 3 adopts a gas flow milling process, which results in an overall larger particle size distribution of the material.

[0283] 7. Electrochemical performance test

[0284] The electrochemical performance of the ion storage material was tested by Shanghai Chenhua CHI660E electrochemical workstation. The test was carried out in a three-electrode system. 10 mg of the ion storage material to be tested was coated on a 9 cm 2 The ITO conductive glass was used as the working electrode, the platinum wire was used as the counter electrode, and the Ag / AgCl was used as the reference electrode. The potential range was -1 V to 1 V, and the cyclic voltammetry curve was tested at a specific scan rate.

[0285] The cyclic voltammetry curves of the ion storage material provided in Example 1 at different scan rates are shown in FIG. Figure 4 As shown, the scanning rates are 5mV / s, 10mV / s, 20mV / s, and 50mV / s respectively. Figure 4 It can be seen that the ion storage material has no obvious redox peak, has capacitive lithium storage characteristics, and has good stability.

[0286] The cyclic voltammetry (CV) curves of the ion storage material were tested after 1000 charge-discharge cycles using the three-electrode system with a potential range of -1V to 1V at a scan rate of 40mV / s. The CV curves of Examples 1-6 and Comparative Examples 1-2 before and after 1000 cycles are shown in Figures 1 and 2. Figure 5A 、 Figure 5B 、 Figure 5C 、 Figure 5D 、 Figure 5E 、 Figure 5F 、 Figure 5G and Figure 5H As shown, the data of the capacitance of the ion storage material calculated from the CV curve is shown in Table 4:

[0287] Table 4

[0288]

[0289] From the test data in Table 4, it can be seen that the initial capacitance of the ion storage materials provided by Examples 1-6 is 42.39-56.88 C / g, and the capacity retention rate after 1000 charge and discharge cycles is 87.7-92.1%, which has high capacity and good cycle stability; while the initial capacity and cycle retention rate of the ion storage materials of Comparative Examples 1-2 are obviously insufficient.

[0290] Application Example 1

[0291] A black-transparent electrochromic device comprises a first conductive layer, a black electrochromic layer (EC layer), an electrolyte layer, an ion storage layer, and a second conductive layer stacked in sequence, wherein the first and second conductive layers are ITO with a thickness of approximately 100 nm; the EC layer is a commercially available product with a thickness of approximately 1400 nm; the electrolyte layer is a commercially available product with a thickness of approximately 30 μm; and the ion storage layer is prepared using the ion storage materials provided in Examples 1-5 and Comparative Examples 1-2, respectively, and has a thickness of 1200 nm.

[0292] A 300 cm × 300 cm black-transparent electrochromic automotive sunroof glass device was prepared according to the aforementioned laminated structure. The optical and electrical properties of the device were tested at 25°C and 85°C using a Lanbo BT2018 battery test system and a Shimadzu UV3600i Plus ultraviolet spectrophotometer.

[0293] The room temperature cycle transmittance spectra of the black-transparent electrochromic devices prepared from the ion storage materials provided in Example 1, Comparative Example 1 and Comparative Example 2 are shown in FIG. Figure 6A 、 Figure 6B 、 Figure 6CAs shown, the results show that the black-transparent electrochromic automotive sunroof glass device formed using the ion storage material provided in Example 1 as the ion storage layer has a wider optical contrast range and maintains good contrast after 20,000 charge-discharge (coloring-fading) cycles at 25°C. In Comparative Example 1, the same EC device prepared using the undoped ion storage material as the ion storage layer exhibits a significantly lower initial color change range than that of Example 1 within the visible light range, and the device's contrast significantly decreases after 20,000 charge-discharge cycles. In Comparative Example 2, the same EC device prepared using the ion storage material modified by a dry process as the ion storage layer exhibits a slightly better initial color change range than that of Comparative Example 1 within the visible light range, but significantly lower than that of Example 1. The remaining contrast of the device after 20,000 charge-discharge cycles is also significantly lower than that of Example 1.

[0294] The detailed optoelectronic test results of the black-transparent electrochromic automobile sunroof glass device are shown in Table 5:

[0295] Table 5

[0296]

[0297]

[0298] It can be seen from the test data in Table 5 that, whether under normal temperature 25°C or high temperature 85°C test conditions, the ion storage materials provided in Examples 1-5 of the present invention are used as ion storage layers, so that the black-transparent electrochromic device has higher initial optical contrast and capacitance in the visible light range, and the contrast retention rate and capacity retention rate after 20,000 charge and discharge cycles are high, the optical and electrical properties are excellent, and the cycle stability is good; while the ion storage materials in Comparative Examples 1-2 are used as ion storage layers, the electrochromic device is obviously insufficient in both initial optical contrast and cycle retention rate.

[0299] Application Example 2

[0300] A high-transmittance consumer electronic electrochromic device comprises a first conductive layer, a purple electrochromic layer (EC layer), an electrolyte layer, an ion storage layer, and a second conductive layer stacked in sequence, wherein the first conductive layer and the second conductive layer are ITO with a thickness of approximately 100 nm; the EC layer is a commercially available product with a thickness of approximately 500 nm; the electrolyte layer is a commercially available product with a thickness of approximately 30 μm; and the ion storage layer is the ion storage material provided in Examples 1-5 and Comparative Examples 1-2, respectively, with a thickness of 650 nm.

[0301] A 10 cm × 10 cm high-transmittance consumer electronic electrochromic device was prepared according to the aforementioned stacked structure. The optical and electrical properties of the device were tested at 25°C and 65°C using a Lanbo BT2018 battery testing system and a Shimadzu UV3600i Plus UV spectrophotometer.

[0302] The room temperature cycle transmittance spectra of the high-transmittance consumer electronic electrochromic devices prepared from the ion storage materials provided in Example 1, Comparative Example 1 and Comparative Example 2 are shown as follows: Figure 7A 、 Figure 7B 、 Figure 7C As shown, the results show that the high-transmittance consumer electronic EC device formed with the ion storage material provided in Example 1 as the ion storage layer has a wider optical contrast range and maintains good contrast after 20,000 charge-discharge (coloring-fading) cycles at 25°C. In Comparative Example 1, the same EC device prepared using the undoped ion storage material as the ion storage layer has an initial color change range far less than that of Example 1 in the visible light range, and the contrast ratio of the device decreases significantly after 20,000 charge-discharge cycles. In Comparative Example 2, the same EC device prepared using the ion storage material modified by a dry process as the ion storage layer has an initial color change range slightly better than that of Comparative Example 1 in the visible light range, but far less than that of Example 1. After 20,000 charge-discharge cycles, the residual contrast ratio of the device is also far less than that of Example 1.

[0303] The detailed photoelectric test results of the high-transmittance consumer electronic electrochromic device are shown in Table 6:

[0304] Table 6

[0305]

[0306] It can be seen from the test data in Table 6 that, whether under normal temperature 25°C or high temperature 65°C test conditions, the ion storage materials provided in Examples 1-5 of the present invention are used as ion storage layers. In the visible light range, the high-transmittance consumer electronic electrochromic device has a higher initial optical contrast and capacitance, and the contrast retention rate and capacity retention rate after 20,000 charge and discharge cycles are high, with excellent optical and electrical properties and cycle stability; while the ion storage materials in Comparative Examples 1-2 are used as ion storage layers, which makes the high-transmittance consumer electronic electrochromic device obviously insufficient in initial optical contrast and cycle retention rate.

[0307] The applicant states that while the above-described embodiments illustrate the ion storage material, preparation method, and application of the present invention, the present invention is not limited to the above-described process steps, nor does it necessarily rely on the above-described process steps for implementation. Persons skilled in the art will appreciate that any improvements to the present invention, equivalent substitutions for the raw materials used, addition of auxiliary components, and selection of specific methods, etc., fall within the scope of protection and disclosure of the present invention.

Claims

1. An ion storage material, characterized in that Including the compound represented by formula (I), Sn x A y M z O m R n (I); in, A is at least one element selected from Group IIIA, Group VA, Group VIIA, Group IIB and Group IIIB; M is selected from at least one element of Group IA, Group IIA, Group IIIA, Group IIB, Group IIIB, Group IVB, Group VB, Group VIB, Group VIIB and Group VIII; R is at least one element selected from Group IA, Group IIIA, Group IVA, Group VA, Group VIA, and Group VIIA; and The value range of x is 0<x≤1; The value range of y is 0≤y≤0.8; The value range of z is 0<z≤0.5; The value range of m is 0<m≤4; The value range of n is 0≤n≤6.

2. The ion storage material according to claim 1, characterized in that A is selected from at least one of In, F, Cl, Br, I, Sb, Al, Bi, Ga, Tl, Zn, Cd and Ce; and / or The M is selected from at least one of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Al, Ga, In, Zn, Cd, Ce, V, Co, W, Cr, Mo, Ti, Ni, Fe, Mn, Rh and Pd; and / or, The R is selected from at least one of H, B, C, Si, N, P, O, S, F, Cl, Br and I.

3. The ion storage material according to claim 1, characterized in that The A is selected from at least one of In, F, Sb, Zn and Al; and / or, The M is selected from at least one of Ce, V, Co, W, Ti and Ni; and / or, The R is selected from at least one of H, C, N, P, O, S, F and Cl.

4. The ion storage material according to claim 1, wherein The A is selected from at least one element of Group IIIA, Group VIIA, Group IIB and Group IIIB; or, the A is selected from at least one element of Group IIIA, Group VA, Group VIIA and Group IIB; and / or, The M is selected from at least one element of Group IA, Group IIA, Group IIIA, Group IIB, Group IVB, Group VB, Group VIB, Group VIIB and Group VIII; and / or, The R is selected from at least one element of Group IA, Group VA, Group VIA and Group VIIA; Preferably, the A is selected from at least one of In, F, Zn and Al; and / or, The M is selected from at least one of V, Co, W, Ti and Ni; and / or, The R is selected from at least one of H, P, O, S and F.

5. The ion storage material according to claim 1, characterized in that The A is selected from at least one element of Group IIIA, Group VA and Group VIIA; and / or, The M is selected from at least one element of Group IIIB, Group VB, Group VIB and Group VIII; or, the M is selected from at least one element of Group VB, Group VIB and Group VIII; and / or, Said R is selected from at least one element in Group VIA; Preferably, the A is selected from at least one of In, F and Sb; and / or, The M is selected from at least one of Ce, V, Co and W; or, the M is selected from at least one of V, Co and W; and / or, The R is selected from at least one of O and S.

6. The ion storage material according to claim 1, characterized in that The ratio of y to x is in the range of 0≤y / x≤0.8; preferably, the ratio of y to x is in the range of 0≤y / x≤0.5; more preferably, the ratio of y to x is in the range of 0.05≤y / x≤0.25; Preferably, the value range of y is 0≤y≤0.5; more preferably, the value range of y is 0.05≤y≤0.

25.

7. The ion storage material according to claim 1, characterized in that The ratio of z to x is in the range of 0<z / x≤0.5; preferably, the ratio of z to x is in the range of 0.001≤z / x≤0.2; More preferably, the ratio of z to x is in the range of 0<z / x<0.01; More preferably, the ratio of z to x is in the range of 0.04<z / x<0.5; More preferably, the value range of z is 0.001≤z≤0.

2.

8. The ion storage material according to claim 1, wherein The value range of m is 0<m≤3.5; Optionally, the value range of n is 0≤n≤3.

9. The ion storage material according to any one of claims 1 to 8, characterized in that The primary particle size of the ion storage material is 10-50 nm; preferably, the primary particle size of the ion storage material is 10-20 nm.

10. The ion storage material according to any one of claims 1 to 8, characterized in that The average particle size of the ion storage material is 10-500 nm; preferably, the average particle size of the ion storage material is 50-200 nm.

11. The ion storage material according to any one of claims 1 to 8, characterized in that The specific surface area of ​​the ion storage material is 10-100m 2 / g; preferably, the specific surface area of ​​the ion storage material is 15-80m 2 / g.

12. The ion storage material according to any one of claims 1 to 8, characterized in that The capacitance of the ion storage material is ≥37C / g; preferably, the capacitance of the ion storage material is ≥40C / g; preferably, the capacitance of the ion storage material is ≥45C / g.

13. The ion storage material according to any one of claims 1 to 8, characterized in that After 1000 charge and discharge cycles at the operating voltage, the capacitance retention rate of the ion storage material is ≥56%; preferably, after 1000 charge and discharge cycles at the operating voltage, the capacitance retention rate of the ion storage material is ≥60%; preferably, after 1000 charge and discharge cycles at the operating voltage, the capacitance retention rate of the ion storage material is ≥70%; preferably, after 1000 charge and discharge cycles at the operating voltage, the capacitance retention rate of the ion storage material is ≥80%; more preferably, after 1000 charge and discharge cycles at the operating voltage, the capacitance retention rate of the ion storage material is ≥85%; wherein, The operating voltage is selected from a voltage between a maximum oxidation potential and a maximum reduction potential of the ion storage material.

14. The ion storage material according to claim 13, characterized in that The operating voltage has a value range of 0 < operating voltage ≤ 3V; preferably, the operating voltage has a value range of 0 < operating voltage ≤ 2V; more preferably, the operating voltage has a value range of 0.5V ≤ operating voltage ≤ 1.5V.

15. A method for preparing an ion storage material, characterized in that: The preparation method comprises: providing a dispersion comprising a combination of a Sn oxide and a solvent; uniformly mixing the dispersion and the M-containing dopant to obtain a mixed solution; performing solid-liquid separation on the mixed liquid to obtain a precursor; The precursor is calcined to obtain Sn x A y M z O m R n Ion storage material; wherein, The definitions of A, M, R, x, y, z, m and n are as described in any one of claims 1 to 14.

16. The preparation method according to claim 15, characterized in that The Sn-containing oxide is selected from at least one of tin oxide and A-doped tin oxide.

17. The preparation method according to claim 15, characterized in that The solvent is a polar solvent; preferably, the solvent is selected from one of water, acidic aqueous solution, alkaline aqueous solution or saline solution; more preferably, the solvent is water or acidic aqueous solution; More preferably, the solvent is selected from one of water, hydrochloric acid, nitric acid, acetic acid, hydrofluoric acid, sulfuric acid, ammonia water, sodium chloride solution, calcium chloride solution, aluminum chloride solution or sodium hydroxide solution; more preferably, the solvent is selected from one of water, hydrochloric acid, nitric acid, acetic acid, hydrofluoric acid or sulfuric acid.

18. The preparation method according to claim 15, characterized in that The mass ratio of the Sn-containing oxide to the solvent is 1:(0.1-100); preferably, the mass ratio of the Sn-containing oxide to the solvent is 1:(0.2-50).

19. The preparation method according to claim 15, characterized in that The primary particle size of the Sn-containing oxide is 10-50 nm; preferably, the primary particle size of the Sn-containing oxide is 10-20 nm.

20. The preparation method according to claim 15, characterized in that The primary particle size of the M-containing dopant is 1-500 nm; preferably, the primary particle size of the M-containing dopant is 10-300 nm; preferably, the primary particle size of the M-containing dopant is 100-200 nm.

21. The preparation method according to claim 15, characterized in that The providing of the dispersion liquid comprises: mixing the Sn-containing oxide with a solvent and then performing wet dispersion grinding to obtain the dispersion liquid.

22. The preparation method according to claim 15, characterized in that The dispersion liquid is mixed evenly with the M-containing dopant to obtain a mixed liquid, comprising: The dispersion liquid and the M-containing dopant are uniformly mixed by wet dispersion grinding to obtain a mixed liquid.

23. The preparation method according to claim 15, characterized in that The M-containing dopant is selected from at least one of an M element, an M-containing oxide, an M-containing acid, an M-containing base, an M-containing salt and an M-containing organic matter; preferably, the M-containing dopant is selected from at least one of an M element, an M-containing oxide and an M-containing salt; more preferably, the M-containing dopant is an M-containing oxide.

24. The preparation method according to claim 15, characterized in that The mass ratio of the Sn-containing oxide to the M-containing dopant is 1:(0.001-0.5); preferably, the mass ratio of the Sn-containing oxide to the M-containing dopant is 1:(0.001-0.2).

25. The preparation method according to claim 15, characterized in that The solid-liquid separation of the mixed liquid to obtain a precursor comprises: The mixed liquid is subjected to solid-liquid separation to obtain a precipitated solid; The precipitated solid is dried and crushed to obtain the precursor.

26. The preparation method according to claim 15, characterized in that The precursor is calcined to obtain Sn x A y M z O m R n Ion storage materials, including: calcining the precursor to obtain an initial ion storage material; Crushing the initial ion storage material to obtain the Sn x A y M z O m R n ion storage materials.

27. The preparation method according to claim 25, characterized in that The drying temperature is 50-140°C; Preferably, the drying time is 2-48 hours.

28. The preparation method according to claim 15, characterized in that The calcination is carried out in a protective atmosphere, which is a vacuum atmosphere or an inert gas atmosphere; Preferably, the calcination temperature is 100-900°C; Preferably, the heating rate of the calcination is 1-10°C / min; Preferably, the calcination time is 1-24 hours.

29. An ion storage membrane, characterized in that The ion storage membrane comprises the ion storage material according to any one of claims 1 to 14 or the ion storage material prepared by the preparation method according to any one of claims 15 to 28.

30. An electrochromic device, characterized in that: The electrochromic device comprises a first conductive layer, an electrochromic layer, an electrolyte layer, an ion storage layer, and a second conductive layer stacked in sequence, or the electrochromic device comprises a first conductive layer, an electrochromic layer, an electrolyte layer, and an ion storage layer stacked in sequence; wherein, The ion storage layer comprises the ion storage material according to any one of claims 1 to 14, or the ion storage material prepared by the preparation method according to any one of claims 15 to 28, or the ion storage membrane according to claim 29.

31. A terminal product, characterized in that: The terminal product includes the ion storage membrane as described in claim 29 or the electrochromic device as described in claim 30, wherein the terminal product includes any one of a rearview mirror, a curtain wall, a car sunroof, a car side window, a car windshield, an electronic product housing, glasses, a vehicle, and a display panel.

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