Thin film ion conducting coating

• US 4,832,463 A
• Filed: 09/08/1987
• Issued: 05/23/1989
• Est. Priority Date: 09/08/1987
• Status: Expired due to Fees

• Current Assignee: Tufts University
• Original Assignee: Tufts University
• Inventors: Seward, George, Goldner, Ronald B., Haas, Terry, Wong, Kwok-Keung
• Primary Examiner(s): LaRoche, Eugene R.
• Assistant Examiner(s): McCutcheon, Nathan W.
• Application Number:
  US07/093,782
• Time in Patent Office: 623 Days
• Field of Search: 350/357, 350/355, 350/353
• US Class Current: 359/275
• CPC Class Codes: G02F 1/1525 characterised by a particular ion transporting layer, e.g. electrolyte
• CPC Class Codes: H01M 10/0562 Solid materials
• CPC Class Codes: H01M 6/185 with oxides, hydroxides or oxysalts as solid electrolytes
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02P 70/50 Manufacturing or production processes characterised by the final manufactured product

Abstract

Durable thin film ion conducting coatings are formed on a transparent glass substrate by the controlled deposition of the mixed oxides of lithium:tantalum or lithium:niobium. The coatings provide durable ion transport sources for thin film solid state storage batteries and electrochromic energy conservation devices.

Claims

1. An electronic device comprising:

a transparent substrate;

a first transparent electronically conductive layer on said substrate;

an electrochromic layer on said first transparent electrically conductive layer;

an ion conductive-electron resistive layer on said electrochromic layer, said ion conductive-electron resistive layer capable of transporting positive metal ions into said electrochromic layer to transform said electrochromic layer into said optically reflective state;

a counter-electrode layer on said ion conductive-electron resistive layer, said counter-electrode layer capable of storing and delivering electrons and ions to be transported into said electrochromic layer to transform said electrochromic layer into said optically reflective state; and

a second transparent electronically conductive layer on said counter-electrode layer, said first and second electrically conductive layers being adapted for connection with an external voltage source, whereby when voltage of a first polarity is applied across said first and second conductive layers said positive metal ions and said electrons are driven into said electrochromatic layer and when voltage of a second opposite polarity is applied across said first and second electrically conductive layers said positive metal ions and said electrons are removed from said electrochromic layer, said ion conductive-electron resistive layer comprising mixed metal oxides said mixed metal oxides layer including lithium oxide and at least one additional oxide selected from the group consisting of, tantalum oxide, and niobium oxide.

4. The electrochromic device of claim 1 wherein said first and second electrically conductive layers comprise indium oxide.

5. The electrochromic device of claim 1 wherein said counter-electrode layer is formed from a compound selected from the group consisting of tantalum oxide, niobium oxide, indium oxide and vanadium oxide.

6. The electrochromic device of claim 1 wherein said counter-electrode layer is selected from the group consisting of lithiated oxides of manganese, chromium, iron, cobalt and nickel, said counter-electrode being colored by removal of lithium and becoming bleached by addition of said lithium.

7. The electrochromic device of claim 1 wherein said transparent substrate comprises plastic or glass.

2. An electrochromic device comprising:

a transparent substrate;

a first transparent electronically conductive layer on said substrate;

an electrochromic layer on said first transparent electrically conductive layer;

an ion conductive-electron resistive layer on said electrochromic layer, said ion conductive-electron resistive layer capable of transporting positive metal ions into said electrochromic layer to transform said electrochromic layer into said optically reflective state;

a counter-electrode layer on said ion conductive-electron resistive layer, said counter-electrode layer capable of storing and delivering electrons and ions to be transported into said electrochromic layer to transform said electrochromic layer into said optically reflective state; and

a second transparent electronically conductive layer on said counter-electrode layer, said first and second electrically conductive layers being adapted for connection with an external voltage source, whereby when voltage of a first polarity is applied across said first and second conductive layers said positive metal ions and said electrons are driven into said electrochromic layer and when voltage of a second opposite polarity is applied across said first and second electrically conductive layers said positive metal ions and said electrons are removed from said electrochromic layer, said ion conductive-electron resistive layer comprising mixed metal oxides said mixed metal oxides layer including lithium oxide and at least one additional oxide selected from the group consisting of, boron oxide, magnesium oxide, calcium oxide, manganese oxide and zinc oxide.

3. An electrochromic device comprising:

a transparent substrate;

a first transparent electronically conductive layer on said substrate;

an electrochromic layer on said first transparent electrically conductive layer;

an ion conductive-electron resistive layer on said electrochromic layer, said ion conductive-electron resistive layer capable of transporting positive metal ions into said electrochromic layer to transform said electrochromic layer into said optically reflective state;

a counter-electrode layer on said ion conductive-electron resistive layer, said counter-electrode layer capable of storing and delivering electrons and ions to be transported into said electrochromic layer to transform said electrochromic layer into said optically reflective state; and

a second transparent electronically conductive layer on said counter-electrode layer, said first and second electrically conductive layers being adapted for connection with an external voltage source, whereby when voltage of a first polarity is applied across said first and second conductive layers said positive metal ions and said electrons are driven into said electrochromic layer and when voltage of a second opposite polarity is applied across said first and second electrically conductive layers said positive metal ions and said electrons are removed from said electrochromic layer, said ion conductive-electron resistive layer comprising mixed metal oxides said mixed metal oxides layer including lithium oxide and at least one additional oxide selected from the group consisting of, gallium oxide, tungsten oxide, molydbenum oxide, germanium oxide, strontium oxide, yttrium oxide and barium oxide.

8. A method of forming durable thin film electrical coatings comprising the steps of:

providing a transparent substrate within a deposition chamber;

depositing a layer of a transparent conductive coating on said transparent substrate;

depositing a layer of electrochromic material on said first conductive layer;

depositing a layer of ion conductive-electron resistive mixed-oxides on said electrochromic layer;

depositing a counter-electrode layer of electron conductive ion resistive material on said ion conductive-electron resistive layer;

depositing a layer of a transparent conductive coating on said electron conductive ion resistive layer said step of depositing a mixed-oxides layer comprising depositing a composition which includes lithium oxide in excess of stoichiometry.

9. The method of claim 8 wherein said mixed oxides are deposited by RF sputtering.

10. The method of claim 8 wherein

said mixed-oxides layer includes stoichiometric lithium oxide.

11. The method of claim 8 including the steps of:

depositing a quantity of lithium from lithium metal or lithium carbonate on said electrochromic layer to lithium-enrich said electrochromic layer; and

depositing said stoichiometric composition on said lithium enriched electrochromic layer.

12. A method of forming durable thin film electrical coatings comprising the steps of:

providing a transparent substrate within a deposition chamber;

depositing a layer of a transparent conductive coating on said transparent substrate;

depositing a layer of electrochromic material on said first conductive layer;

preparing mixed-oxides of lithium oxide and tantalum oxide in excess of stoichiometry

depositing said mixed-oxides simultaneously on said electrochromic layer to form an ion conductive-electron resistive layer;

depositing a counter-electrode layer of electron conductive ion resistive material on said ion conductive-electron resistive layer; and

depositing a layer of a transparent conductive coating on said electron conductive ion resistive layer.

13. A method of forming durable thin film electrical coatings comprising the steps of:

providing a transparent substrate within a deposition chamber;

depositing a layer of a transparent conductive coating on said transparent substrate;

depositing a layer of electrochromic material on said first conductive layer;

preparing mixed-oxides of lithium oxide and niobium oxide in excess of stoichiometry;

depositing said mixed-oxides simultaneously on said electrochromic layer;

depositing a counter-electrode layer of electron conductive ion resistive material on said ion conductive-electron resistive layer; and

depositing a layer of a transparent conductive coating on said electron conductive ion resistive layer.