CA1076238A - Paper counter-electrode for electrochromic devices - Google Patents

Paper counter-electrode for electrochromic devices

Info

Publication number
CA1076238A
CA1076238A CA276,497A CA276497A CA1076238A CA 1076238 A CA1076238 A CA 1076238A CA 276497 A CA276497 A CA 276497A CA 1076238 A CA1076238 A CA 1076238A
Authority
CA
Canada
Prior art keywords
electrochromic
counter
electrode
paper
sheet
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
CA276,497A
Other languages
French (fr)
Inventor
Robert D. Giglia
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wyeth Holdings LLC
Original Assignee
American Cyanamid Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by American Cyanamid Co filed Critical American Cyanamid Co
Application granted granted Critical
Publication of CA1076238A publication Critical patent/CA1076238A/en
Expired legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
    • G02F1/1523—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/163—Operation of electrochromic cells, e.g. electrodeposition cells; Circuit arrangements therefor
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/153—Constructional details
    • G02F1/155—Electrodes
    • G02F2001/1555—Counter electrode

Abstract

???71 PAPER COUNTER-ELECTRODE FOR
ELECTROCHROMIC DEVICES

ABSTRACT OF THE DISCLOSURE

Disclosed is a method for forming a counter-elec-trode in a variable light modulating device of the electro-chromic type, The counter-electrode is a paper composition of fibrous pulp and carbon.

Description

~L0 ~ 6'~3~3 The invention relates to electro-optical devices whose electro-ma~netic radi~tion absorption char~cteristics can be selectively altered by the influence of a suitably controlled electric field. More particularly, the invention relates to variable light transmission devices which contain a layer of persistent electrochromic material as a light modulating material, and a counter-electrode separated by an ion conducting material. In specific, the invention is directed to a simplified, effective counter-electrode for electrochromic devices and a method for forming such counter-electrodes.
~ lectrochromic devices are known in the art and are described in prior, commonly assigned, U.S. Patents, such as 3,521,9~1 which issued on July 28, 1970 to Deb, et al, 3,70~,057 which issued on November 28, 1972 to Beegle, 3,708,220 which issued on January 2, 1973 to Meyers, et al, 3,8~3,232 which issued on October 22, 197~ to Berets, and 3,8~7,468 which issued on November 12, 197~ to Clasen, et al. These patents disclose suitable materials and methods for forming the overall electrochromic device of the present invention. These patents further show various counter-electrode arrangements which previously have been utilized. U.S. Patent No. 3,521,941 utilizes a gold film counter-electrode, while U.S. Patent No. 3,843,232 introduces a counter-electrode made from palladium. Another development is shown in U.S.
Patent No. 3,704,057, wherein electrochromic material is used -for the counter-electrode as well as for the display area.
Although the prior counter-electrode structures have successfully operated in electrochromic devices, the present counter-electrode invention is designed to provide improved reversibility and longer li~e at a comparably low cost.
According to one aspect of the present invention, there is provided in a variable light modulating device of the electrochromic type having an arrangement comprising a light transmitting substrate having a persistent ; el~ctrochromic material as a light modulating material and a counter-elec-trode separated from said electrochromic material by an ion-conducting material, an improved counter-electrode structure consisting essentially of a paper sheet comprising a web of filaments permeated wi~h carbon.

'76~3~

According to another aspect of the present invention, there is provided a process for making a paper material for a paper counter-electrode for an electrochromic variable light modulating device comprising: blending an aqueous suspension of fibrous material with powdered carbon to form an aqueous mixture, forming a sheet of the solids from said aqueous mixture, drying and pressing said sheet to form a paper material to be used as a counter-electrode for an electrochromic device.
The foregoing and other features, objects and advantages of the invention will become more apparent by reference to the following more detailed description read in conjunction with the accompanying drawing.

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6i238 .

Fi8, 1 i9 an e~ploded per~pective vlew Or ~n elec-trochromic device including the paper counter-electrode o~
the present invention.
A~ ~hown ln Fig, 1, the pr~erred embod~ment o~ the electrochr~mic di~play i8 a sandwich &rrangement o~ a trQn~-p~r~nt sub~trate 3 ¢o~ted wlth a ¢onduc~ive m~terlal ll, such as tin o~id~. Thi~ ~ubstrate and conductive coating ~ oon-veniently be provided ~ a unlt by commerc~ally avall~ble B 10 NB~A glas~, which i~ a product having ~ transp~rent coating : o~ conductive tln o~ide on one sur~ace o~ a gla89 ~heet. ~he electrochromic material l~yer 4 may be deposited on the t~n o~de la~er b~ kn~wn vacuum depo~ition tochniques, Ion con-. ducting layer 5 ma~ ¢onsi~t Or a 11quid, semi-~olid or solld l~ a~ disclosed ln the prior art cited, In ~ccordance with the pre~ent lnventlon, a p~per ~ ele~trode 6 i~ utll~zed ~9 the counter-electrode. 3ub~trate : 7 m~y be gla~3, metal or pl~tic~ and the li~e ~nd ne~d not b~ tran~parent, depe~dlng on the desired product application.
me p~per el~ctrode may be bonded to the ~ubstr~te b~ means o~ an adhesive, I~ the ~hs~ive is elsckrioally oonductive and the ~ubstrate ~l~o i9 eleotricall~ ¢onduotive, ~lectrioal connection ma~sr be more oonveniently made to the sub~trate rather than to the paper electrode dlrectly, The paper oounter-~lff¢trode ba~lo~ a carbon-rllled ~ibr3u~ sheet. A prererred ~iber u~ed 1~ ~n ~cx~ylic er a~d a rluerooarbo~ ra~in ~ueh as a Terlon (polgtetra- .
~luoroethylene) binder mag be incorpor~ted to pro~ide ~ mors ¢ohe~ivs ~heet, An electrochromi¢ ~terial m~y al~o be ~n-corpor~ted on th~ ~heet. A pre~erabl~ m~kerial 19 W03.
The ~ollowine i~ a~ ex~mpl~e o~ ~ paper countar-elsctrod~ prep~ration~
ad e ~a P ~,~

,, .. . ,. . .. ,., , : ., .: : . - - : :

9~76Z3~

EX~PLE 1 A mixture OI 160 ml o~ 1.17,9~ 9su~pension o~ C~an~mid T98 acrylic fiber pulp in H2J 3~ gm o~ United Carbon 6310-4 (a high surr~ce area carbon powder), 2.0 ml o~ 0~2% aquaou9 5 solution Or C~anQmid M1653C ~locculating agent (a highlg active, hi~h molecular wei~ht liquld c~tionic ~locculRnt), 1.0 ml Or 10~ Je~ferson Chemlcal Company Sur~onic N120 non-ion~c ~ur~Qce ~ctlve agent ~re~ctlon product o~ nonyl phenol ~nd ethylene oxide), 2.0 ml o~ 60% Teflon TF~ 30-B (pol~
tetra~luoroethylene~ Qnd 200 ml o~ H20 wa~ blendad at low speed ~o.r 15 seoonds :followed by 15 seconds Or high speed blending, A sheet Or carbon impregnated ~ibrous acrylic mate-rial wa9 thon rormed by ~tAndard p~per~naking procedure and then drled und~r pre~ure at 70C, to 120C. The dried ~heet next W~B soQked ~or 2 hour~ in 10% H2S04 in i~opropanol in order to remove impurit~ e~ introduced in processing. Following this ~oaking, the ~heet rurther wa~ rinsed ln i~opropanol ~or 1 hour and v~cuwn drled ror 1/2 hour ~t 80C.
~ In ~ome electrochromic applicatlon~, lt ma~ be pre~-:l . 20 rerable to includs eleatrochromic m~terlal in the counter-ele¢troda. Ac¢ordingl~, the ~ollowing ex~unple o~ application procedure m~y be u~ed: .
EXAUPLE Z
A~tsr vacuum dr~ing the i~opropanol rln~ed sheat, aa in ~xample l, both ~ldes o~ the ~heet wers3 c~ted with Q
aolutlon ol' eleotrochromic W03 ln NH40H. Tha coated 3heet then wa~ vacuum dried ~t 80G, ~or 1 hour. The ~heet wa~ then so~ked in 10~ H2S04 tn i~oprop~nol for 1 hour, Fin~lly, the ~heet W8E~ rln3sd in i~propPnol ~or 2 hours and vaouum dried at Booc, ~he ah~et WR~I pressed ~t 1.2 kg/cm2 to produce Q
.012 ~nch thiolr sheet which o~n be out to de~ired ~ize, In comparatlvo te~tin~S5 the p~per counter-electrode, 1~76;~3l~

prepared as de3cribed above, demon~trated improved re~ults o~er prior known counter-electrodes, For ex~mple, when the present invention W~8 ~ub~tituted ror the counter-electrode material as incorporated ln the electrochromic m~rror device ~hown in U.S~ Patent ~o, 3,844,636, switching ~peed wa3 au~-mented rrom 30 ~econds to color and 1 1/ minute~ ror era~ure to o~ly 10 ~econds to color and lesq t~an 1 m~nu~e to sr~e.
Further, when the in~ented paper counter-electrode WB8 used to replace the c~mmon counter-elsctrodes in the elec-trochromic numeric di~play~ as shown in ~.S. P~tent Nos.
39839,857 and 3,827,784~ life-tlme was enhanced ~rom 4 x lo6 c~clas to be~ond 7 ~ 106 cycles wlthout r~llure.

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Claims (13)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. In a variable light modulating device of the electrochromic type having an arrangement comprising a light transmitting substrate having a persistent electrochromic material as a light modulating material and a counter-electrode separated from said electrochromic material by an ion-conducting material, an improved counter-electrode structure consisting essentially of a paper sheet comprising a web of filaments permeated with carbon.
2. The combination according to claim 1, wherein said filaments are acrylic fibers.
3. The combination according to claim 1 wherein said paper sheet includes a fluorocarbon resin binder material.
4. The combination according to claim 3 wherein said paper sheet includes an electrochromic material.
5. The combination according to claim 4 wherein said electrochromic material is WO3.
6. A process for making a paper material for a paper counter-electrode for an electrochromic variable light modulating device comprising: blending an aqueous suspension of fibrous material with powdered carbon to form an aqueous mixture, forming a sheet of the solids from said aqueous mixture, drying and pressing said sheet to form a paper material to be used as a counter-electrode for an electrochromic device.
7. The process of claim 6 wherein said fibrous material is an acrylic fiber.
8. The process of claim 7 wherein a binder is blended into said aqueous mixture so as to form a more cohesive paper sheet.
9. The process of claim 8 wherein said binder is a fluorocarbon resin.
10. The process of claim 9 wherein a flocculating agent and a surfact-ant are blended into said aqueous mixture.
11. The process of claim 10 including the additional finishing steps of washing the dried and pressed paper sheet in acid and alcohol, and drying the washed sheet.
12. The process of claim 9 including the additional step of applying an electrochromic material to the washed sheet.
13. The process of claim 12 wherein said electrochromic material is WO3.
CA276,497A 1976-05-27 1977-04-19 Paper counter-electrode for electrochromic devices Expired CA1076238A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US05/690,446 US4088395A (en) 1976-05-27 1976-05-27 Paper counter-electrode for electrochromic devices

Publications (1)

Publication Number Publication Date
CA1076238A true CA1076238A (en) 1980-04-22

Family

ID=24772491

Family Applications (1)

Application Number Title Priority Date Filing Date
CA276,497A Expired CA1076238A (en) 1976-05-27 1977-04-19 Paper counter-electrode for electrochromic devices

Country Status (13)

Country Link
US (1) US4088395A (en)
JP (1) JPS52146256A (en)
BE (1) BE855078A (en)
BR (1) BR7703113A (en)
CA (1) CA1076238A (en)
CH (1) CH616006A5 (en)
DE (1) DE2721735C2 (en)
FR (1) FR2353076A1 (en)
GB (1) GB1561527A (en)
IT (1) IT1077721B (en)
MX (1) MX146434A (en)
NL (1) NL7705811A (en)
SE (1) SE442068B (en)

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Also Published As

Publication number Publication date
BR7703113A (en) 1978-02-08
IT1077721B (en) 1985-05-04
FR2353076B1 (en) 1982-07-02
BE855078A (en) 1977-11-28
SE442068B (en) 1985-11-25
GB1561527A (en) 1980-02-20
US4088395A (en) 1978-05-09
FR2353076A1 (en) 1977-12-23
DE2721735C2 (en) 1985-10-24
JPS52146256A (en) 1977-12-05
SE7706202L (en) 1977-11-28
CH616006A5 (en) 1980-02-29
MX146434A (en) 1982-06-28
DE2721735A1 (en) 1977-12-08
NL7705811A (en) 1977-11-29

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