Electrochromic elements, materials for use in such element, processes for making such elements 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 an alkali metal or Ag ion, 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 TII and TIII are divalent and trivalent forms of a transition metal T;
M is selected from the group consisting of an alkali metal, Ag, a mixture of alkali metals, a mixture of at least one alkali metal and Ag, a mixture of Ag and hydrogen, a mixture of at least one alkali metal and hydrogen and a mixture of at least one alkali metal with Ag and hydrogen;
x is a first mole fraction of M+ ions and y is a second mole fraction of M+ ions incorporated into said second inorganic electrochromic layer such as 0<
x≦
1.0, -x≦
y≦
+x and y≧
2x-1; and
wherein the composition undergoes a maximum transmissitivity change when y varies between -x and +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 first and second inorganic electrochromic layers are different and are capable of exhibiting color-forming properties complementary to one another upon the incorporation of an alkali metal or Ag ion, a mixture of alkali metal or Ag ions or a mixture of alkali metal or Ag and hydrogen ions. 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 forming by reacting the copolymer with triisocyanate, along with an ionizable salt. The second inorganic electrochromic layer comprises a transition metal oxide which exhibits a color change when shifting between the +2 and +3 valence states. The second inorganic electrochromic layer may be produced by an electrochemical process, a chemical process, or by a physical process. The electrochromic element may also comprise a plurality of five-layer structure in tandem, each pair separated by a substrate.
75 Citations
36 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 an alkali metal or Ag ion, 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+y T.sup.II.sub.1-2x+y T.sup.III.sub.x-y O,
wherein TII and TIII are divalent and trivalent forms of a transition metal T;
M is selected from the group consisting of an alkali metal, Ag, a mixture of alkali metals, a mixture of at least one alkali metal and Ag, a mixture of Ag and hydrogen, a mixture of at least one alkali metal and hydrogen and a mixture of at least one alkali metal with Ag and hydrogen;
x is a first mole fraction of M+ ions and y is a second mole fraction of M+ ions incorporated into said second inorganic electrochromic layer such as 0<
x≦
1.0, -x≦
y≦
+x and y≧
2x-1; and
wherein the composition undergoes a maximum transmissitivity change when y varies between -x and +x.- View Dependent Claims (2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25)
-
26. 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 inorganic electrochromic counter electrode layer;
a second transparent conductive electrode, a transparent substrate;
a third transparent conductive electrode;
a second 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 inorganic electrochromic counter electrode layers;
said first and second inorganic electrochromic layers and said first and second inorganic electrochromic counter electrode layers are capable of exhibiting electrochromic properties upon the incorporation of an alkali metal or Ag ion, a mixture of alkali metal or Ag and hydrogen ions, or a mixture of alkali metal or Ag ions;
wherein the electrochromic properties of said first and second inorganic electrochromic layers are complementary to the electrochromic properties of said first and second inorganic electrochromic counter electrode layers, and wherein at least one of said first and second inorganic electrochromic counter electrode layers comprises the composition
space="preserve" listing-type="equation">M.sub.x+y T.sup.II.sub.1-2x+y T.sup.III.sub.x-y O,wherein TII and TIII are divalent and trivalent forms of a transition metal T;
M is selected from the group consisting of an alkali metal, Ag, a mixture of alkali metals, a mixture of at least one alkali metal and Ag, a mixture of Ag and hydrogen, a mixture of at least one alkali metal and hydrogen and a mixture of at least one alkali metal with Ag and hydrogen;
x is a first mole fraction of M+ ions and y is a second mole fraction of M+ ions incorporated into said first and second inorganic electrochromic counter electrode layers such that 0<
x≦
1.0, -x≦
y≦
+x and y≧
2x-1; and
wherein the composition undergoes a maximum transmissivity change when y varies between -x and +x. - View Dependent Claims (27, 28)
- a first transparent conductive electrode;
-
29. An electrochromic material having the formula:
- Mx+y TII1-2x+y TIIIx-y O, wherein M is selected from the group consisting of an alkali metal, Ag, a mixture of alkali metals, a mixture of at least one alkali metal and Ag, a mixture of Ag and hydrogen, a mixture of at least one alkali metal and hydrogen and a mixture of at least one alkali metal with Ag and hydrogen;
TII and TIII are divalent and trivalent forms of a transition metal T;
x is a first mole fraction of M+ ions and y is a second mole fraction of M+ ions incorporated into the electrochromic material such that O<
x≦
1.0, -x<
y<
+x and y>
2x-1; and
wherein said electrochromic material undergoes a maximum transmissivity change when y varies between -x and +x. - View Dependent Claims (30, 31)
- Mx+y TII1-2x+y TIIIx-y O, wherein M is selected from the group consisting of an alkali metal, Ag, a mixture of alkali metals, a mixture of at least one alkali metal and Ag, a mixture of Ag and hydrogen, a mixture of at least one alkali metal and hydrogen and a mixture of at least one alkali metal with Ag and hydrogen;
-
32. A process for producing an 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 a basic 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 a member selected from the group consisting of an alkali metal, Ag, a mixture of alkali metals and a mixture of at least one alkali metal with Ag, to incorporate (x+y) cations from the ionizable salt into the layer consisting essentially of TO and TOOH to form an electrochromic material having the composition Mx+y TII1-2x+y TIIIx-y O; wherein T is a transition metal selected from Ni, Co, Mn and Fe;
M is selected from the group consisting of an alkali metal, Ag, a mixture of alkali metals, a mixture of at least one alkali metal and Ag, a mixture of Ag and hydrogen, a mixture of at least one alkali metal and hydrogen and a mixture of at least one alkali metal with Ag and hydrogen;
TII and TIII are divalent and trivalent forms of transition metal T and x and y are mole fractions such that 0<
x≦
1.0, -x≦
y≦
x and y≧
2x-1.
-
-
33. A process for producing an electrochromic material comprising:
-
a first step of sputtering a target of M.sub.α
T1-α
O, wherein O<
α
≦
1.0, to form a thin film of Mm TnII TpIII O, m, n and p being mole fractions;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 a member selected from the group consisting of an alkali metal, Ag, a mixture of alkali metals and a mixture of at least one alkali metal with Ag, to incorporate (x+y) cations from the ionizable salt into the thin film to form an electrochromic material having the composition Mx+y TII1-2x+y TIIIx-y O; wherein T is a transition metal selected from Ni, Co, Mn and Fe;
TII and TIII are divalent and trivalent forms of transition metal T;
M is selected from the group consisting of an alkali metal, Ag, a mixture of alkali metals, and a mixture of at least one alkali metal and Ag; and
x and y are mole fractions such that 0<
x≦
1.0, -x≦
y≦
x and y≧
2x-1.
-
-
34. An electrochromic material having the formula Mx+y TII1-2x+y TIIIx-y O, wherein TII and TIII are divalent and trivalent forms of a transition metal T;
- M is selected from the group consisting of an alkali metal, Ag, a mixture of alkali metals and a mixture of at least one alkali metal and Ag;
x and y are a first mole fraction and a second mole fraction of M+ ions incorporated into the electrochromic material such that 0<
x≦
1.0, -x<
y<
x and y<
2x-1; and
wherein said electrochromic material undergoes a maximum transmissivity change when y varies between -x and +x. - View Dependent Claims (35)
- M is selected from the group consisting of an alkali metal, Ag, a mixture of alkali metals and a mixture of at least one alkali metal and Ag;
-
36. 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 an alkali metal or Ag ion, wherein the electrochromic properties of said first and second inorganic electrochromic layers are complementary and wherein the second inorganic electrochromic layer comprises an electrochromic material having the formula Mx+y TII1-2x+y TIIIx-y O, wherein TII and TIII are divalent and trivalent forms of a transition metal T, M is selected from the group consisting of an alkali metal, Ag, a mixture of alkali metals and a mixture of at least one alkali metal and Ag, x and y are a first mole fraction and a second mole fraction of M+ ions incorporated into the electrochromic material such that 0<
- x<
1.0, -x≦
y≦
x and y≧
2x-1, said electrochromic material undergoing a maximum transmissivity change when y varies between -x and +x.
- x<
Specification