Electrochemical device

• US 5,985,486 A
• Filed: 09/18/1997
• Issued: 11/16/1999
• Est. Priority Date: 09/18/1996
• Status: Expired due to Fees

• Current Assignee: Saint-Gobain Vitrage
• Original Assignee: Saint-Gobain Vitrage
• Inventors: Giron, Jean-Christophe
• Primary Examiner(s): Nuzzolillo, Maria
• Assistant Examiner(s): Martin, Angela J.
• Application Number:
  US08/933,141
• Time in Patent Office: 789 Days
• Field of Search: 429/188, 429/219, 429/231.9, 429/231.95, 429/233, 429/304, 429/30, 429/33
• US Class Current: 429/188
• CPC Class Codes: C03C 17/3417 all coatings being oxide coatings
• CPC Class Codes: E06B 9/24 Screens or other constructions affording protection against light, especially against sunshine; Similar screens for privacy or appearance; Slat blindsoperating, guiding or securing devices or arrangements for roll-type closures E06B9/56; free-hanging flexible screens A47H23/00
• CPC Class Codes: G01N 27/4074 for detection of gases other than oxygen
• 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 10/347 with solid electrolyte
• CPC Class Codes: H01M 6/181 with polymeric electrolytes
• CPC Class Codes: H01M 6/185 with oxides, hydroxides or oxysalts as solid electrolytes
• CPC Class Codes: H01M 6/505 Cells combined with indicating means for external visualization of the condition, e.g. by change of colour or of light intensity
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

The subject of the invention is an electrochemical device which includes at least one substrate (1, 7), at least one electronically conductive layer (2, 6), at least one electrochemically active layer capable of inserting ions reversibly, especially cations of the H⁺, Li⁺, Na⁺ and Ag⁺ type, and an electrolyte. This electrolyte (4) comprises at least one layer of essentially inorganic material, of the oxide type, the ionic conduction of which is generated or increased by incorporating a hydrogen-containing and/or nitrogen-containing, in particular nitride-containing, compound or compounds.

Claims

1. Electrochemical device which includes at least one substrate, at least one electronically conductive layer, at least one electrochemically active layer capable of inserting ions reversibly, in particular cations of H⁺, Li⁺, Na⁺ Ag⁺, and an electrolyte, characterized in that the electrolyte comprises at least one layer of essentially inorganic of the oxide type material of the oxide type, the ionic conduction of which is generated or increased by incorporating at least one of a hydrogen-containing and nitrogen-containing, and nitride-containing, compound or compounds.

2. Device according to claim 1, characterized in that the hydrogen-containing compound or compounds have at least one labile hydrogen atom H, bonded covalently or ionically to a carbon atom C, a nitrogen atom N, an oxygen atom O, a phosphorous atom P or a sulphur atom S.

3. Device according to claim 1, characterized in that the hydrogen-containing and/or nitrogen-containing compound (s) comprises/comprise at least one Br.o slashed.nsted-Lowry acid or a Br.o slashed.nsted-Lowry base.

4. Device according to claim 1, characterized in that the hydrogen-containing compound(s) comprises/comprise an organic compound having a hydroxyl, carboxylic, ketone/enol, aldehyde or hydroperoxide functional group.

5. Device according to claim 1, characterized in that the hydrogen-containing and/or nitrogen-containing compound or compounds comprises/comprise nitrogen, in particular in the form of amine, imine, hydrazine, N₂ O or ammonia NH₃.

6. Device according to claim 1, characterized in that the hydrogen-containing compound or compounds comprises/comprise water H₂ O or hydrogen peroxide H₂ O₂.

7. Device according to claim 6, characterized in that the hydrogen-containing compound is water H₂ O, in particular incorporated in the form of water of adsorption and/or water of constitution of the oxide or of the mixture of oxides of which the layer of the electrolyte is composed.

8. Device according to claim 1, characterized in that the layer having a hydrogen-containing and/or nitrogen-containing compound or compounds is based on a chalcogenide of transition, alkali, alkaline-earth or rare-earth metals.

9. Device according to claim 1, characterized in that the layer having a hydrogen-containing and/or nitrogen-containing compound or compounds is based on at least one oxide belonging to the family of oxides of transition metals, especially those of Groups IVB and VB of the Periodic Table and/or Groups IVA and VA of the Periodic Table, especially of the type comprising chromium oxide, indium oxide, thorium oxide, zirconium oxide, hafnium oxide, antimony oxide, tantalum oxide, titanium oxide, germanium oxide, silicon oxide and mixed oxides of these metals, such as a tantalum/titanium mixed oxide, or a mixed oxide of one of these metals with a metal oxide exhibiting properties of reversible ion insertion of the electrochromic type.

10. Device according to claim 1, characterized in that the layer having a hydrogen-containing and/or nitrogen-containing compound or compounds is based on aluminosilicates of the mica or feldspar type.

11. Device according to claim 1, characterized in that the layer having a hydrogen-containing and/or nitrogen-containing compound or compounds is based on a heteropolyacid of the acid phosphate type, especially of the Zno(H₃ PO₄)₂.nH₂ O type.

12. Device according to claim 1, characterized in that the layer having a hydrogen-containing and/or nitrogen-containing compound or compounds is based on an ionically conductive material capable of inserting protons reversibly but whose overall oxidation state is maintained essentially constant, which includes in particular at least one of the following compounds:

the oxides of tungsten W, of niobium Nb, of tin Sn, of bismuth Bi, of vanadium Va, of nickel Ni and of iridium Ir, and comprising, optionally, an additional metal such as titanium, tantalum or rhenium.

13. Device according to claim 1, characterized in that the layer having a hydrogen-containing and/or nitrogen-containing compound or compounds is based on a material capable of inserting lithium ions Li⁺ reversibly but whose oxidation state is maintained essentially constant, in particular one based on at least one metal oxide which may or may not be lithiated, such as nickel oxide NiO_x, lithiated nickel oxide LiNiO_x, a mixture of titanium and cerium oxides Ce/TiO_x, and the oxides of tungsten W, niobium Nb, vanadium Va and iridium Ir.

14. Device according to claim 1, characterized in that the layer having a hydrogen-containing and/or nitrogen-containing compound or compounds is in the form of a hydrated oxide or of an oxynitride which may or may not be hydrated, optionally also containing a halogen of the fluorine type, especially of the hydrated tantalum oxide, hydrated antimony oxide or hydrated mixed tantalum/tungsten oxide or hydrated mixed antimony/tungsten oxide type.

15. Device according to claim 1, characterized in that the layer having a hydrogen-containing and/or nitrogen-containing compound or compounds is electronically insulating.

16. Device according to claim 1, characterized in that the electrolyte is a multilayer stack which includes, in addition to the layer having a hydrogen-containing and/or nitrogen-containing compound or compounds, at least one other layer of an essentially inorganic material.

17. Device according to claim 1, characterized in that the electrolyte is a multilayer stack comprising at least two layers having a hydrogen-containing and/or nitrogen-containing compound or compounds, especially in the form of a (hydrated Ta₂ O₅ /hydrated Sb₂ O₅)n sequence where n>

0.

18. Electrochemical device according to claim 1, characterized in that the electrolyte is a multilayer electrolyte, the latter and preferably all of the layers of the said device containing only layers of solid material, especially an electrolyte of the WO₃ /(Ta₂ O₅ or Sb₂ O₅) or (nickel oxide/WO₃) or (SnO₂ /Ta₂ O₅), (SnO₂ /Sb₂ O₅), (NiO_x /Ta₂ O₅) or (Nio_x /Sb₂ O₅) type, at least one of these oxides containing hydrogen and/or nitrogen.

19. Device according claim 1, characterized in that the electrolyte is a multilayer stack which also includes a layer of an ionically conductive material chosen in the form of an anhydrous or aqueous liquid or a liquid based on a gel or gels, or on a polymer or polymers, especially an electrolyte of the (layer having a hydrogen-containing and/or nitrogen-containing compound or compounds/POE:

H₃ PO₄) type.

20. Device according to claim 1, characterized in that at least one of the electrochemically active layers, especially that exhibiting cathodic colouring electrochromic properties, of the WO₃ type, is pre-inserted with cations, especially with protons, while it is being formed.

21. Electrochromic window, characterized in that it includes the electrochemical device according to claim 1, having in particular a variable light and/or energy transmission, with the transparent substrate or all the transparent substrates made of glass or plastic, preferably fitted into multiple glazing and/or laminated glass.

22. Energy storage element, characterized in that it includes the electrochemical device according to claim 1.

23. Gas sensor, characterized in that it includes the electrochemical device according to claim 1.

24. Process for manufacturing an electrochemical device according to claim 1, characterized in that the layer having a hydrogen-containing and/or nitrogen-containing compound or compounds of the electrolyte is deposited using a vacuum technique of the sputtering, evaporation or plasma CVD type or using synthesis via a sol-gel route, especially of the dipping, spray-coating or roll-coating type, or else liquid-phase or pulverulent-phase or gas-phase pyrolysis.

25. Process according to claim 24, characterized in that the layer having a hydrogen-containing and/or nitrogen-containing compound or compounds is deposited using reactive sputtering in an atmosphere containing the hydrogen-containing and/or nitrogen-containing compounds, or the "precursors" of the said compounds, especially, in the case of an electrolyte in the form of a hydrated oxide, in an atmosphere containing H₂ O or an H₂ /O₂ mixture or else an N₂ O/H₂ mixture;

and, in the case of an electrolyte in the form of a nitride-containing oxide, in an atmosphere containing NH₃.

26. Process according to claim 24, characterized in that the layer having a hydrogen-containing and/or nitrogen-containing compound or compounds is deposited using thermal evaporation, optionally assisted by an electron beam, the hydrogen-containing and/or nitrogen-containing compounds or their "precursors" being introduced into the layer in gaseous form and/or being contained in the material intended to be evaporated.

27. Process according to claim 24, characterized in that the layer having a hydrogen-containing and/or nitrogen-containing compound or compounds is deposited by synthesis via a sol-gel route, by controlling the content of hydrogen-containing and/or nitrogen-containing compound or compounds of the layer by the choice of the composition of the solution, the atmosphere during deposition and/or the temperature of deposition/temperature of curing of the layer.

28. Process according to claim 24, characterized in that at least one of the electrochemically active layers is deposited using a vacuum technique, especially using reactive sputtering under conditions allowing its pre-insertion, during its deposition, with cations.

29. Use of the electrochromic window according to claim 21 as a window for a building, a window for a motor vehicle, a window for industrial or public-transport vehicles, a railway window, an aircraft window, rear-view mirrors and other mirrors, as optical components such as camera lenses, as the front face or element to be arranged on the front face of display screens of appliances such as computers or televisions.

30. Use of the energy storage element according to claim 22 in appliances involving electronic and/or computing means and in appliances requiring an energy storage device which is specific to them, autonomous or not, especially computers, televisions or telephones.

31. The electrochemical device according to claim 1 further comprising at least one seal made of epoxy resin.

32. The electrochromic window according to claim 21 having a laminated structure of one of a first and second type structure wherein said first type structure comprises, in order, a first rigid substrate, a functional stack, a polymer insert and a second rigid substrate and wherein said second type are layers of the polyethylene terephthalate (PET) type.

33. The electrochromic window according to claim 32, wherein said first and second rigid substrate comprises one of glass and polycarbonate and wherein said polymer insert is one of polyurethane, polyvinyl butyral and ethylene vinyl acetate, with preferably the following, in order, composition of glass, a functional stack, ethylene vinyl acetate or polyurethane and a second glass.