Electrochromic element, materials for use in such element, processes for making such element and such materials and use of such element in an electrochromic glass device
First Claim
1. An electrochromic element comprising a pair of conductive electrodes at least one of which is transparent, first and second inorganic electrochromic layers interposed between said pair of conductive electrodes and an ion conducting layer of an electrolyte interposed between said first and second inorganic electrochromic layers, wherein said first and second inorganic electrochromic layers are different and are capable of exhibiting electrochromic properties upon the incorporation of at least one ion of an element selected from the group consisting of H, Li, Na, K, Ag, Cu and Tl, wherein said second inorganic electrochromic layer is amorphous, wherein the electrochromic properties of said first and second inorganic electrochromic layers are complementary, and wherein said second inorganic electrochromic layer comprises the composition
wherein x, y, z, u≧
0, 2≦
n≦
3, 1≦
m≧
2, n+m≦
4;
T is a fourth period transition element selected from Ni, Co, Mn, Cr, V, Ti or Fe;
M is at least one element selected from H, Li, Na, K, Ag, Cu and Tl;
X is selected from O, S, F and Cl;
n, n+m and u are oxidation numbers; and
x is the moles of M+ ions incorporated into said second inorganic electrochromic layer, y is the moles of T at the oxidation number n and z is the moles of X.
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Abstract
An electrochromic element useful in an electrochromic glass or mirror device and a process for making such element. The element is a five-layered structure including an electrolyte ion conducting layer interposed between first and second inorganic electrochromic layers which are interposed between a pair of conductive electrodes. The second inorganic electrochromic layer is amorphous. The first and second inorganic electrochromic layers are different and are capable of exhibiting color-forming properties complementary to one another upon the incorporation of at least one H, Li, Na, K, Ag, Cu or Tl ion. The electrolyte ion conducting layer may be a copolymer of ethylene oxide, butylene oxide or methyl glycidyl ether, and optionally a small amount of allyl glycidyl ether, along with an ionizable salt, or may be a polyurethane gel formed by reacting the copolymer with triisocyanate, along with an ionizable salt. The second inorganic electrochromic layer comprises a transition element chalconide or halide which exhibits a color change when shifting between the +2 and +3 valence states or between the +3 and +4 valence states. The second inorganic electrochromic layer may be produced by an electrochemical process, a chemical process, a physical process or by a solid state process. The electrochromic element may also comprise a plurality of five-layer structures in tandem, each pair separated by a substrate. The electrochromic element of the invention is also useful as a supercapacitor.
82 Citations
34 Claims
- 1. An electrochromic element comprising a pair of conductive electrodes at least one of which is transparent, first and second inorganic electrochromic layers interposed between said pair of conductive electrodes and an ion conducting layer of an electrolyte interposed between said first and second inorganic electrochromic layers, wherein said first and second inorganic electrochromic layers are different and are capable of exhibiting electrochromic properties upon the incorporation of at least one ion of an element selected from the group consisting of H, Li, Na, K, Ag, Cu and Tl, wherein said second inorganic electrochromic layer is amorphous, wherein the electrochromic properties of said first and second inorganic electrochromic layers are complementary, and wherein said second inorganic electrochromic layer comprises the composition
- space="preserve" listing-type="equation">M.sub.x T.sup.n.sub.y T.sup.n+m.sub.(uz-ny-x)/(n+m) X.sup.u.sub.z,
wherein x, y, z, u≧
0, 2≦
n≦
3, 1≦
m≧
2, n+m≦
4;
T is a fourth period transition element selected from Ni, Co, Mn, Cr, V, Ti or Fe;
M is at least one element selected from H, Li, Na, K, Ag, Cu and Tl;
X is selected from O, S, F and Cl;
n, n+m and u are oxidation numbers; and
x is the moles of M+ ions incorporated into said second inorganic electrochromic layer, y is the moles of T at the oxidation number n and z is the moles of X.- View Dependent Claims (2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 29, 30, 33, 34)
- 14. The element of claim 1, wherein X is O.
- 15. The element of claim 14, wherein M is Li.
- 16. The element of claim 1, wherein said M+ ions can be inserted into said second inorganic electrochromic layer by applying a voltage differential between said pair of conductive electrodes.
- 17. The element of claim 12, wherein said M+ ions can be inserted into said first inorganic electrochromic layer by applying a voltage differential between said pair of conductive electrodes.
- 18. An electrochromic device comprising the element of claim 7 interposed between a pair of transparent substrates.
- 19. The electrochromic device of claim 18, wherein said pair of transparent substrates are glass.
- 20. The electrochromic device of claim 18, wherein said pair of transparent substrates are plastic.
- 29. A process of manufacturing the device of claim 18, comprising:
-
sputtering a layer of a conductive electrode material on a first substrate; sputtering a layer of an inorganic electrochromic material onto said conductive electrode layer on said first substrate; sputtering a layer of a conductive electrode material on a second substrate; sputtering a layer of an amorphous inorganic electrochromic material onto said conductive electrode layer on said second substrate; and assembling an ion conducting layer of a solid polymeric electrolyte between the sputtered sides of said first and second substrates.
- 30. The process of claim 29, further comprising electrochemically processing at least one of said amorphous inorganic electrochromic material and said inorganic electrochromic material prior to assembling said ion conducting layer between said first and second substrates.
- 33. An electrochromic mirror device comprising the electrochromic element of claim 1, 2, or 3, interposed between a pair of substrates, wherein one of the conductive electrodes is reflective and the other is transparent.
- 34. An electrochromic device comprising a plurality of electrochromic elements as recited by claims 1, 2, or 3, in juxtaposed surface to surface relation, wherein a transparent substrate is interposed between each pair of electrochromic elements and the plurality of electrochromic elements are interposed between a pair of transparent substrates.
-
21. An electrochromic element comprising the following layers, in order:
- a first transparent conductive electrode;
a first inorganic electrochromic layer;
a first ion conducting layer of an electrolyte;
a first amorphous inorganic electrochromic counter electrode layer;
a second transparent conductive electrode, a transparent substrate;
a third transparent conductive electrode;
a second amorphous inorganic electrochromic counter-electrode layer;
a second ion conducting layer of an electrolyte;
a second inorganic electrochromic layer and a fourth conductive electrode which may be transparent or reflective;
wherein said first and second inorganic electrochromic layers are different from said first and second amorphous inorganic electrochromic counter electrode layers;
said first and second inorganic electrochromic layers and said first and second amorphous inorganic electrochromic counter electrode layers are capable of exhibiting electrochromic properties upon the incorporation of ions of at least one element selected from H, Li, Na, K, Ag, Cu and Tl; and
the electrochromic properties of said first and second inorganic electrochromic layers are complementary to the electrochromic properties of said first and second amorphous inorganic electrochromic counter electrode layers, and wherein at least one of said first and second inorganic electrochromic layers comprises the composition
space="preserve" listing-type="equation">M.sub.x T.sup.n.sub.y T.sup.n+m.sub.(uz-ny-x)/(n+m) X.sup.u.sub.z,wherein x, y, z, u≧
0, 2≦
n≦
3, 1≦
m≦
2, n+m≦
4;
T is a fourth period transition element selected from Ni, Co, Mn, Cr, V, Ti or Fe;
M is at least one element selected from H, Li, Na, K, Ag, Cu and Tl;
X is selected from O, S, F and Cl;
n, n+m and u are oxidation numbers; and
x is the moles of M+ ions incorporated into said first and second inorganic electrochromic layers, y is the moles of T at the oxidation number n and z is the moles of X. - View Dependent Claims (22, 31, 32)
- a first transparent conductive electrode;
-
23. An amorphous electrochromic material having the formula:
- Mx Tny Tn+m.sub.(uz-ny-x)/(n+m) Xuz, wherein x, y, z, u≧
0, 2≦
n≦
3, 1≦
m≦
2, n+m≦
4;
M is at least one element selected from H, Li, Na, K, Ag, Cu and Tl;
X is selected from O, S, F and Cl;
T is selected from Ni, Co, Mn, Cr, V, Ti and Fe;
n, n+m and u are oxidation numbers; and
x is the moles of M+ ions incorporated into the amorphous electrochromic material, y is the moles of T at the oxidation number n and z is the moles of X. - View Dependent Claims (24, 25, 28)
- Mx Tny Tn+m.sub.(uz-ny-x)/(n+m) Xuz, wherein x, y, z, u≧
-
26. A process for producing an amorphous electrochromic material comprising:
-
a first step of forming an original thin film consisting essentially of a mixture of TO, T(OH)2 and TOOH by sputtering a target comprising T with an O2 /H2 plasma; a second step of electrochemically processing the original thin film in alkali metal hydroxide solution to give a layer consisting essentially of TO and TOOH; a third step of electrochemically processing the layer consisting essentially of TO and TOOH in a liquid electrolyte comprising a polar solvent and an ionizable salt of a strong acid and an element selected from H, Li, Na, K, Ag, Cu and Tl, to incorporate xM+ ions into the layer consisting essentially of TO and TOOH to form an amorphous electrochromic material having the composition Mx Tny Tn+m.sub.(2z-ny-x)/(n+m) Oz ; wherein T is a transition element of the fourth period of the periodic table having an oxidation number ranging from 2 to 4 and is selected from Ni, Co, Mn, Cr, V, Ti and Fe;
n and n+m represent oxidation numbers; and
x, y and z represent moles.
-
-
27. A process for producing an amorphous electrochromic material comprising:
-
a first step of sputtering a target of M.sub.α
T1-α
O, wherein 0<
α
≦
1.0, to form a thin film which comprises M, Tn,Tn+m and O;a second step of electrochemically processing the thin film in a liquid electrolyte comprising a polar solvent and an ionizable salt of a strong acid and an element selected from H, Li, Na, K, Ag, Cu and Tl, to incorporate M+ ions in the thin film to form an amorphous electrochromic material having the composition Mx Tny Tn+m.sub.(2z-ny-x)/(n+m) Oz ; wherein T is a transition element of period four of the periodic table selected from Ni, Co, Mn, Cr, V, Ti and Fe;
n and n+m represent oxidation numbers and x, y and z represent moles.
-
Specification