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Title:
ELECTROCHROMIC MEDIA WITH CONCENTRATION-ENHANCED STABILITY, PROCESS FOR THE PREPARATION THEREOF AND USE IN ELECTROCHROMIC DEVICES
Document Type and Number:
WIPO Patent Application WO/2000/066679
Kind Code:
A2
Abstract:
Increased stability of electrochromic devices containing an electrochromic medium having two or more electroactive compounds is accomplished by establishing current limiting concentrations of electroactive compounds with the larger redox potential difference. A process for production of electrochromic devices uses targeted concentrations of electroactive materials during preparation of the electrochromic medium which results in substantially no devices being produced wherein the current is limited by an electroactive compound having a low redox potential difference.

Inventors:
GUARR THOMAS F
THEISTE DAVID A
CAMMENGA DAVID J
ANDERSON JOHN S
Application Number:
PCT/US2000/011813
Publication Date:
November 09, 2000
Filing Date:
April 28, 2000
Export Citation:
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Assignee:
GENTEX CORP (US)
International Classes:
C09K9/02; G02B5/23; G02F1/1503; (IPC1-7): C09K9/00
Domestic Patent References:
WO1998044386A11998-10-08
WO1998044384A11998-10-08
WO1997034186A11997-09-18
Foreign References:
EP0612826A11994-08-31
Other References:
USHAKOV O A ET AL: "CALCULATION OF STEADY-STATE ELECTROCOLORATION PARAMETERS OF ELECTROCHROMIC SYSTEMS" SOV ELECTROCHEM JUL 1985, vol. 21, no. 7, July 1985 (1985-07), pages 857-860, XP002146912
Attorney, Agent or Firm:
Factor, Jody L. (LLC Suite 100 17 West 10th Street Holland, MI, US)
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Claims:
WHAT IS CLAIMED IS:
1. An electrochromic medium, comprising: a) a solvent b) an anodic electroactive material which exhibits at least two chemically reversible waves in a cyclic voltammogram in said solvent at room temperature, c) a cathodic electroactive material which exhibits at least two chemically reversible waves in a cyclic voltammogram in said solvent at room temperature; wherein at least one of said electroactive materials is electrochromic, and wherein the electroactive material having the smaller potential difference between the chemically reversible waves has a concentration in the electrochromic medium greater than that required to achieve a balanced concentration.
2. The electrochromic medium of claim 1, comprising two electroactive materials, both of which are electrochromic.
3. The electrochromic medium of claim 1, comprising at least three electroactive materials, at least two of which are electrochromic.
4. The electrochromic medium of claim 3, wherein at least three electrochromic materials are present.
5. The electrochromic medium of claim 1, wherein said solvent is contained in a gel or a swellable polymer.
6. The electrochromic medium of claim 1, wherein said anodic electroactive materials are 5,10dihydrophenazines.
7. The electrochromic medium of claim 1, wherein said cathodic electroactive materials are bipyridinium salts.
8. The electrochromic medium of claim 1, wherein said electroactive material having the smaller potential difference between the chemically reversible waves has a concentration in the electrochromic medium which is greater by 3 equivalent percent or more over the balanced concentration.
9. The electrochromic medium of claim 1, wherein said electroactive material having the smaller potential difference between the chemically reversible waves has a concentration in the electrochromic medium which is greater by 5 equivalent percent or more over the balanced concentration.
10. An electrochromic medium comprising a) an anodic electroactive material, b) a cathodic electroactive material, wherein at least one of said electroactive materials is electrochromic, wherein one of said electroactive materials has only one electrochemically activated state, and wherein a second electroactive material has at least two chemically electrochemically activated states, and wherein the electroactive material with at least two electrochemically activated states has a concentration in the electrochromic medium greater than that required to achieve a balanced concentration.
11. The electrochromic medium of claim 10, wherein said electrochemical medium comprises at least one electroactive material having at least two chemically reversible waves in a cyclic voltammogram.
12. The electrochromic medium of claim 10, wherein said electroactive material with at least two activated states is present in said electrochromic medium in a concentration which is greater by 3 equivalent percent or more over the balanced concentration.
13. The electrochromic medium of claim 10, wherein said electroactive material with at least two activated states is present in said electrochromic medium in a concentration which is greater by 5 equivalent percent or more over the balanced concentration.
14. An electrochromic medium, comprising: a) an anodic electroactive material, b) a cathodic electroactive material, wherein one of said anodic electroactive material (s) and said cathodic electroactive material (s) has an electrochemically activated state which exhibits greater reactivity than the electrochemically activated state of other of said electroactive materials, wherein the electroactive material exhibiting said greater reactivity is present in concentration greater than that required to achieve a balanced concentration.
15. The electrochromic medium of claim 14, wherein said anodic electroactive material has an electrochemically activated state which exhibits the greater reactivity, and said anodic electroactive material is present in a concentration greater than that required to achieve a balanced concentration.
16. The electrochromic medium of claim 14, wherein said cathodic electroactive material has an electrochemically activated state which exhibits the greater reactivity, and said cathodic electroactive material is present in a concentration greater than that required to achieve a balanced concentration.
17. The electrochromic medium of claim 14, wherein said electroactive material which exhibits greater reactivity is present in a concentration of 3 equivalent percent or more greater than the balanced concentration.
18. The electrochromic medium of claim 14, wherein said electroactive material which exhibits greater reactivity is present in a concentration of 5 equivalent percent or more greater than the balanced concentration.
19. An electrochromic device comprising front and rear spaced elements each having front and rear surfaces, said rear surface of said front element having a transparent conductive material disposed thereon, said front surface of said rear element having a conductive material disposed thereon or said rear element itself being conductive, wherein said front and rear elements are sealably bonded together in a spaced apart relationship to define a cavity, where said cavity contains the electrochromic medium of claim 1.
20. An electrochromic device comprising front and rear spaced elements each having front and rear surfaces, said rear surface of said front element having a transparent conductive material disposed thereon, said front surface of said rear element having a conductive material disposed thereon or said rear element itself being conductive, wherein said front and rear elements are sealably bonded together in a spaced apart relationship to define a cavity, where said cavity contains the electrochromic medium of claim 2.
21. An electrochromic device comprising front and rear spaced elements each having front and rear surfaces, said rear surface of said front element having a transparent conductive material disposed thereon, said front surface of said rear element having a conductive material disposed thereon or said rear element itself being conductive, wherein said front and rear elements are sealably bonded together in a spaced apart relationship to define a cavity, where said cavity contains the electrochromic medium of claim 3.
22. An electrochromic device comprising front and rear spaced elements each having front and rear surfaces, said rear surface of said front element having a transparent conductive material disposed thereon, said front surface of said rear element having a conductive material disposed thereon or said rear element itself being conductive, wherein said front and rear elements are sealably bonded together in a spaced apart relationship to define a cavity, where said cavity contains the electrochromic medium of claim 4.
23. An electrochromic device comprising front and rear spaced elements each having front and rear surfaces, said rear surface of said front element having a transparent conductive material disposed thereon, said front surface of said rear element having a conductive material disposed thereon or said rear element itself being conductive, wherein said front and rear elements are sealably bonded together in a spaced apart relationship to define a cavity, where said cavity contains the electrochromic medium of claim 10.
24. An electrochromic device comprising front and rear spaced elements each having front and rear surfaces, said rear surface of said front element having a transparent conductive material disposed thereon, said front surface of said rear element having a conductive material disposed thereon or said rear element itself being conductive, wherein said front and rear elements are sealably bonded together in a spaced apart relationship to define a cavity, where said cavity contains the electrochromic medium of claim 11.
25. An electrochromic device comprising front and rear spaced elements each having front and rear surfaces, said rear surface of said front element having a transparent conductive material disposed thereon, said front surface of said rear element having a conductive material disposed thereon or said rear element itself being conductive, wherein said front and rear elements are sealably bonded together in a spaced apart relationship to define a cavity, where said cavity contains the electrochromic medium of claim 14.
26. An electrochromic device comprising front and rear spaced elements each having front and rear surfaces, said rear surface of said front element having a transparent conductive material disposed thereon, said front surface of said rear element having a conductive material disposed thereon or said rear element itself being conductive, wherein said front and rear elements are sealably bonded together in a spaced apart relationship to define a cavity, where said cavity contains the electrochromic medium of claim 15.
27. An electrochromic device comprising front and rear spaced elements each having front and rear surfaces, said rear surface of said front element having a transparent conductive material disposed thereon, said front surface of said rear element having a conductive material disposed thereon or said rear element itself being conductive, wherein said front and rear elements are sealably bonded together in a spaced apart relationship to define a cavity, where said cavity contains the electrochromic medium of claim 16.
28. The electrochromic device of claim 19, wherein said device is an electrochromic mirror.
29. The electrochromic device of claim 20, wherein said device is an electrochromic mirror.
30. The electrochromic device of claim 21, wherein said device is an electrochromic mirror.
31. The electrochromic device of claim 22, wherein said device is an electrochromic mirror.
32. The electrochromic device of claim 23, wherein said device is an electrochromic mirror.
33. The electrochromic device of claim 24, wherein said device is an electrochromic mirror.
34. The electrochromic device of claim 25, wherein said device is an electrochromic mirror.
35. The electrochromic device of claim 26, wherein said device is an electrochromic mirror.
36. The electrochromic device of claim 27, wherein said device is an electrochromic mirror.
37. A process for the preparation of an electrochromic device wherein an electrochromic medium is introduced into a cavity in said device, said electrochromic medium containing at least one anodic electroactive compound and at least one cathodic electroactive compound, at least one of said electroactive compounds being an electrochromic compound, the improvement comprising: adjusting the concentrations of said electroactive compounds to establish an increased relative concentration of the electroactive material having the smaller redox potential difference such that said increased concentration is greater than that required to achieve a balanced concentration.
38. The process of claim 37, wherein said increased concentration is sufficient to substantially eliminate production of devices having the electroactive material having the smaller redox potential difference as the current limiting species or less than that required to achieve a balanced concentration due to variations in measuring the relative amounts of electroactive compounds when preparing said electrochromic medium.
39. The process of claim 37, wherein at least one anodic electroactive compound (A,) which exhibits two chemically reversible waves in a cyclic voltammogram is present and at least one cathodic electroactive compound (C,) which exhibits two chemically reversible waves is present, the electroactive compound (Al) or (C) having the largest redox potential difference being present in a concentration less than that required to achieve a balanced concentration.
40. The process of claim 37, wherein at least one anodic electroactive compound (A,) which exhibits two chemically reversible waves in a cyclic voltammogram is present and at least one cathodic electroactive compound (C,) which exhibits two chemically reversible waves is present, the electroactive compound (A,) or (C,) having the smallest redox potential difference being present in a concentration greater than that required to achieve a balanced concentration.
41. The process of claim 37, wherein one of said electroactive materials is an anodic electroactive compound (A,) or a cathodic electroactive compound (C,) which exhibits two chemically reversible waves in a cyclic voltammogram, and one of said electroactive materials is an electroactive compound (A2) which exhibits only one electrochemically activated state, or a cathodic electroactive compound (C,) which exhibits only one electrochemically activated state, wherein said electroactive compound (A2) or (C2) is present in a concentration less than that required to achieve a balanced concentration.
42. The process of claim 37, wherein at least one of said electroactive materials exhibits an electrochemically activated state which is less chemically stable than the electrochemically activated states of other electroactive materials in said electrochromic medium, said electroactive material which exhibits said less chemically stable electrochemically activated state being present in a concentration greater than that required to achieve a balanced concentration.
Description:
INTERNATIONALSEARCH REPORT _ Inte ional Application No PCT/US 00/11813 C. (Continuation) DOCUMENTS CONSIDERED TO BE RELEVANT Category ° Citabon of document, with indication, where appropriate, of the relevant passages Relevant to claim No. A USHAKOV 0 A ET AL :"CALCULATION OF 1-42 STEADYtrSTATE ELECTROCOLORATION PARAMETERS OF ELECTROCHROMIC SYSTEMS" SOV ELECTROCHEM JUL 1985, vol. 21, no. 7, July 1985 (1985-07), pages 857-860,XP002146912 the whole document 2 iroernational application No. PCT/US 00/11813 INTERNATIONAL SEARCH REPORT Box I Observations where certain claims were found unsearchable (Continuation of item 1 of first sheet) This International Search Report has not been established in respect of certain claims under Article 17 (2) (a) for the following reasons: 1. ClaimsNos.: because they relate to subject matter not required to be searched by this Authority, namely: 2. Claims Nos. : 1-42 because they relate to parts of the International Application that do not comply with the prescribed requirements to such an extent that no meaningful international Search can be carried out, specifically : see FURTHER INFORMATION sheet PCT/ISA/210 3. Claims Nos.: because they are dependent claims and are not drafted in accordance with the second and third sentences of Rule 6.4 (a). Box 11 Observations where unity of invention is lacking (Continuation of item 2 of first sheet) This Intemational Searching Authority found multiple inventions in this international application, as follows : 1. As all required additional search fees were timely paid by the applicant, this International Search Report covers all searchable ciaims. 2. As all searchable claims could be searched without effort justifying an additional fee, this Authority did not invite payment of any additional fee. 3. As only some of the required additional search fees were timely paid by the applicant, this International Search Report covers only those claims for which fees were paid, specifically claims Nos.: 4. nj No required additional search fees were timely paid by the applicant. Consequently, this International Search Report is restricted to the invention first mentioned in the claims ; it is covered by claims Nos.: Remark on Protest 7 The additional search fees were accompanied by the applicant's protest. No protest accompanied the payment of additional search fees. LJ International Application No. PCT/US 00/11813 FURTHER INFORMATION CONTINUED FROM PCTIISA/210 Continuation of Box I. 2 Claims Nos.: 1-42 Present claims 1-42 relate to an electrochromic medium comprising an anodic electroactive material and a cathodic electroactive material defined by reference to the parameter"the electroactive material having the smaller potential difference between the chemically reversible waves has a concentration in the electrochromic medium greater than that required to achieve a balanced concentration". The method of calculating the"balanced concentration"is not indicated in the description although it is indicated that the"balanced concentration"is the concentration required to achieve a balanced current. The use of this parameter in the present context is considered to lead to a lack of clarity within the meaning of Article 6 PCT. It is impossible to compare the parameter the applicant has chosen to employ with what is set out in the prior art. The lack of clarity is such as to render a meaningful complete search impossible. Consequently the search has been restricted to the examples provided in the description. The applicant's attention is drawn to the fact that claims, or parts of claims, relating to inventions in respect of which no international search report has been established need not be the subject of an international preliminary examination (Rule 66.1 (e) PCT). The applicant is advised that the EPO policy when acting as an International Preliminary Examining Authority is normally not to carry out a preliminary examination on matter which has not been searched. This is the case irrespective of whether or not the claims are amended following receipt of the search report or during any Chapter II procedure. INTERNATIONAL SEARCH REPORT Ir, ational Application No Information on patent family members PCT/US 00/11813 PCT/US 00/11813 Patent document Publication Patent family Publication cited in search report date member (s) date WO 9844386 A 08-10-1998 US 5940201 A 17-08-1999 AU 6776198 A 22-10-1998 EP 0990194 A 05-04-2000 US 6057956 A 02-05-2000 WO 9844384 A 08-10-1998 US 6020987 A ûl-û2-2ûûû AU 6778098 A 22-10-1998 EP 0972227 A 19-01-2000 EP 0612826 A 31-08-1994 EP 1004649 A 31-05-2000 JP 7070218 A 14-03-1995 US 6002511 A 14-12-1999 US 5910854 A 08-06-1999 WO 9734186 A 18-09-1997 US 5928572 A 27-07-1999 AU 2212297 A 01-10-1997 CA 2248861 A 18-09-1997 EP 0886803 A 30-12-1998 JP 2000506627 T 30-05-2000