Electrochemical device

• US 6,277,523 B1
• Filed: 03/27/1997
• Issued: 08/21/2001
• Est. Priority Date: 03/27/1996
• Status: Expired due to Term

• Current Assignee: Saint-Gobain Vitrage
• Original Assignee: Saint-Gobain Vitrage
• Inventors: Giron, Jean-Christophe
• Primary Examiner(s): Chaney, Carol
• Assistant Examiner(s): Ruthkosky, Mark
• Application Number:
  US08/825,100
• Time in Patent Office: 1,608 Days
• Field of Search: 429/192, 429/304, 429/33
• US Class Current: 429/304
• CPC Class Codes: C03C 17/3417 all coatings being oxide coatings
• CPC Class Codes: G02F 1/1525 characterised by a particular ion transporting layer, e.g. electrolyte
• CPC Class Codes: G02F 2001/1536 additional, e.g. protective, layer inside the cell
• CPC Class Codes: G02F 2001/1555 Counter electrode
• CPC Class Codes: Y10T 29/49115 including coating or impregnating

Abstract

An all solid electrochemical device comprising at least one substrate (1,7), at least one electroconductive layer (2,6) at least one electrochemically active layer (3,5) capable of reversibly injecting ions, and an electrolyte (4), wherein the electrolyte (4) is a layer or an inorganic, multilayer stack comprising at least one layer (4b) made of an tonically conductive material capable of reversibly injecting said ions but whose overall degree of oxidation is maintained essentially constant.

Claims

1. An electrochemical device, comprising:

at least one substrate (1,7), at least one electroconductive layer (2,6), at least one electrochemically active layer (3,5) capable of reversibly inserting ions, and an electrolyte (4), wherein the electrolyte (4) is a layer or a multilayer stack of inorganic material(s) comprising at least an electron insulating layer and an inhibited electrochromic layer whose overall degree of oxidation is maintained constant and which exists in a decolored or a slightly colored state, wherein all the layers of the device are formed of solid materials.

2. The electrochemical device according to claim 1, wherein said inserted ions are H⁺, Li⁺, Na⁺, Ag⁺ or K⁺.

3. The electrochemical device according to claim 1, wherein the overall degree of oxidation of the layer (4b) of the electrolyte (4) is maintained essentially constant by electrically insulating the said layer (4b) from at least one of the electron sources of the device by interposing at least one layer (4a, 4d) of an electronically insulating material.

4. The electrochemical device according to claim 3, wherein the layer(s) (4a,4d) made of electronically insulating material is ionically conductive/ion-permeable.

5. The electrochemical device according to claim 4, wherein the layer(s) (4a,4d) made of electronically insulating material forms part of the multilayer electrolyte (4) in direct contact with at least one of the faces of the layer (4b) having an overall degree of oxidation maintained essentially constant.

6. The electrochemical device according to claim 1, wherein the overall degree of oxidation of the layer (4b) of the electrolyte (4) is maintained essentially constant by keeping the potential of said layer (4b) at values outside the range of potentials causing a variation in the degree of ion insertion of the material of which it is composed.

7. The electrochemical device according to claim 1, which comprises:

in succession, an electroconductive layer (2), an electrochemically active layer (3) capable of reversibly inserting cations, the electrolyte (4) comprising layer (4b) made of ionically conductive material capable of reversibly inserting the cations but whose overall degree of oxidation is maintained essentially constant, and optionally at least one electronically insulating layer (4a,4c), a second electrochemically active layer (5) capable of reversibly inserting cations, and an electroconductive layer (6).

8. The electrochemical device according to claim 7, wherein said layer (3) is a cathodic electrochromic material and said layer (5) is of an anodic electrochromic material.

9. The electrochemical device according to claim 1, wherein the material of layer (4b), which is capable of reversibly inserting the ions but whose degree of oxidation is maintained essentially constant, is a material exhibiting an electrochromic property.

10. The electrochemical device according to claim 7, wherein the material of layer (4b) is maintained in the decolored state or in an intermediate state of coloration.

11. The electrochemical device according to claim 1, which operates by reversible insertion of protons from the electrochemically active layer or layers (3,5) and in that the material of the layer (4b) of the electrolyte (4), which is capable of reversibly inserting protons, but whose degree of oxidation is maintained essentially constant, is based on a metal oxide or a mixture of metal oxides, optionally hydrated, and selected especially from the group consisting of tungsten oxide, optionally hydrated, WO₃.nH₂O, niobium oxide, optionally hydrated, Nb₂O₅.nH₂O, nickel oxide, optionally hydrated, NiO_xH_y.nH₂O, tin oxide, optionally hydrated, SnO₂.nH₂O, bismuth oxide, optionally hydrated, Bi₂O₃.nH₂O, titanium oxide, optionally hydrated, TiO₂.nH₂O, vanadium oxide, optionally hydrated V₂O₅.nH₂O, molybdenum oxide, optionally hydrated, MoO₃.nH₂O₄ where n≧

2 and optionally comprising an additive metal, which can be hydrated, of titanium, tantalum, or rhenium.

12. The electrochemical device according to claim 1, which operates by reversible insertion of lithium ions Li⁺ from the electrochemically active layer or layers (3,5), the material of said layer (4b) of the electrolyte (4), which is capable of reversibly inserting lithium ions Li⁺ but whose degree of oxidation is maintained essentially constant, being based on a metal oxide or a mixture of metal oxides, which optionally are lithiated, selected from the group consisting of nickel oxide, lithiated nickel oxide, a mixture of titanium and cerium oxides, tungsten oxide, niobium oxide, vanadium oxide and lithiated vanadium oxide.

13. The electrochemical device according to claim 3, wherein the layer or layers (4a,4d) of electronically insulating material includes at least one oxide of a metal of column VB of the Periodic Table and at least one metal oxide selected from the group consisting of antimony oxide Sb₂O₅, zirconium oxide ZrO₂, titanium oxide TiO₂, silicon oxide SiO₂, chromium oxide CrO₃, these oxides being optionally hydrated and optionally comprising a hydratable metal additive of W, Re or an alkali metal.

14. The electrochemical device of claim 13, wherein said metal oxide is a mixed Ta—

Ti oxide, GeO₃ or ZnO(H₃PO₄)₂.nH₂O.

15. The electrochemical device according to claim 3, wherein the layer(s) (4a, 4c) of electronically insulating material is selected from the group consisting of CeF₃, hexa-uranylphosphate, MgF₂, CaF₂, SiO_x, LiF, Na₃AlF₆, Li₃N, LiTaO₃, LiAlF₄, Li₃PO₄, LiPO₂, LiN, LiNbO₃, MgF₂POLi and Li₂WO₄, said device operating by reversible insertion of lithium ions from the electrochemically active layer or layers (3,5).

16. The electrochemical device according to claim 1, wherein the materials which form the layer (4b) are capable of reversibly inserting the ions but whose degree of oxidation is maintained essentially constant and the materials forming the layer(s) (4a,4d), made of electronically insulating material, are nitrided, phosphatized or both nitrided and phosphatized.

17. The electrochemical device according to claim 4, wherein the layer(s) (4a,4d) of electronically insulating oxide material is a material whose electrical insulation properties are obtained by blocking its ability to insert ions by controlling its potential.

18. The electrochemical device according to claim 1, wherein the electrochemically active layer(s) comprises a layer (3) of anodic electrochromic material comprising a transition metal chalcogenide containing an ion which undergoes reversible injection.

19. The electrochemical device according to claim 18, wherein said chalcogenide is S, O or Se.

20. The electrochemical device according to claim 1, wherein at least one of the electroconductive layer(s) (2,6) comprises (i) at least one doped metal oxide selected from the group consisting of ITO and SnO₂:

F, (ii) gold, silver or aluminum, (iii) Ni—

Cr alloy or (iv) several superposed layers of these materials.

21. The electrochemical device according to claim 1, wherein the multilayer electrolyte (4) and all of the layers of the said device contain only layers of solid material.

22. A display element of the information screen or advertising panel type, comprising:

a plurality of juxtaposed electrochemical devices according to claim 1.

23. A energy storage element, comprising the electrochemical device according to claim 1.

24. The electrochemical device according to claim 1, wherein the electrochemically active layer(s) of the device which operates by reversible insertion of lithium ions Li⁺ or protons comprises a layer (5) of cathodic electrochromic material selected from the group consisting of tungsten oxide WO₃, molybdenum oxide MoO₃, vanadium oxide V₂O₅, niobium oxide Nb₂O₅, titanium oxide TiO₂, a cermet material of the WO₃/Au or WO₃/Ag type, a mixture of tungsten and rhenium oxides WO₃/ReO₃, and phosphotungstic acid, metallophthalocyanines or metallodibenzophthalocyanines of transition metals or of rare earth metals, which are optionally nitrided.

25. The electrochemical device according to claim 1, wherein the electrochemically active layer(s) (3,5) of the device which operates by reversible insertion of protons H⁺ comprises a layer (5) of cathodic electrochromic material selected from the group consisting of tungsten oxide WO₃, molybdenum oxide MoO₃, vanadium oxide V₂O₅, niobium oxide Nb₂O₅, titanium oxide TiO₂, a cermet material of the WO₃/Au or WO₃/Ag type, a mixture of tungsten and rhenium oxides WO₃/ReO₃, and phosphotungstic acid, metallophthalocyanines or metallodibenzophthalocyanines of transition metals or of rare earth metals, which are optionally nitrided or hydrated.

31. The electrochemical device according to claim 1, wherein the electrochemically active layer(s) comprises a layer (3) of anodic electrochromic material, with respect to the reversible insertion of protons, is selected from the group consisting of lithiated nickel oxide, hydrogenated iridium oxide, hydrogenated, nitrided iridium oxide, nickel oxide, hydrogenated nickel oxide, hydrogenated, nitrided nickel oxide, rhodium oxide, cobalt oxide, chromium oxide, manganese oxide, and a hydride of a rare earth, of a lanthanide or of transition metals, and hexacyanometalates of formula M[M′

(CN₆)], with M and M′

being transition metals and/or rare earths.

32. The electrochemical device according to claim 1, wherein the electrochemically active layer(s) comprises a layer (3) of anodic electrochromic material, with respect to the reversible insertion of lithium ions Li⁺, is selected from the group consisting of nickel oxide, manganese oxide, iridium oxide, nickel oxide, cerium oxide, titanium oxide, cerium oxide-titanium oxide, rhodium oxide, cobalt oxide, chromium oxide, vanadium oxide, rhenium oxide, platinum oxide, iron oxide, osmium oxide, copper oxide and praseodymium oxide, these compounds being optionally lithiated, nitrided or a combination thereof, and a hexacyanometalate of formula M[M′

(CN₆)], with M and M′

being transition metals and/or rare earths.

34. The electrochemical device according to claim 1, wherein said multilayer stack is an all-solid split electrolyte of at least two layers of hydrogenated and hydrated nickel oxide/hydrated tungsten oxide or of at least two layers of hydrated tantalum oxide/hydrated tungsten oxide.

26. An electrochemical device, comprising:

at least one substrate (1,7), at least one electroconductive layer (2,6), at least one electrochemically active layer (3,5) capable of reversibly inserting ions, and an electrolyte (4), wherein the electrolyte (4) is a layer or a multilayer stack of solid inorganic materials comprising at least an electron insulating layer and an inhibited electrochromic layer of WO₃, Nb₂O₃, SnO₂, Bi₂O₃, TiO₂, V₂O₅, hydrogenated nickel oxide or MoO₃ material which exists in a decolored or only slightly colored state and whose overall degree of oxidation is maintained constant, wherein all the layers of the device are formed of solid materials.

27. The electrochemical device according to claim 26, wherein said electrolyte stack is a two layer stack of a Ta₂O₅.nH₂O layer and a WO₃.nH₂O layer.

28. The electrochemical device according to claim 26, wherein said electrolyte stack is a three layer stack of a Ta₂O₅.nH₂O layer, a WO₃.nH₂O layer and a Ta₂O₅.nH₂O layer.

29. The electrochemical device according to claim 26, wherein said electrolyte layer is a single layer of WO₃.nH₂O.

30. The electrochemical device according to claim 26, wherein said electrolyte layer comprises a layer of an electron insulating layer and an inhibited electrochromic layer of WO₃.nH₂O.

33. The electrochemical device according to claim 26, wherein said electrolyte is a multilayer stack of at least two layers of hydrogenated and hydrated nickel oxide/hydrated tungsten oxide or of at least two layers of hydrated tantalum oxide/hydrated tungsten oxide.

35. The electrochemical device according to claim 26, wherein said multilayer stack is an all-solid split electrolyte of at least two layers of hydrogenated and hydrated nickel oxide/hydrated tungsten oxide or of at least two layers of hydrated tantalum oxide/hydrated tungsten oxide.