阅读说明：本技术 电致变色材料及其制造方法 (Electrochromic material and method for producing same ) 是由 弗拉基米尔·伊戈列维奇·什切里亚科夫 安东·米哈伊洛维奇·马纳霍夫 尼古拉·安纳托利维奇·波哥列 于 2019-07-08 设计创作，主要内容包括：无机电致变色材料及制造方法利用反应性PDC磁控管,其中电致变色材料的共溅射合成如下进行：(1)直接从碳化物靶材；(2)从相关的过渡金属和石墨靶材,以及诸如Si、Ge、P、B等非金属元素；(3)直接从复合靶材(过渡金属、非金属元素和石墨粉的细粉混合物)。溅射可以立即从1到4种靶材进行。对于共溅射,可以使用以下气体混合物的组合：Ar/O-2/N-2、Ar/H-2/N-2/O-2、Ar/NH-3/O-2、Ar/CO/N-2/O-2、Ar/CO/H-2/N-2/O-2、Ar/CH-4/N-2/O-2和Ar/NH-3/CO/N-2/O-2。这允许获得具有增加的电子和离子传导性、更高的着色和良好的循环(使用寿命)的电致变色材料。而且,可以获得不同的蓝色色调和对眼睛呈中性的灰色、黑色及棕色。溅射的电致变色膜通过“热分裂”预嵌入的薄膜而进一步改善。这可以实现更快的着色和漂白速度及更长的使用寿命。(The inorganic electrochromic material and the manufacturing method utilize a reactive PDC magnetron, wherein the co-sputtering synthesis of the electrochromic material is carried out as follows: (1) directly from the carbide target; (2) from the relevant transition metal and graphite targets, and non-metallic elements such as Si, Ge, P, B; (3) directly from the composite target (a fine powder mixture of transition metal, non-metallic elements and graphite powder). Sputtering can be carried out immediately from 1 to 4 targets. For co-sputtering, a combination of the following gas mixtures may be used: Ar/O 2 /N 2 、Ar/H 2 /N 2 /O 2 、Ar/NH 3 /O 2 、Ar/CO/N 2 /O 2 、Ar/CO/H 2 /N 2 /O 2 、Ar/CH 4 /N 2 /O 2 And Ar/NH 3 /CO/N 2 /O 2 . This allows to obtain electrochromic materials with increased electronic and ionic conductivity, higher coloration and good cycle (lifetime). Furthermore, different shades of blue and gray, black and brown which are neutral to the eye can be obtained. Sputtered electrochromic films are further improved by "heat splitting" the pre-embedded thin film. This may allow for faster coloring and bleaching rates and longer service lives.)

1. Has formula WO_2.4-2.9M1, M2, E1, E2, E3, wherein

M1 is a dopant selected from Mo, Ti, Ni, Zr, V, Cr, Al, Nb, Ta, Co, Mn;

m2 is an optional dopant selected from Mo, Ti, Ni, Zr, V, Cr, Al, Nb, Ta, Co, Mn;

e1 is a dopant selected from H, N, C, Si, Ge, P, B;

e2 is a dopant selected from H, N, C, Si, Ge, P, B; and is

E3 is an optional dopant selected from H, N, C, Si, Ge, P, B,

so that M1 ≠ M2, E1 ≠ E2 ≠ E3.

2. The electrochromic material of claim 1, having formula M (I)_0.1-3.0WO_2.4-2.9M1: M2: E1: E2: E3, wherein M (I) is selected from the following group 1 elements: li⁺、Na⁺、K⁺。

3. The electrochromic material of claim 1 having the formula M (II)_0.1-1.5WO_2.4-2.9M1: M2: E1: E2: E3, wherein M (II) is selected from the following group 2 elements: mg (magnesium)²⁺、Ca²⁺、Ba²⁺、Zn²⁺。

4. The electrochromic material of claim 1 having the formula M (III)_0.1-1.0WO_2.4-2.9M1: M2: E1: E2: E3, wherein M (III) is selected from the following group 3 elements: sc (Sc)³⁺、Y³⁺And lanthanides having atomic numbers 57-71.

5. The electrochromic material of claim 1, wherein the electrochromic material is used to form a positive electrode.

6. The electrochromic material of claim 1, wherein the electrochromic material is used to form a negative electrode.

7. The electrochromic material of claim 1 wherein the electrochromic material is at least partially crystalline.

8. A method of making an electrochromic material characterized in claim 1, comprising post-annealing at a temperature between about 100 ℃ and about 550 ℃.

9. The method of claim 8, wherein the post-annealing is performed at a temperature between about 450 ℃ and about 550 ℃.

10. The method of claim 8, further comprising using Li⁺Pre-embedding followed by said post-annealing at a temperature between about 250 ℃ and about 450 ℃.

11. The method of claim 8, further comprising administering Na⁺Or K⁺Pre-intercalation followed by the post-annealing at a temperature between about 250 ℃ and about 450 ℃ and then de-intercalation.

12. The method of claim 8, further comprising using Mg²⁺、Ca²⁺、Ba²⁺Or Zn²⁺Pre-intercalation followed by the post-annealing at a temperature between about 250 ℃ and about 450 ℃ and then de-intercalation.

13. The method of claim 8, further comprising administering Sc³⁺、Y³⁺And lanthanide pre-insertion with atomic numbers 57-71, followed by said post-annealing at a temperature between about 100 ℃ and about 250 ℃, and then de-insertion.

14. The method of any one of claims 10-13, wherein the post-annealing is performed to provide cleaving.

15. The method of any one of claims 10-13, wherein the pre-embedding is performed in a liquid battery.

16. The method of any one of claims 11-13, wherein the de-intercalation is performed in a liquid cell.

17. The method of claim 16, wherein the de-embedding is performed at negative polarity at about room temperature.

18. The method of claim 8, wherein the electrochromic material is obtained using magnetron co-sputtering of a metal and a carbide-based material or a metal and a graphite-based material.

19. The method of claim 18, wherein the magnetron co-sputtering is magnetron reactive co-sputtering performed in a gas mixture comprising one of the following combinations: Ar/O₂/N₂、Ar/H₂/N₂/O₂、Ar/NH₃/O₂、Ar/CO/N₂/O₂、Ar/CO/H₂/N₂/O₂、Ar/CH₄/N₂/O₂And Ar/NH₃/CO/N₂/O₂。

20. The method of claim 19, wherein the pressure of the gas mixture is in a range of about 5 mtorr to about 15 mtorr.

21. The method of claim 19, wherein the flow rate of the gas mixture is in a range of about 80 seem to about 100 seem.

Technical Field

The present invention relates to the field of electrochromism, and in particular to an Electrochromic (EC) material that is neutral to the color of the eye and a method for manufacturing the same. More specifically, the present invention relates to the field of inorganic EC materials with advanced properties and their manufacturing techniques aimed at obtaining optimal material structures. Such materials have an extended color range (blue, grey, black, brown hues) and higher conductivity, which allows thicker EC layers (up to 10 μm) to be deposited without significant degradation of their performance. In addition, these materials are expected to be useful as positive electrode materials in primary or secondary energy sources.

Background

Tungsten oxide (WO) over the past decades₃) Have been extensively studied due to their interesting physical and chemical properties. WO₃Showing a strong reversible field-assisted ion intercalation behavior. Such as Li⁺、Na⁺、K⁺The plasma can be easily introduced into the main WO₃In the matrix. This ion intercalation is combined with strong changes in the electronic and optical properties of the oxide and, due to its low power consumption and high energy efficiency, this effect is used for example in large area telecommunications1-4 are widely used in EC devices such as information displays, rearview mirrors, smart windows for automobiles and energy-saving buildings]. Amorphous WO synthesized by magnetron sputtering₃Membranes have proven to be excellent candidates for EC applications [5,6]. When ions are embedded, charge compensating electrons enter a localized state. WO₃The electronic structure of (a) is modified, which greatly changes the optical properties of the material, from transparent to deep blue. Many WO's for doping host amorphous with transition metal and non-metal elements have been studied₃Doping of materials and methods to enhance their EC and electrochemical performance [ 7-16]。

U.S. patent publication No. 2007097480A1 discloses a formula W_1-xTa_xO_3-x/2Wherein x has a value in the range of about 0.15 to about 0.5, as a thin film by pulsed laser deposition. Specifically, U.S. patent publication No. 2007097480A1 discloses H at-0.7V⁺Under ion implantation, Ta_0.1W_0.9O_2.95From light pink to navy blue, and Ta_0.3W_0.7O_2.85The color of (a) changes from light green to light brown green. Electrochromic materials can be used in "smart" windows, mirrors, information displays, and variable emission surfaces. However, U.S. patent publication No. 2007097480a1 fails to provide a neutral color in a colored and bleached state.

U.S. patent publication No. 2009323157a1 discloses an electrochromic material comprising at least one of the following compounds: oxides of tungsten (W), niobium (Nb), tin (Sn), bismuth (Bi), vanadium (V), nickel (Ni), iridium (Ir), antimony (Sb) and tantalum (Ta), alone or in mixtures, and optionally including additional metals such as titanium (Ti), rhenium (Re) or cobalt (Co), can switch the glass between a bleached state and a colored state, which is characterized by a light transmission of 55/2.5%, 50/1%, 40/0.01%. However, U.S. patent publication No. 2009323157a1 does not mention providing neutral color in colored and bleached states.

U.S. patent publication No. 2010245973A1 discloses a WO-based solution_3-y(0 < y ≦ 0.3) electrochromic material in which lithium ions are intercalated into oxygenTungsten oxide is caused to change from a transparent (bleached state) to a blue (colored state) in tungsten oxide, and it is generally mentioned that nickel tungsten oxide changes from a transparent state to a brown state. However, U.S. patent publication No. 2009323157a1 does not mention the chemical composition of "nickel tungsten oxide".

U.S. patent publication No. 2014002884a1 discloses an electrochromic material selected from hydrated metal oxides, preferably amorphous, such as hydrated tungsten oxide H, and mixtures of two or more of these oxides_XWO₃·nH₂O, wherein x is 0 to 1 and n is an integer of 1 to 2. However, U.S. patent publication No. 2014002884a1 does not mention providing neutral color in colored and bleached states.

U.S. patent publication No. 2014043666A1 discloses a lithium salt selected from the group consisting of Li_1.82NiW_0.45O_x、Li_1.97NiZr_0.23O_x、Li_0.51NiZr_0.16La_0.19O_x、Li_2.22NiZr_0.14Mo_0.25O_x、Li_3.12NiZr_0.15Ta_0.15O_xAnd Li_2.65NiZr_0.18V_0.60O_xAn electrochromic material of the group consisting of where x ranges from about 0.1 to about 50, from about 1 to about 6, or from about 1.6 to about 5.4, which is suggested for use in combination with a dark blue electrochromic tungsten oxide to produce a more neutral gray-dark state for the entire electrochromic coating. However, U.S. patent publication No. 2009323157a1 does not mention the chemical composition of "tungsten oxide". Further, this document indicates that one sample exhibits a repeatable bleaching time of about 11 seconds and a coloring time of about 11 seconds, wherein the light transmittance at 670nm of the corresponding bleached and dark state is 98/50%, and the other sample exhibits corresponding values of about 25 seconds, about 12 seconds, and about 94/26%, so that the electrochromic material of U.S. patent publication No. 2009323157a1 is rather slow.

U.S. patent publication No. 2017003564A1 discloses electrochromic materials that can be binary metal oxides (e.g., including oxides of two metals in addition to lithium or other transported ions; e.g., NiWO), ternary metal oxidesA compound (e.g. an oxide comprising three metals, such as NiWTaO) or an even more complex material. Generally, they are doped or otherwise combined with one or additional other elements. In each case, the additional element may include at least one non-alkali metal. The electrochromic material may comprise one or more additional elements selected from the group consisting of: silver (Ag), aluminum (Al), arsenic (As), gold (Ag), barium (Ba), beryllium (Be), bismuth (Bi), calcium (Ca), cadmium (Cd), cerium (Ce), cobalt (Co), chromium (Cr), copper (Cu), europium (Eu), iron (Fe), gallium (Ga), gadolinium (Gd), germanium (Ge), hafnium (Hf), mercury (Hg), indium (In), iridium (Ir), lanthanum (La), magnesium (Mg), manganese (Mn), molybdenum (Mo), niobium (Nb), neodymium (Nd), osmium (Os), protactinium (Pa), lead (Pb), palladium (Pd), praseodymium (Pr), zirconium (Pm), polonium (Po), platinum (Ra), rhenium (Re), rhodium (Rh), ruthenium (Ru), antimony (Sb), scandium (Sc), selenium (Se), silicon (Si), samarium (Sm), tin (Sn), strontium (Sr), tantalum (Tb), terbium (Tb), tellurium (Tc), tellurium (Te), thorium (Th), antimony (Sb), selenium (Sc), thorium (Se), thorium (Si), gadolinium (Sm), gadolinium (Gd), yttrium (Gd), hafnium (Hf), and, Titanium (Ti), thallium (Tl), uranium (U), vanadium (V), tungsten (W), yttrium (Y), zinc (Zn), zirconium (Zr), and combinations thereof. In certain embodiments, the additional element may include at least one element selected from the group consisting of tantalum, tin, niobium, zirconium, silicon, aluminum, and combinations thereof. In particular, it discloses a Li_aNiW_xA_yO_zThe material of (1), wherein: a is 1 to 10; x is 0 to 1; y is 0 to 1; and z is at least 1; and wherein a, x, y, z and a are independently selected for each of the first and second sublayers of the counter electrode layer, and the NiWTaO comprises about 7% or 14% tantalum. However, U.S. patent publication No. 2017003564a1 does not mention providing neutral color in colored and bleached states.

U.S. patent publication No. 2017329200a1 discloses an electrochromic material comprising any one or more of a variety of metal oxides, including tungsten oxide (WO)₃) Molybdenum oxide (MoO)₃) Niobium oxide (Nb)₂O₅) Titanium oxide (TiO)₂) Copper oxide (CuO), iridium oxide (Ir)₂O₃) Chromium oxide (Cr)₂O₃) Manganese oxide (Mn)₂O₃) Vanadium oxide (V)₂O₅) Nickel oxide (Ni)₂O₃) Cobalt oxide (Co)₂O₃) And the like. The metal oxide may be doped with one or more dopants, such as lithium, sodium, potassium, molybdenum, niobium, vanadium, titanium, and/or other suitable metals or metal-containing compounds. Mixed oxides (such as W-Mo oxides, W-V oxides) may also be used, and thus the electrochromic layer may comprise two or more of the above-mentioned metal oxides. However, U.S. patent publication No. 2017329200a1 does not mention providing neutral color in colored and bleached states.

U.S. Pat. No. 6266177B1 discloses the production of electrochromic materials such as Cu_0.064W_0.93O_y、K_0.1W_0.9O_y、Na_0.1W_0.9O_y、Li_0.1W_0.9O_y、Ba_0.1WO_0.9O_y、(Li_0.1Cr_0.1W_0.8)O_y、(Li_0.1Co_0.1W_0.8)O_yThe technique of (1). However, U.S. patent No. 6266177B1 is silent about providing neutral color in colored and bleached states.

Patent documents WO2011028253a2, WO2011028254a2 disclose a method of providing an electrochromic material with improved color characteristics. In terms of color/hue, certain embodiments may reduce the yellowish hue in the clear state and the multiple colors that sometimes appear in the colored state by ensuring a Δ E that may be less than about 1.5eV, more preferably less than about 1.25eV, and still more preferably less than about 1eV, with the value of x preferably being 2.4 eV, but rather providing a more neutral color in the clear state by selecting one of the multiple colors in the colored state<x<3; more preferably in the sub-stoichiometric WO_xMedium is 2.6<x<3。

WO2011137080A1, WO2011137104A1 and WO2012177790A2 disclose an electrochromic material WO_3–y(0 < y.ltoreq.0.3) and a nickel tungsten oxide (NiWO) counter electrode with a tantalum dopant to provide a neutral color in the bleached state. However, WO2011137080a1 is silent on providing a neutral color in the colored state.

WO2013013135A1 disclosesDiscloses an electrochromic material Li_xNi(II)_(1–y)Ni(III)_(y)W_zO_{(i+0.5x+0.5y+3z)}. However, WO2013013135a1 is silent on providing neutral color in colored and bleached states.

Patent documents WO2014113796a1 and WO2014113801a1 disclose a lithium tungsten nickel oxide film as an electrochromic material. However, WO2014113796a1 is silent on providing neutral color in colored and bleached states.

Patent document WO2014143410a1 discloses an electrochromic material in which the atomic ratio of the amount of lithium in the electrochromic layer to the total amount of nickel and tungsten (i.e., Li: [ Ni + W ]) or to the total amount of nickel, molybdenum and tungsten (i.e., Li: [ Ni + Mo + W ]) is typically at least about 0.4:1, 0.75:1, 0.9:1, and typically less than 1.75: 1. This document also discloses an electrochromic material having an atomic ratio of the combined amount of molybdenum and tungsten to the combined amount of nickel, molybdenum and tungsten (i.e., [ Mo + W ]: [ Ni + Mo + W ]) of greater than about 0.8:1, 0.7:1, 0.6:1, or 0.5: 1. This document also discloses an electrochromic material having an atomic ratio of the combined amount of molybdenum, tungsten, and bleach state stabilizing element M to the combined amount of nickel, molybdenum, tungsten, and bleach state stabilizing element M In the electrochromic lithium nickel oxide material (i.e., [ Mo + W + M ]: Ni + Mo + W + M ], where M is Y, Ti, Zr, Hf, V, Nb, Ta, B, Al, Ga, In, Si, Ge, Sn, P, Sb, or a combination thereof) of less than about 0.8:1, 0.7:1, 0.6:1, or 0.5:1, but greater than about 0.075: 1. However, WO2014143410a1 is silent on providing neutral color in colored and bleached states.

Patent document WO2017034847a1 discloses an electrochromic material in the form of cubic or hexagonal cesium-doped tungsten oxide nanoparticles with improved color properties, in particular Cs_xWO₃(wherein 0.2)<x<0.4)、Cs₁WO_6–σ(wherein 0)<σ<0.3)、NbO_x、TiO₂、MoO₃、NiO₂、V₂O₅Or a combination thereof. For example, to produce a blue color, the electrochromic material may contain about 100% by weight of WO₃As the first nanostructure, and the second nanostructure may be omitted; to produce the green color, electrochromic materialsMay contain about 60% by weight of Cs_0.29WO₃Hexagonal lattice structure nanocrystals and about 40 wt% indium tin oxide (e.g., Sn: In)₂O₃) A nanocrystal; to produce the brown color, the electrochromic material may comprise about 100 wt% NbO_xNanoparticles (e.g., Nb)₂O_5–σWhere 0 < σ < 0.1) as the first nanostructure, and the second nanostructure may be omitted; to produce a purple color, the electrochromic material may contain about 100 wt% Nb to TiO₂Nanocrystals as the first nanostructure, and the second nanostructure may be omitted; to produce a neutral gray color, the first nanostructure can comprise amorphous niobium oxide nanoparticles (e.g., Nb₂O_5–σWherein 0 is<σ<0.1), and the second nanostructure may comprise cesium-doped tungsten oxide nanoparticles (e.g., CsW) having a cubic lattice structure₂O_6–σNanocrystals of which 0<σ<0.3)。

WO2017136243A1 suggests the use of 5% to 10% by weight of amorphous nanostructured materials such as NbO_xTo color balance the absorption of visible light in electrochromic materials due to the polarizer type shift in the spectral absorption of doped transition metal oxide bronzes, such as Cs₁W₂O_6–xWherein 0 is<x<0.1。

WO2017165834A1 discloses a composition consisting essentially of WO_xThe resulting electrochromic material, wherein x is between about 2.7 and 3.5. However, WO2017165834a1 is silent on providing neutral color in colored and bleached states.

Non-patent document [18]Discloses WO used in electrochemical element and electrochromic device₃The atoms of Li, Na and Ca in the lattice are involved in the intercalation and transformation processes.

Non-patent document [19 ]]Discloses amorphous WO₃The effect of medium lithium concentration on the optical properties of the tungsten oxide based film.

Non-patent document [20]Discloses amorphous WO₃Spectral dependence of medium lithium concentration on transmission and reflection factors of tungsten oxide based filmsThe influence of (c).

Non-patent document [21] discloses a lithium intercalation method involving different electrolytes in an electrochromic material based on tungsten oxide and nickel oxide.

Non-patent document [22 ]]Disclose WO₃Influence of the lithium concentration on the spectral dependence of the optical properties.

Non-patent document [23 ]]Discloses nitrogen-doped pair WO₃The influence of the electrochromic properties of (a).

Non-patent document [24]Disclose WO₃Degree of reduction to WO₃The influence of the electrochromic properties of (a).

Non-patent document [25 ]]Disclose WO₃Type of lattice structure of (2) to WO₃The influence of the electrochromic properties of (a). Indicates the doping of WO with titanium₃The possibility of (a).

Non-patent document [26]Discloses providing a composition based on WO₃Different aspects of the combined electrochromic/storage device of (1).

Non-patent document [27 ]]Discloses doping WO with molybdenum₃To WO₃The spectral dependence of the optical performance of (a).

Non-patent document [28]Disclose WO₃Degree of reduction to WO₃The influence of the electrochromic properties of (a).

Non-patent document [29 ]]Discloses a common tungsten oxide WO₃In contrast, annealed to W with stoichiometric content₁₈O₄₉The optical properties of tungsten oxide.

Conventional electrochromic materials obtained according to the known art have a fixed hue color, mainly blue, which may be uncomfortable for some users and may even be unsuitable in some cases, for example for safety reasons. By fixed color is meant that the prior art generally does not provide any choice of available colors during the production process. Furthermore, conventional electrochromic materials have a limited lifetime. In addition, conventional electrochromic materials have a long transition time when changing from a colored state to a transparent state and back.

Accordingly, there is a need in the art for relatively inexpensive electrochromic materials and techniques for industrial and/or domestic applications that will extend the hue range (including optically neutral colors such as gray or brown), extend service life, and shorten transition times. Preferably, such materials will also be structurally and technically compatible with photovoltaic devices such as solar cells and with energy storage devices such as lithium batteries or supercapacitors. This compatibility will allow the use of uniform technology and provide a combination device such as smart glasses that has controllable transparency and is capable of generating and storing electrical energy.

Disclosure of Invention

Magnetron sputtering and co-sputtering for producing EC materials can be carried out by the PDC method in several ways: (1) directly from carbide-based material targets, such as WC, MoC, CrC, SiC, VC, Ni₃C、Co₂C、NbC-Nb₂C、TaC、SiC、Mn₅C₂Etc.; (2) from the relevant transition metals W, Mo, Cr, Al, Ti, Zr, Nb, Ni, V, Ta, Mn and graphite-based materials targets and non-metallic elements such as Si, Ge, P, B, etc.; (3) directly from the composite target (a fine powder mixture of transition metal, non-metallic elements and graphite powder). In each case, sputtering can be carried out from 1 to 4 targets at once.

The proposed sputtering method allows to obtain EC materials with increased electronic and ionic conductivity, higher coloration and good cycle (lifetime). In addition, the inventors have obtained other shades of blue and gray, black and brown that are neutral to the eye.

The proposed technique provides a solution having the formula WO_2.4-2.9M1, M2, E1, E2, E3, wherein M1 is a dopant selected from Mo, Ti, Ni, Zr, V, Cr, Al, Nb, Ta, Co, Mn; m2 is an optional dopant selected from Mo, Ti, Ni, Zr, V, Cr, Al, Nb, Ta, Co, Mn; here, E1 is a dopant selected from H, N, C, Si, Ge, P, B; e2 is a dopant selected from H, N, C, Si, Ge, P, B; e3 is an optional dopant selected from H, N, C, Si, Ge, P, B, M1 ≠ M2, E1 ≠ E2 ≠ E3.

In particular, the electrochromic material may be M (I)_0.1-3.0WO_2.4-2.9:M1:M2:E1:E2:E3, wherein m (i) is selected from the following group 1 elements: li⁺、Na⁺、K⁺(ii) a Can be M (II)_0.1-1.5WO_2.4-2.9M1: M2: E1: E2: E3, wherein M (II) is selected from the following group 2 elements: mg (magnesium)²⁺、Ca²⁺、Ba²⁺、Zn²⁺(ii) a Or M (III)_0.1-1.0WO_2.4-2.9M1: M2: E1: E2: E3, wherein M (III) is selected from the following group 3 elements: sc (Sc)³⁺、Y³⁺、La³⁺And other lanthanides, i.e. Ce³⁺、Pr³⁺、Nd³⁺、Pm³⁺、Sm³⁺、Eu^{3 +}、Gd³⁺、Tb³⁺、Dy³⁺、Ho³⁺、Er³⁺、Tm³⁺、Yb³⁺、Lu³⁺。

For co-sputtering, a combination of the following gas mixtures may be used: Ar/O₂/N₂、Ar/H₂/N₂/O₂、Ar/NH₃/O₂、Ar/CO/N₂/O₂、Ar/CO/H₂/N₂/O₂、Ar/CH₄/N₂/O₂And Ar/NH₃/CO/N₂/O₂. The pressure of the gas mixture may be between about 5 millitorr and about 15 millitorr, and the flow rate of the gas mixture may be between about 80sccm (standard cubic centimeters per minute) and about 100 sccm.

Furthermore, the EC material may be pre-embedded with Li⁺、Na⁺Or K⁺. Alternatively, the EC material may be pre-embedded with Mg²⁺、Ca^{2 +}、В²⁺Or Zn²⁺. Still alternatively, the EC material may be pre-embedded with Sc³⁺、Y³⁺、La³⁺、Ce³⁺、Pr³⁺、Nd³⁺、Pm³⁺、Sm³⁺、Eu^{3 +}、Gd³⁺、Tb³⁺、Dy³⁺、Ho³⁺、Er³⁺、Tm³⁺、Yb³⁺、Lu³⁺. The pre-intercalation can be carried out in a liquid cell in an argon atmosphere using an absolute organic or inorganic electrolyte.

Further processing depends on the pre-embedding option described above. If the EC material is not pre-embedded, it is post-annealed at a temperature between about 450 ℃ and about 550 ℃. In this case, de-intercalation is not required.

If the EC material is pre-embedded with Li⁺、Na⁺Or K⁺It is thermally cleaved by post annealing at a temperature between about 250 ℃ and about 450 ℃ and further de-intercalated (using Na) in liquid cell ions at about room temperature in negative polarity⁺Or K⁺In the case of pre-intercalation of ions). Using Li⁺When ionic, no de-intercalation step is required.

If the EC material is pre-embedded with Mg²⁺、Ca²⁺、Ba²⁺Or Zn²⁺It is thermally split by post annealing at a temperature between about 250 ℃ and about 450 ℃ and further de-intercalated in the liquid cell at about room temperature under negative polarity.

If the EC material is pre-embedded with Sc³⁺、Y³⁺、Ln³⁺(lanthanide) which is then thermally cleaved by post annealing at a temperature between about 100 ℃ and about 250 ℃ and further de-intercalated in the liquid cell at about room temperature under negative polarity.

When the EC material is pre-embedded with large atoms (e.g., Zn)²⁺、Ca²⁺、Y³⁺Etc.), splitting (i.e., forming vertical nanochannels to promote Li during operation of the EC material⁺Movement of ions) can occur at lower temperatures, sometimes even at room temperature. The larger the pre-embedded atomic radius, the lower the cleavage temperature may be.

Post-annealing allows for fast switching and deep coloration/decolorization of EC materials with stable electrochemical properties and long service life.

The EC material obtained by the above method is at least partially a crystalline material. Depending on the configuration of the EC device layer stack, it may be used as a positive electrode material or a negative electrode material.

Thus, the inventors obtained heavily doped metals M1, M2 ═ Mo, Ti, Ni, Zr, V, Cr, Al, Nb, Ta, Co, Mn and non-metals E1, E2, E3Tungsten oxide EC material of H, N, C, Si, Ge, P, B (WO)_2.4-2.9M1, M2, E1, E2 and E3). In each case, the predominant element was W, with the concentration of tungsten oxide being about 50% greater than the dopant concentration in the final deposited film.

Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by the practice of the invention. The advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.

It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are intended to provide further explanation of the invention as claimed.

Drawings

The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, and together with the description serve to explain the principles of the invention.

In the drawings:

FIG. 1 shows an electrochromic stack;

FIGS. 2A and 2B show a "wet" cell for lithium intercalation (FIG. 2A) and deintercalation (FIG. 2B) for optical measurements;

FIG. 3 shows optical transmittance (T) of EC layer versus Li⁺Correlation of the degree of intercalation, where 1C is the average rapid reversible capacity (about 13mAh/g) of the cells with various heavily doped EC materials used as the positive electrode. Transmittance according to WO_xLi embedded in a base material⁺The ions increase and decrease.

FIG. 4 shows EC-doped tungsten oxide Li in the visible range_xWAlСNO_2.9Transmissivity of (WAlCON) material and Li in the embedding material⁺Correlation of concentration.

Detailed Description

Reference will now be made in detail to the preferred embodiments of the present invention, examples of which are illustrated in the accompanying drawings.

Based on heavily doped tungsten oxide WO_2.4-2.9M1, M2, E1, E2, E3 (which areM1 and M2 ═ Mo, Ti, Ni, V, Cr, Al, Nb, Ta, Co, Mn; e1, E2, E3 ═ H, N, C, Si, Ge, P, B), Electrochromic (EC) materials were developed. When these materials are metal ion-embedded positive electrode materials, they are not only strongly colored in various shades of blue (cool blue, violet, grayish blue, etc.), but in some cases, the new materials are colored in such "neutral" colors as gray, black and brown. The clarity of the resulting material ranges from T ≧ 76% in the bleached state to T ≦ 0.3% in the colored state and exceeds many existing commercial products. In some cases where the sample is fully colored, the film may be completely opaque in the visible range.

Doping of WO_xThe host material is carried out by magnetron reactive co-sputtering of metal and carbide materials or by reactive co-sputtering of metal and graphite. The use of carbide materials as targets or co-sputtering of metals and graphite is the WO material that yields EC materials with advanced properties_2.4-2.9M1, M2, E1, E2 and E3.

The resulting material was post annealed at higher temperatures (450 ℃. 550 ℃). Thus, the material is crystalline. Different publications often show a diametrically opposite view on the effectiveness of amorphous and crystalline EC materials based on tungsten oxide. The inventors have studied a number of doping materials WO_2.4-2.9Samples of M1: M2: E1: E2: E3 and concluded that the crystalline structure is more efficient and stable when used as an EC layer. The maximum temperature of post-annealed EC sputtered materials, known from published sources, is typically no more than 350-]Whereas sol-gel techniques typically use higher temperatures (up to 800 ℃) when sintering small particles to form EC layers.

The EC film obtained by this method has increased electron conductivity and a more porous structure. It is favorable for positive ion (H)⁺、Li⁺、Na⁺、K⁺、Ca²⁺、Mg²⁺、Zn²⁺、Y³⁺、Sc³⁺、La³⁺Etc.) to avoid damage to the EC coating. In addition, the proposed method allows the application of a fairly thick EC layer (up to 10 μm thick) while maintaining acceptable coloring and bleaching rates.Thus, it can achieve more intense coloration in the depth of the EC coating. This is particularly important where the necessary colour or depth of shade may not be obtainable by other methods. In other words, when the color intensity of the material itself is low, the thickness of the coating is large [30 ]]Therefore, a desired transmittance (T) can be obtained in a colored state in the visible light range.

WO obtained by the inventors based on the value of the electrochemical potential of the counter electrode used in the battery_2.4-2.9M1, M2, E1, E2 and E3 materials can be used as positive or negative EC materials. When the counter electrode is made of metal foil or graphite-based material or some oxide-based material or phosphate-based material such as Li₄Ti₅O₁₂、CeO₂、LiMnO₂、Nb₂O₅、TiO₂、LiFePO₄Etc. all have a relatively low electrochemical potential (typically a ratio of Li/Li)⁺Small 3.3-3.5V), WO_2.4-2.9M1, M2, E1, E2 and E3 materials can be used as the positive electrode EC material. In other words, when a battery containing the positive electrode EC material is discharged (without any stored charge), the EC layer is fully embedded (e.g., by Li)⁺Ions) and in a colored state. Thus, in this configuration, no power is consumed to maintain the EC material in a colored state. This option can save energy if the EC material must be in a colored state most of the time. For example, it may be advantageous when EC materials are used to provide facade glass that can be operated under high sun conditions. In this case, the EC material can be de-energized most of the time, and the interior space can still be secured from solar radiation, and can be energized for a short time when the glass needs to be in a colorless state.

When the counter electrode is made of a material having a high electrochemical potential (typically a ratio of Li/Li)⁺3.3-3.5V) larger than the total volume of the material, e.g. V₂O₅、LiCoO₂、LiNiO₂、LiNiCoO₂When made of, etc., WO_2.4-2.9M1, M2, E1, E2 and E3 materials can be used as the negative electrode EC material. In other words, when the battery containing the negative electrode EC material is discharged (without any stored charge), the EC layer is completely de-intercalated and in a colorless state. Therefore, in this kindIn construction, no power is consumed to maintain the EC material in a colorless state. This option can save energy if the EC material must be in a colorless state most of the time. It may be advantageous when the EC material is used in applications where it is desirable to pass as much sunlight or other light as possible most of the time, for example in a home solution or automotive dimmable glass.

Furthermore, the EC material WO obtained by co-sputtering carbides and co-sputtering with graphite_2.4-2.9The membrane of M1: M2: E1: E2: E3 can be used for electrodes with advanced properties for electrochemical power capacitors such as batteries, supercapacitors (pseudo-capacitors or hybrid capacitors) [31 ]]. These materials would have greater potential if compared to existing conventional positive electrode materials based on cobalt, nickel and manganese oxides, since they would be for Li/Li⁺May be much higher, have a service life many times longer, and have a fairly broad operating temperature range (-50 … +150 ℃). This greatly expands the range of applications for such power supplies.

Material

Magnetron sputtering of all materials was performed on rigid and flexible substrates (a) (fig. 1). The buffer layer (b) may be sputtered before the conductive layer (c). Combinations of the following (a), (b), and (c) may be used: (glass or ceramic)/SiO₂ITO, glass/SiC_xO_yFTO, (PET or PEN)/SiO₂ITO film (in some cases at relatively low temperatures) or any other transparent substrate for transparent electrode assemblies as well as non-transparent or mirror electrodes, such as (glass or ceramic)/M,/SiO₂/ITO、(vi) M, (PEN or PET)/M (M ═ Al, Ti, Mo, Cr, NiCr, or any suitable reflective metal) to perform optical and electrochemical measurements in a liquid cell (fig. 2A, fig. 2B). The thickness of the substrate may also vary. For flexible polymer films or some thin flexible ceramics, the thickness is typically 20 to 250 μm, and for glass, ceramics and other rigid substratesThe thickness of the material is usually 0.45 to 4 mm. The buffer layer (b) in some substrates must be applied with a thickness in the range of 50 to 200 nm. The thickness of the electronic conducting layer (c) is about 150-250nm for ITO, 900nm for FTO and 350nm for 250-350nm for metal conductor. Commercially available custom-made substrates with conductive layers can be used.

EC material (d) was synthesized by magnetron co-sputtering of several different targets and simultaneous deposition. By varying the power of the magnetron gun, it is possible to operate in the main WO_xA plurality of doping elements are used in the matrix. This facilitates the manufacture of a variety of EC materials with satisfactory coloration and electrochemical properties.

Production Process A

Co-sputtering from 2 targets was used. One target is W or WC and the second target is MC_{Carbide(s) and method of making the same}–MoC、CrC、SiC、VC、Ni₃C、Co₂C、NbC-Nb₂C、TaC、SiC、Mn₅C₂Etc., and non-metallic carbides, such as EC ═ SiC or composite targets M (or E) C_{Composite material}(M ═ Al, Nb, V, Ti, Ta, Co, Mn, NiV 7; E ═ Si, Ge, P, B; C ═ graphite). Composite targets may be used when carbide materials are not available, or simply to reduce material costs.

Combining the target materials: w (WC) -M1(E1) C_{Carbide(s) and method of making the same}And W (WC) -M1(E1) C_{Composite material}。

Gas mixture: Ar/O₂/N₂、Ar/H₂/N₂/O₂、Ar/NH₃/O₂、Ar/CO/N₂/O₂、Ar/CO/H₂/N₂/O₂、Ar/CH₄/N₂/O₂And Ar/NH₃/CO/N₂/O₂。

Post annealing: slow annealing was performed in a muffle furnace or Rapid Temperature Annealing (RTA) was performed in air at 450-.

By this method, for example, WO_2.6-2.9E1, E2, E3 and WO_2.6-2.9M1E 1E 2E 3(M1 is Ti, NiV7, V, Cr, Al, Nb, Ta, Co, Mn; E1, E2, E3 is H, N, C, Si, Ge, P, B). M1 and of E1, E2, E3The presence makes the tungsten oxide matrix more crystalline and provides more surface area. The presence of nanoscale vertical channels in EC membranes improves M (I, II, III)ⁿ⁺The penetration depth of the ions. Thus, almost the entire volume of WO_xThe base material may be used to interact with the M (I, II, III) ion. The presence of the dopant also enhances the electronic conductivity of the material. That is why it is compatible with pure WO₃Oxygen-deficient WO_2.4-2.9And even some of the well-known doped WO_xBase material and nitrogen-doped tungsten oxide (WNO) [14 ]]The reason for faster coloration and higher strength in the EC layer is compared.

Production method B

Co-sputtering from 3 targets was used.

Combining the target materials: W-M1(E1) C_{Carbide(s) and method of making the same}-M2 and W-M1(E1) C_{Composite material}-M2。

Gas mixture: Ar/O₂/N₂、Ar/H₂/N₂/O₂、Ar/NH₃/O₂、Ar/CO/N₂/O₂、Ar/CO/H₂/N₂/O₂、Ar/CH₄/N₂/O₂And Ar/NH₃/CO/N₂/O₂。

Post annealing: slow annealing was performed in a muffle furnace or Rapid Temperature Annealing (RTA) was performed in air at 450-.

By this method, for example, WO₃M1M 2E 1E 2E 3(M1, M2 is Ti, NiV7, V, Cr, Al, Nb, Ta, Co, Mn; E1, E2, E3 is H, N, C, Si, Ge, P, B). The presence of M1, M2 and E1, E2, E3 dopants (such as in method a) makes the tungsten oxide film more conductive to M (I, II, III) ions and electrons. In addition, the oxidation state in the tungsten oxide matrix is 3⁺、4⁺And 5⁺The combination of dopants helps to suppress "deep trap" ion intercalation during the coloration process [31]. Thus, almost the entire volume of material is available for interaction with the M (I, II, III) ion, and the reaction is fully reversible. The EC layer is pigmented faster and has a higher color intensity.

Production method C

Co-sputtering from 4 targets was used.

Combining the target materials: W-M1(E1) -M2-C_Graphite

Gas mixture: Ar/O₂/N₂、Ar/H₂/N₂/O₂、Ar/NH₃/O₂、Ar/CO/N₂/O₂、Ar/CO/H₂/N₂/O₂、Ar/CH₄/N₂/O₂And Ar/NH₃/CO/N₂/O₂。

By this method, the same materials as in method B can be synthesized, but instead of using carbides or graphite composites, co-sputtering with a separate graphite target is used to obtain approximately the same results. This method is more complex in view of sputtering 4 targets simultaneously, but makes the process cheaper and more flexible. For example, it is not necessary to manufacture expensive and complex composite targets or refractory carbide targets.

Optical measurement

In order to identify the color intensity, the coloration kinetics and the color coordinates of the EC material, liquid cells or half-cells (fig. 2A, 2B) placed in containers (cuvettes) made of PMMA or quartz glass were used.

Samples of EC film (d) on substrates (a) - (c) were placed into 1M LiClO₄Or LiPF₆In solution in purified Propylene Carbonate (PC). The cell comprises a positive electrode (d), an electrolyte (e) and a negative electrode (f), and thus forms a galvanic cell (secondary cell). Therefore, to color (ion-intercalate) the positive electrode material, a fixed load (e.g., 10, 100, or 1000 ohms) of the galvanic cell discharge may be used, a reverse voltage of DC may be applied, and a potentiostat/galvanostat may be used. A foil made of Li, Na, K, Mg, Ca, Zn, Sc, Y, La, etc. may be used as the negative electrode (f) metal. Lithium metal, calcium, magnesium and zinc are mainly used. When lithium is used as the negative electrode, the OCV value is 3.2 to 3.4V. By batteries WO_2.4-2.9:M1:M2:E1:E2:E3|PC+LiClO₄The discharge curve of Li monitors the coloration time. A discharge of 6% -10% of the liquid cell is considered to be the maximum rapid reversible coloring state. To create the transmittance change curve, points corresponding to different degrees of discharge were used (fig. 3). In addition to this, the present invention is,the EC sample (e.g., substrate Si/SiO) that has been discharged to the requisite condition₂/Ti/WO_2.4-2.9M1: M2: E1: E2: E3) were taken out of the cell and washed with an organic absolute aprotic solvent. Then, the reflectance (transmittance) and the color coordinates CIE L a b of the EC layer were measured. Almost all operations are carried out in a dry gas or inert gas atmosphere.

Other methods of EC film modification to achieve higher performance

WO is obtained from a target material containing carbide and graphite by using a reactive magnetron sputtering method_2.4-2.9M1, M2, E1, E2, E3 and the synthesis of new materials is highly satisfactory. This method allows to obtain EC materials with improved porosity, increased number of metal ion diffusion channels and improved ion conductivity. In addition, the performance characteristics of the above materials are much improved, including significantly increased surface area and porosity of the material, and extended service life due to the use of pre-embedded samples of pre-embedded and "split" EC films.

Method I surface modification by M (I) ion Pre-intercalation and post-annealing

Base material: Si/SiO₂(M-Ti, Mo, Cr, NiCr or stainless steel), glass/SiO₂ITO or glass/SiC_xO_yFTO or the like.

Source materials: WO_2.4-2.9M1, M2, E1, E2 and E3, as described above.

Monovalent metal ions (Li) were separated by EC materials maximum (irreversible) capacity 1/8, 1/4, 1/2, 3/4 and 1C using potentiostat/galvanostat⁺，Na⁺And K⁺) Pre-embedded in the original sample. For intercalation, the same cell with liquid electrolyte as shown in fig. 2A was used. In addition, a pre-embedded material M (I) having a similar structure to the original amorphous pre-embedded material is formed_0.1-0.65WO_2.4-2.9M1, M2, E1, E2 and E3.

The resulting samples were post annealed at +250 … +450 ℃ under argon. During this time, partially "split" EC films and nearly regularly shaped vertical channels were formed. The diameter of the channel is about 30 nm.

By this method the material is modified with an alternation speed between bleached and colored state which is 5-10 times faster than the unmodified material. This may be important in some applications where switching speed is important (e.g. in displays, rear view mirrors, dynamic optics).

Method II surface modification by M (II, III) ion Pre-intercalation with and without post-annealing

In addition to monovalent metal ions for pre-intercalation, divalent or trivalent metal ions (e.g. Mg)²⁺、Ca^{2 +}、Ba²⁺、Zn²⁺、Sc³⁺、Y³⁺And La³⁺). The relevant material was used as the negative electrode, and a similar battery was used (fig. 2A). Similar to the case of monovalent metal ions, potentiostats/galvanostatics were also used for intercalation at 1/8, 1/4, 1/2, 3/4, and 1C, which are the maximum capacities of EC materials. During the subsequent post-annealing, "splitting" of the EC film occurs, thus forming vertical channels and a significant increase in surface area. During this time, crystallite formation was observed, the crystallites having M (II, III)_xWO_2.4-2.9M1, M2, E1, E2, E3, where for M (II)²⁺0.1 … 0.25.25 for M (III)³⁺，x＝0.1…0.15。

In the case of intercalation of multivalent metal ions, their ionic radius is greater than that of lithium ions, thus achieving "splitting" of the EC film and increasing its surface area at lower temperatures by a subsequent post-annealing process, which is important when organic substrates are used.

The EC film obtained by this method can be used for a film having monovalent metal ions (Li)⁺、Na⁺Or K⁺) In the battery of (1). Their coloring speed is also significantly increased. Furthermore, the cycle resistance of the material constructed by this method is significantly improved.

It should be noted that from a technical point of view, a method of increasing the surface area without post-annealing (or with low temperature post-annealing) may be more attractive, since in this case no additional high temperature post-annealing operation is required. However, EC materials with nanocrystallites formed using post-annealing at high temperatures (450 ℃ - & 550 ℃) have better cycle resistance.

New heavy doping EC materials WO are proposed_2.4-2.9M1, M2, E1, E2, E3, which are colored blue, grayish blue, gray, black and brown after ion intercalation. These materials are synthesized by reactive magnetron co-sputtering, which imposes the use of one or several carbon-containing targets (carbides, graphite composites or pure graphite). High temperature post annealing and pre-embedding are also used. Materials synthesized according to this method exhibit higher electronic and ionic conductivities.

Can be pre-intercalated by monovalent and multivalent ions to form compositions M (I)_0.1-0.65WO_2.4-2.9:M1:M2:E1:E2:E3、M(II)_0.1-0.25WO_2.4-2.9M1, M2, E1, E2, E3 and M (III)_0.1-0.15WO_2.4-2.9M1, M2, E1, E2 and E3. When multivalent ions are used, the coloring speed is higher.

According to the invention, a method is proposed for modifying a material by pre-embedding an EC layer during post-annealing and then "thermal splitting". In this case, the EC material is constructed in such a manner that: vertical nano-sized channels are formed, which facilitate the subsequent intercalation and de-intercalation of metal ions during normal operation of the EC material. Thus, the speed of coloring and bleaching is increased by 5-10 times. In addition, the crystallites formed under high temperature post-annealing have better resistance to cycling, and thus the lifetime of the EC material is substantially increased.

Table 1 below shows the dependence on Li_xWAlCNO_2.6EC material transmittance T of the EC material capacity of (a).

TABLE 1

In Table 1, 1C is based on WO₃Average 100% reversible tinting power of the doped EC material of the matrix. The reversible coloring power is defined inThe ability to completely reverse color and bleach is provided in EC materials. With organic liquid electrolytes, there is technically no degradation and "deep ion trapping" effect at 1C.

In some cases, the obtained EC material had a large theoretical capacity of 300-320mAh/g and some dopant material in the tungsten oxide matrix, with an actual capacity measured during the test of 240-250mAh/g, which greatly exceeded the capacity of currently used lithium ion battery positive electrode materials (LiCoO)₂Has a theoretical capacity of 140mAh/g and LiMn₂O₄Has a theoretical capacity of 148mAh/g and LiFePO₄Theoretical capacity of-170 mAh/g etc. [20 ]]. Therefore, the material obtained by the inventor is expected to be used as a positive electrode material in an electrochemical current source.

On the one hand, high capacity may be advantageous when the EC material is used in electrochemical current sources, for example, in combined EC/photovoltaic devices. On the other hand, such high capacity may be a disadvantage for some EC devices, as the transition from the bleached state to the colored state or vice versa may require more energy. In view of this, it should be noted that although Li is obtained according to the invention_xWO_2.4-2.9M1: M2: E1: E2: E3 have very high theoretical capacity (theoretically, the material can be intercalated with lithium ions, up to x ═ 3), and its EC effect becomes apparent when only 6% to 10% of the theoretical capacity is charged or discharged, which corresponds to an intercalation value of about x ═ 0.18 … 0.3.3 (fig. 3). In other words, the high capacity of these materials is not a serious limitation in power consumption for EC device applications. Furthermore, the lifetime of such devices will be longer due to the mild cycling conditions in EC mode.

Examples

Further provided is WO constructed by the inventors during prototype fabrication_2.4-2.9Examples of samples M1: M2: E1: E2: E3 are described to demonstrate that the claimed technical results are obtained.

Example 1

W_0.89O_2.6:Al_0.39:C_0.02:N_0.01The positive electrode EC material is prepared from W, Al and graphite target materials in Ar/O₂/N₂In an atmosphere by heating at room temperatureThe lower PDC was synthesized by magnetron co-sputtering onto a glass/FTO substrate. The thickness of the EC layer was 500-1000 nm. Sputtering pressure of 10mT, total gas flow of 80sccm, wherein O₂Is 6sccm, N₂Is 24 sccm. The post-annealing was carried out in a muffle furnace in air at 500 ℃. Optical, electrochemical and kinetic switching measurements were performed in liquid cells. The EC material obtained is dark blue in the colored state and is in PC-LiClO₄LiFePO is used at 1.0-2.0V in the electrolyte₄Exhibits an excellent switching time as a counter electrode (about 20 to 60 seconds for both the colored state and the decolored state). The maximum transmission of the film in the visible range is about 76% in the bleached state and less than 0.3% in the colored state. In Li⁺After de-intercalation, there was no residual blue color in the bleached state.

Example 2

W_0.9O_2.6:Cr_0.22:C_0.12:N_0.01The EC material of the positive electrode is prepared by using W and Cr target materials in Ar/O₂/N₂Synthesized in an atmosphere by PDC reaction magnetron co-sputtering onto a glass/FTO substrate at room temperature. The thickness of the EC layer is 350-1000 nm. Sputtering pressure of 10mT, total gas flow of 80sccm, wherein O₂Is 24sccm, N₂Was 6 sccm. The post-annealing was carried out in a muffle furnace in air at 450 ℃. Optical, electrochemical and kinetic switching measurements were performed in liquid cells. The EC material obtained is graphite-grey in the colored state and is in PC-LiClO₄Use of LiFePO at 2.0V in electrolytes₄The counter electrode showed excellent switching times (about 20-30 seconds for both the colored and bleached states). The maximum transmission in the visible range is about 71% in the bleached state and below 4% in the colored state. The sputtered film has a very small brown tint (in a discolored state) after post-annealing, and this tint becomes less after a number of intercalation/de-intercalation cycles.

Example 3

W_0.9O_2.6:Cr_0.23:C_0.14:H_0.01:N_0.01The positive electrode EC material is prepared from W, Cr and graphite target materials in Ar/CH₄/N₂/O₂Synthesized in an atmosphere by PDC reaction magnetron co-sputtering onto a glass/FTO substrate at room temperature. The thickness of the EC layer is 350-1000 nm. Sputtering pressure of 10mT, total gas flow of 80sccm, wherein O₂Is 24sccm, N₂Was 6 sccm. The post-annealing was carried out in a muffle furnace in air at 450 ℃. Optical, electrochemical and kinetic switching measurements were performed in liquid cells. The EC material obtained is virtually black in the colored state and is in PC-LiClO₄Use of LiFePO at 2.0V in electrolytes₄The counter electrode still showed excellent switching times (about 60 seconds for the colored state and about 90 seconds for the bleached state). The maximum transmission in the visible range is about 65% in the bleached state and less than 1% in the colored state. The sputtered film was brown in color (in a bleached state) after post-annealing, and the color remained almost unchanged after multiple insertion/extraction cycles.

Example 4

W_0.61O_2.6:Al_0.78:C_0.13:H_0.01:N_0.02The positive electrode EC material is prepared from W, Al and graphite target materials in Ar/NH₃/CO/N₂/O₂Synthesized in an atmosphere by PDC reaction magnetron co-sputtering onto a glass/FTO substrate at room temperature. The thickness of the EC layer was 500-1000 nm. Sputtering pressure of 10mT, total gas flow of 80sccm, wherein O₂Is 4sccm, N₂Was 26 sccm. Post annealing was performed in a muffle furnace in air at 550 ℃. Optical, electrochemical and kinetic switching measurements were performed in liquid cells. The EC material obtained is blue in the colored state and is in PC-LiClO₄LiFePO is used at 1.0-2.0V in the electrolyte₄Or LiCoO₂The average switching time (about 90 seconds for the colored state and about 150 seconds for the bleached state) was exhibited as the counter electrode. The maximum transmission of the film in the visible range is about 62% in the bleached state and less than 10% in the tinted state. In Li⁺After de-intercalation, there is still some residual blue color (in a bleached state) which cannot be removed if the layer thickness exceeds 500 nm.

Example 5

W_0.89O_2.9:Nb_0.28:C_0.12:N_0.01The positive electrode EC material is prepared from W, Nb and graphite target materials in Ar/N₂/O₂Synthesized in an atmosphere by PDC reaction magnetron co-sputtering onto a glass/FTO substrate at room temperature. The thickness of the EC layer was 500-1000 nm. Sputtering pressure of 10mT, total gas flow of 80sccm, wherein O₂Is 10sccm, N₂Is 20 sccm. The post-annealing was carried out in a muffle furnace in air at 450 ℃. Optical, electrochemical and kinetic switching measurements were performed in liquid cells. The EC material obtained is almost blue in the colored state and is in PC-LiClO₄LiFePO is used at 1.0-2.0V in the electrolyte₄The counter electrode showed an average switching time (about 120 seconds for the colored state and about 240 seconds for the bleached state). The maximum transmission in the visible range is about 75% in the bleached state and less than 2% in the colored state. The sputtered film did not have any color tone (in a discolored state) after post-annealing and appeared rather colorless in the visible range. However, if the layer thickness exceeds 1500nm, then in Li⁺After de-intercalation, the material may have some residual blue color (in a bleached state).

Example 6

W_0.9O_2.6:Ni_0.28:V_0.06:Si_0.12:C_0.05:N_0.01The positive electrode EC material is prepared from W, NiV7 and SiC target materials in Ar/N₂/O₂Synthesized in an atmosphere by PDC reaction magnetron co-sputtering onto a glass/FTO substrate at room temperature. The thickness of the EC layer was 500-2500 nm. Sputtering pressure of 10mT, total gas flow of 80sccm, wherein O₂Is 8sccm, N₂Is 22 sccm. The post-annealing was carried out in a muffle furnace in air at 500 ℃. Optical, electrochemical and kinetic switching measurements were performed in liquid cells. The EC material obtained is a "dirty" blue in the coloured state and is present in the PC-LiClO₄LiFePO is used at 1.0-2.0V in the electrolyte₄The counter electrode showed excellent switching times (about 90 seconds for the colored state and about 120 seconds for the bleached state). The maximum transmission in the visible range is about 66% in the bleached stateAnd less than 3% in the colored state. The sputtered film was light brown (in a discolored state) and lost most of the color after post annealing. If the layer thickness exceeds 1000nm, then in Li⁺After de-intercalation, the material may have some residual color.

Example 7

W_1.05O_2.6:Al_0.07:Si_0.06:B_0.05:C_0.02:(N_0.001) The positive electrode EC material is formed by W, AlSi compound and BC compound in Ar/O₂/N₂Synthesized in an atmosphere by PDC reaction magnetron co-sputtering onto a glass/FTO substrate at room temperature. The thickness of the EC layer was 500-2500 nm. The sputtering pressure is 10-15mT, the total gas flow is 80sccm, wherein O₂Is 11sccm, N₂Was 19 sccm. Post annealing was performed in a muffle furnace in air at 550 ℃. Optical, electrochemical and kinetic switching measurements were performed in liquid cells. The EC material obtained is dark grayish blue in the colored state and is present in PC-LiClO₄LiFePO is used at 1.0-2.0V in the electrolyte₄The counter electrode showed very excellent switching times (about 60 seconds for the colored state and about 120 seconds for the bleached state). The maximum transmission in the visible range is about 70% in the bleached state and less than 1% in the colored state. The sputtered film was in a light gray shade (in a bleached state) after post annealing. In Li⁺After de-intercalation, the material had little residual blue color.

Example 8

W_0.58O_2.9:Ni_0.63:B_0.07:P_0.05:C_0.02:(N_0.001) The positive electrode EC material is formed by WNi and BPC compound two targets in Ar/O₂/N₂Synthesized in an atmosphere by PDC reaction magnetron co-sputtering onto a glass/FTO substrate at room temperature. The thickness of the EC layer was 500-2500 nm. The sputtering pressure is 10-15mT, the total gas flow is 80sccm, wherein O₂Is 4sccm, N₂Was 26 sccm. Post annealing was performed in a muffle furnace in air at 550 ℃. Optical, electrochemical and kinetic switching measurements were performed in liquid cells. The EC material obtained is brown in the colored stateAnd in PC-LiClO₄LiFePO is used at 1.5-2.0V in the electrolyte₄The counter electrode showed an average switching time (about 120 seconds for the colored state and about 240 seconds for the bleached state). The maximum transmission in the visible range is about 62% in the bleached state and less than 3% in the colored state. The sputtered film was light brown (in a bleached state) after post-annealing in Li⁺Some residual brown color remained after de-intercalation.

Example 9

W_0.9O_2.6:Al_0.16Mn_0.08:C_0.02:N_0.01The positive electrode EC material is prepared by mixing three target materials of W, Al and MnC compound in Ar/CO/N₂/O₂Synthesized in an atmosphere by PDC reaction magnetron co-sputtering onto a glass/FTO substrate at room temperature. The thickness of the EC layer was 500-2500 nm. Sputtering pressure of 10mT, total gas flow of 80sccm, wherein O₂Is 6sccm, N₂Is 24 sccm. The post-annealing was carried out in a muffle furnace in air at 500 ℃. Optical, electrochemical and kinetic switching measurements were performed in liquid cells. The EC material obtained is dark blue in the colored state and is in PC-LiClO₄LiFePO is used at 1.0-2.0V in the electrolyte₄The counter electrode showed excellent switching times (about 80 seconds for the colored state and about 160 seconds for the bleached state). The maximum transmission in the visible range is about 73% in the bleached state and less than 1% in the colored state. The sputtered film was almost colorless after post annealing. In Li⁺After deintercalation, the material had no residual blue color (in a bleached state).

Example 10

Split W_1.0O_2.6:Al_0.06:C_0.15:N_0.01The positive electrode EC material is prepared from W, Al and graphite target materials in Ar/O₂/N₂Synthesized in an atmosphere by PDC reaction magnetron co-sputtering onto a glass/FTO substrate at room temperature. The thickness of the EC layer was 500-1000 nm. Sputtering pressure of 10mT, total gas flow of 80sccm, wherein O₂Is 24sccm, N₂Was 6 sccm. In the presence of PC-LiClO₄Electrolyte and Li foil as counter electrode solutionIn a bulk battery, by Li⁺The ions are pre-intercalated to provide about Li_(0.22-0.64)W_1.0O_2.6:Al_0.06:C_0.15:N_0.01And (3) a membrane. The material was post annealed in an RTA oven at 450 ℃ in an argon atmosphere. After post annealing, reverse Li is performed⁺And (4) de-intercalation. Optical, electrochemical and kinetic switching measurements were performed in liquid cells. The EC material obtained is dark blue in the colored state and is in PC-LiClO₄LiFePO is used at 1.0-2.0V in the electrolyte₄Exhibit excellent switching times as counter electrodes (25-70 seconds for both the colored and bleached states). The maximum transmission of the split film in the visible range is about 75% in the bleached state and less than 0.2% in the colored state. In Li⁺There was some residual blue color (in a bleached state) after de-intercalation.

Example 11

Split W_0.97O_2.8:Cr_0.23:C_0.04:N_0.01The positive electrode EC material is prepared from W, Cr and graphite target materials in Ar/O₂/N₂Synthesized in an atmosphere by PDC reaction magnetron co-sputtering onto a glass/FTO substrate at room temperature. The thickness of the EC layer was 500-2500 nm. Sputtering pressure of 10mT, total gas flow of 80sccm, wherein O₂Is 24sccm, N₂Was 6 sccm. In the presence of PC-LiClO₄In a liquid battery having an electrolyte and a Li foil as a counter electrode, by Li⁺The ions are pre-intercalated to provide about Li_(0.18-0.25)W_0.97O_2.8:Cr_0.23:C_0.04:N_0.01And (3) a membrane. The material was post annealed in an RTA oven at 450 ℃ in an argon atmosphere. After post annealing, reverse Li is performed⁺And (4) de-intercalation. Optical, electrochemical and kinetic switching measurements were performed in liquid cells. The EC material obtained is black in the colored state and is PC-LiClO₄Use of LiFePO at 2.0V in electrolytes₄The counter electrode showed excellent switching times (about 20 seconds for the colored state and about 60 seconds for the bleached state). The maximum transmission in the visible range is about 70% in the bleached state and less than 3% in the colored state. The split films were light brown after post annealing. In Li⁺After deintercalation, the material had almost no residual color (in a decolored state).

Example 12

Split W_1.0O_2.6:Al_0.06:C_0.15:H_0.01:N_0.02The positive electrode EC material is prepared from W, Al and graphite target materials in Ar/NH₃/CO/N₂/O₂Synthesized in an atmosphere by PDC reaction magnetron co-sputtering onto a glass/ITO substrate at room temperature. The thickness of the EC layer was 500-2500 nm. Sputtering pressure of 10mT, total gas flow of 80sccm, wherein O₂Is 24sccm, N₂Was 6 sccm. In the presence of PC-Zn (ClO)₄)₂In a liquid battery having an electrolyte and a Zn foil as a counter electrode, Zn passes through²⁺Ions are pre-intercalated to provide about Zn_(0.1-0.15)W_1.0O_2.6:Al_0.06:C_0.15:H_0.01:N_0.02And (3) a membrane. The material was post annealed at 250 ℃ in an argon atmosphere. After low-temperature post-annealing, reverse Zn is carried out²⁺And (4) de-intercalation. In the presence of PC-LiClO₄Optical, electrochemical and kinetic switching measurements were performed in liquid cells of electrolyte. The EC material obtained is dark blue in the colored state and is in PC-LiClO₄Use of LiFePO at 2.0V in electrolytes₄The counter electrode showed excellent switching times (about 90 seconds for the colored state and about 240 seconds for the bleached state). The maximum transmission in the visible range is about 71% in the bleached state and less than 3% in the colored state. Post-annealing at low temperatures and subsequent Li⁺After the intercalation/deintercalation cycle, the low temperature split film was pale blue (in a decolored state). After the splitting process, the material may contain some "trapped" Zn²⁺Ions.

Conclusion

The inventors have developed a new EC material WO by a tungsten oxide deep doping method_2.4-2.9M1, M2, E1, E2, E3, which have a fairly broad range of colors-blue, grayish blue, gray, black and brown hues. They are deposited simultaneously in several gases from several targets by reactive magnetron co-sputteringIn a mixture of (a). One of the targets should always be a carbonaceous material, such as a metal or non-metal carbide, a composite mixture of metal and graphite, or pure graphite. The reactive gas mixture in which the sputtering takes place always contains N₂Or NH₃A nitrogen source in the form of carbon-containing gas and possibly carbon-containing gas₄. In most cases, it is important to post-anneal the EC film at very high temperatures (450-. The method of the present invention results in the formation of EC materials with much higher electronic and ionic conductivity, which enables the production of thicker EC layers without reducing the coloration and bleaching rate.

New EC material structuring methods have also been proposed, namely a pre-embedding method followed by "thermal splitting" in a post-anneal. Pre-intercalation is performed by monovalent and/or polyvalent metal ions.

It should be noted that the use of multivalent ions speeds up the coloration speed of the EC material, because one charged particle carries twice or three times the total charge during one action, and the process of reducing tungsten with the dopant is faster. However, since multivalent ions generally have a large ionic radius, their back diffusion during bleaching of EC materials may be hindered.

Furthermore, the resulting materials and applied structuring methods are promising for the production of positive electrode materials for primary and secondary electrochemical power sources. Such positive electrode materials have a large capacity and power and can remain functional over a wide temperature range without visible degradation, which may be critical for many applications of such power supplies.

The terms "about" or "substantially" are used herein to indicate that the relevant numerical value or values may vary reasonably, for example, depending on manufacturing tolerances and/or measurement accuracy. In some cases, this may mean that the actual value may vary by ± 5% or ± 10% from the indicated value.

Having thus described the preferred embodiments, it will be apparent to those skilled in the art that certain advantages of the described methods and apparatus have been achieved. It will be obvious to those skilled in the art that the above examples are merely illustrative of the claimed invention and that they are not physically capable of covering all combinations of the claimed feature ranges. To cover all of these combinations, the inventors would have to perform thousands of experiments, which would be very expensive and time consuming, and thus providing all possible examples is economically disadvantageous. However, common general knowledge of EC theory and some experiments conducted by the inventors have led them to indicate that any combination of the parameters cited in the claims provides at least one of the following benefits: different colors of EC materials may be obtained; the coloring and/or decoloring speed is improved; the service life is prolonged; the working temperature range of the EC material is expanded; it is possible to realize EC/photovoltaic combination devices with competitive properties.

It should also be appreciated that various modifications, adaptations, and alternative embodiments thereof may be made within the scope and spirit of the present invention. The invention is further defined by the following claims.

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