GB2246872A - Electrochromic material - Google Patents

Electrochromic material Download PDF

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Publication number
GB2246872A
GB2246872A GB9115423A GB9115423A GB2246872A GB 2246872 A GB2246872 A GB 2246872A GB 9115423 A GB9115423 A GB 9115423A GB 9115423 A GB9115423 A GB 9115423A GB 2246872 A GB2246872 A GB 2246872A
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GB
United Kingdom
Prior art keywords
electrochromic material
electrochromic
polymer
alkali metal
layer
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.)
Withdrawn
Application number
GB9115423A
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GB9115423D0 (en
Inventor
Paul Radmall
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.)
Dowty Electronic Components Ltd
Original Assignee
Dowty Electronic Components Ltd
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 Dowty Electronic Components Ltd filed Critical Dowty Electronic Components Ltd
Publication of GB9115423D0 publication Critical patent/GB9115423D0/en
Publication of GB2246872A publication Critical patent/GB2246872A/en
Withdrawn legal-status Critical Current

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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
    • G02F1/1525—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 characterised by a particular ion transporting layer, e.g. electrolyte
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
    • C09K9/02—Organic tenebrescent materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
    • H01M6/181—Cells with non-aqueous electrolyte with solid electrolyte with polymeric electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
    • H01M6/164—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solvent

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)

Abstract

An electrochromic device comprises an ionic conducting layer comprising a complex of a solid polymer and an alkali metal salt, which polymer is capable of forming donor-acceptor type bonds with alkali metal ions and is capable of conducting alkali metal ions, wherein the complex is associated with a mixture of more than one substituted or unsubstituted 1,3-dioxolane-2-ones. Polymer complexes of the invention possess ionic conductivities that make them especially suitable for use in shoot or film material for smart windows". For example, they possess ionic conductivities 10<-3> to 10<-4> at ambient temperatures and over a range below, for example down to -20 DEG C. The polymer may be a homopolymer of copolymer or both; a preferred polymer is poly(ethene oxide) - PEO. A preferred alkali metal is lithium - Li and a preferred alkali metal salt is lithium perchlorate - LiClO4. <IMAGE>

Description

ELECTROCHROMIC MATERIAL Technical Field This invention relates to transparent sheet or film material which is adapted so that an electrical signal can be applied to it to reversibly modulate the transmission of light through the material. Such material, hereinafter referred to as electrochromic material, has been proposed for use in "smart windows" to control glare and improve the energy efficiency of buildings and vehicles.
Electrochromic material comprises a multilayer laminate of transparent materials including an electrochromic layer and a counterelectrode layer separated by an ionic conducting layer. The electrochromic layer is electronically and ionically conducting and has a structure such that metallic ions are insertable therein which cause it to "colour" when an electrical current pulse signal is applied between the electrochromic layer as the cathode and the counterelectrode as the anode. Suitable ions are lithium ions. The counterelectrode layer is also electronically and ionically conducting and has a structure such that either it "colours" as a result of ion extraction or is unaffected and remains transparent. The ionic conducting layer is ionically conducting to allow the rapid transfer of ions between the other two layers but is not electrically conducting.
Additionally, outer electronically conducting transparent layers may be provided on the electrochromic layer and counterelectrode layer to facilitate the flow of electrons into and out of the laminate material.
In a typical example, the electrochromic layer comprises a lithium-insertable rf sputter deposited polycrystalline W03 film, the counterelectrode comprises a lithium-insertable rf sputter deposited In203 film or a thermally deposited V205 film, and the ionic conducting layer comprises rf sputter deposited LiNbO3 film.
Disclosure of the Invention An object of the present invention is to provide improved electrochromic material for "smart windows".
This is achieved according to the present invention by providing material comprising electrochromic and counterelectrode layers separated by an ionic conducting layer comprising a complex of a solid polymer and an alkali metal salt, which polymer is capable of forming donoracceptor type bonds with alkali metal ions and is capable of conducting alkali metal ions, wherein the complex is associated with a mixture of more than one substituted or unsubstituted 1,3 dioxolane - 2 - ones.
Polymer complexes of the invention possess ionic conductivities that make them especially suitable for use in sheet or film material for "smart windows". For example, they possess ionic conductivities 10-3 to 1o-4 at ambient temperatures and over a range below, for example down to -2O0C.
The polymer may be a homopolymer or copolymer or both; a preferred polymer is poly(ethene oxide) PEO. A preferred alkali metal is lithium - Li and a preferred alkali metal salt is lithium perchlorate - Lilo4.
Preferred 1,3 - dioxolane - 2 - ones, also called alkylene carbonate are ethylene carbonate - EC and propylene carbonate - PC, where a mixture of ethylene carbonate and propylene carbonate is particularly preferred.
More particularly it has been found that solid polymer complexes, the molar ratios of whose constituents are represented by the general formula (I) below are especially useful: [ PEOa : [ xEC : yPC ] ] = : Lix (I) where each of a, b, x, y and n is finite and represents a molar quantity, and X is an anion.
Moreover, a number of polymer complexes of the formula (I) where a = b = 1 have been investigated and it has been found that particularly advantageous results may be obtained when the ratio of EC to PC is 2:2 (i.e. x = y = 2), n = 20, and X is ClO4#. Thus, a preferred polymer complex within the formula (I) may be represented by the formula (II) below: [PEO : [2EC : 2PC1 ] 20 : Lilo, (II) where all numbers represent molar quantities. A polymer complex of the formula (II) has been found to possess an acceptable ionic conductivity within the temperature range of -400C to +700C as will be illustrated in the example herein and is completely amorphous above -400C.
Also, another example of a noteworthy polymer complex within the formula (I) may be represented by the formula (III) below: [PEO : [3EC : PC ] ] 20 : LiClo4 (III) where all numbers represent molar quantities.
Electrochromic material according to the invention may be incorporated into a "smart window or similar product by depositing the various layers on a transparent substrate such as glass or plastics or other transparent material using any of the known technologies. The solid polymer complex of the ionic conducting layer may be cast onto release paper in the form of a film from a solution of the complex using a doctor blade.
The resulting film is sticky and may be transferred to the electrochromic or counterelectrode layer by contact therewith.
Alternatively, the polymer complex may be cast directly onto the electrochromic or counterelectrode layer.
Description of the Drawings This invention will now be described by way of example with reference to the accompanying drawings in which: Figure 1 is a schematic drawing of electrochromic material suitable for use as a "smart window" according to the invention, Figure 2 is a graph of the ionic conductivity G within the temperature range 700C to -20 C, of one example of a polymer complex used as the ion conductive layer of the electrochromic material of Figure 1, Figure 3 is a similar graph to that of Figure 2 for a second example of a polymer complex used as the ion conductive layer of the electrochromic material of Figure 1.
Mode of Carrying Out the Invention The electrochromic material illustrated in Figure 1 comprises a multi-layer laminate of transparent materials comprising an electrochromic layer 1 and a counterelectrode layer 2 separated by an ionic conducting layer 3. The electrochromic layer 1 comprises a lithium-insertable rf sputter deposited polycrystalline W03 film, and the counterelectrode comprises a lithium insertable rf sputter deposited In203 film. Outer electronically conducting layers 4 and 5 of undoped In203 are provided on the electrochromic layer 1 and the counterelectrode layer 2.
Electrical terminals 6 and 7 are connected to these conducting layers 4, 5 for the application of an electrical current pulse signal so as to change the "colour" of the electrochromic material when in use as a "smart window", the electrochromic material then being incorporated in a laminate between outer sheets of clear glass 8 and 9, as shown in Figure 1.
The ionic conducting layer 3 is a polymer complex comprising a solution of poly(ethene oxide) - PEO, lithium perchlorate - Lilo4, ethylene carbonate EC and propylene carbonate - PC in acetonitrile.
This was was cast onto release paper and the solvent allowed to evaporate to give a polymer film (thickness 50-100 um). The composition of the solution was such that the composition of the film was: (PEO)loLiClO4 plus 70% by weight of EC and PC together where the ratio of EC to PC was 3:1 (weight:weight). This film was applied to the electrochromic material by contacting it with another layer of the material, either the electrochromic layer 1 or the counterelectrode layer 2.
In an alternative method of manufacture, the above polymer may be applied directly to either the electrochromic layer 1 or the counterelectrode layer 2.
The ionic conductivity of this ionic conducting layer 3 was measured at different temperatures.
The results are summarised in Figure 2 from which it will be seen that satisfactory values were obtained in the temperature range of -200C to 700C.
A second example of a polymer complex used for the ionic conducting layer 3 comprises a solution of PEO, LiCl04, EC and PC in acetonitrile cast onto release paper and the solvent allowed to evaporate to give a polymer film (thickness - 50 micrometres). The composition of the film was: [ PEO : [2EC : 2PC ] ] 20 : Lilo, i.e. of the formula (II) herein.
The ionic conductivity of this layer 3 was measured as a function of temperature using the standard complex impedance data collected by a Solartron 1254 FRA and 1286 ECI combination.
The results are summarised in the Figure 3 of the accompanying drawings from which it will be seen that ionic conductivity rises from about 10-40hm-lcm-l at -400C to about 10-2ohm-lcm-l at +700C.
According to another feature of the invention, the electrochromic layer 1 and counterelectrode layer 2 may also each comprise a polymer complex which incorporates electronically and ionically conducting material such as, for example, copper trifluoromethane sulphonate Cu (CF3 SO3)2 as described in EP 0295830. The advantage of such layers over rf sputtered layers is that they are less costly to manufacture.These layers can be cast and transferred, or cast directly, onto the glass sheets 8 and 9 or the electrochromic and counterelectrode layers 1 and 2 so as to build up the complete laminate of the "smart window" The density and size of the conducting particles in the polymer complex of the electrochromic and counterelectrode layers 1 and 2, and the thickness of the layers, are determined to control the transparency of the layers when in the nonenergised clear state. The electrochromic layer 1 incorporates suitable electrochromic particulate material which may comprise two or more different materials with different optical responses, for example, different colours. The distribution of the electrochromic particulate material throughout the area of the layer 1 can be varied so as to obtain gradations of the optical effects.
Also, according to another feature of the invention, the electrochromic material may be divided into different areas, each electrically separate so that each can be energised separately.
For this purpose, preferably only the electrochromic layers 1 and counterelectrode layers 2 need to be separate.

Claims (17)

1. Electrochromic material comprising electrochromic and counterelectrode layers separated by an ionic conducting layer comprising a complex of a solid polymer and an alkali metal salt, which polymer is capable of forming donoracceptor type bonds with alkali metal ions and is capable of conducting alkali metal ions, wherein the complex is associated with a mixture of more than one substituted or unsubstituted 1,3 - dioxolane - 2 ones.
2. Electrochromic material according to claim 1 wherein the mixture comprises ethylene carbonate and propylene carbonate.
3. Electrochromic material according to claim 1 or claim 2 wherein the solid polymer is poly(ethene oxide) or poly(propene oxide).
4. Electrochromic material according to any one of the preceding claims wherein the alkali metal is lithium.
5. Electrochromic material according to claim 1 wherein the molar ratios of the constituents therein are represented by the general formula (I) below: CPEO, : txEC : yPCl ] = : Lix (I) where PEO represents poly(ethene oxide) EC represents ethylene carbonate PC represents propylene carbonate and each of a, b, x, y and n is finite and represents a molar quantity, and X is an anion.
6. Electrochromic material according to claim 5 wherein the molar ratios of the constituents therein are represented by the formula (II) below: (PEO : [2EC : 2PC ] ] 20 : LiCl04 (Il) where PEO, EC and PC are defined as in claim 5 and the numbers represent molar quantities.
7. Electrochromic material as claimed in any one of the preceding claims in which the electrochromic layer comprises a polymer complex incorporating electronic and ionic conducting material.
8. Electrochromic material as claimed in claim 7 in which the electronic and ionic conducting material comprises copper trifluoromethane sulphonate.
9. Electrochromic material as claimed in any one of the preceding claims in which the counterelectrode layer comprises a polymer complex incorporating electronic and ionic conducting material.
10. Electrochromic material as claimed in claim 9 in which the electronic and ionic conducting material comprises copper trifluoromethane sulphonate.
11. Electrochromic material as claimed in claim 7 in which the polymer complex incorporates at least two electronic and ionic conducting materials with different optical responses.
12. Electrochromic material as claimed in claim 7 in which the electronic and ionic conducting material is varied in its distribution in the polymer complex.
13. Electrochromic material as claimed in any one of the preceding claims in which the electrochromic layer is formed in at least two electrically separate areas and the counterelectrode is formed with an equivalent number of electrically separate areas to correspond to the separate areas of the electrochromic layer.
14. A laminate comprising a transparent substrate and electrochromic material as claimed in any one of the preceding claims.
15. A laminate as claimed in claim 14 in which the electrochromic material lies between two transparent substrates.
16. Electrochromic material substantially as herein described with reference to the accompanying drawings.
17. A laminate comprising a transparent substrate and electrochromic material substantially as herein described with reference to the accompanying drawings.
GB9115423A 1990-07-20 1991-07-17 Electrochromic material Withdrawn GB2246872A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB9016009A GB9016009D0 (en) 1990-07-20 1990-07-20 Electrochromic material

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GB9115423D0 GB9115423D0 (en) 1991-09-04
GB2246872A true GB2246872A (en) 1992-02-12

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GB9115423A Withdrawn GB2246872A (en) 1990-07-20 1991-07-17 Electrochromic material

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993004507A1 (en) * 1991-08-14 1993-03-04 British Technology Group Ltd. Solid polymer electrolytes
WO2014118672A3 (en) * 2013-01-29 2015-03-05 Koninklijke Philips N.V. Control unit for controlling the color of a window

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115185130B (en) * 2022-08-16 2024-02-20 福耀玻璃工业集团股份有限公司 Partitioned electrochromic device

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6028630A (en) * 1983-07-27 1985-02-13 Nippon Kogaku Kk <Nikon> Electrochromic display element using lithium ions
JPS6454422A (en) * 1987-08-25 1989-03-01 Tokai Rika Co Ltd Production of electrochromic display element
JPH0324164A (en) * 1989-06-22 1991-02-01 Yuasa Battery Co Ltd Solid polyelectrolyte
JPH0388209A (en) * 1989-08-29 1991-04-12 Yuasa Battery Co Ltd High polymer solid electrolyte

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6028630A (en) * 1983-07-27 1985-02-13 Nippon Kogaku Kk <Nikon> Electrochromic display element using lithium ions
JPS6454422A (en) * 1987-08-25 1989-03-01 Tokai Rika Co Ltd Production of electrochromic display element
JPH0324164A (en) * 1989-06-22 1991-02-01 Yuasa Battery Co Ltd Solid polyelectrolyte
JPH0388209A (en) * 1989-08-29 1991-04-12 Yuasa Battery Co Ltd High polymer solid electrolyte

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993004507A1 (en) * 1991-08-14 1993-03-04 British Technology Group Ltd. Solid polymer electrolytes
US5581394A (en) * 1991-08-14 1996-12-03 British Technology Group Limited Solid polymer electrolytes
WO2014118672A3 (en) * 2013-01-29 2015-03-05 Koninklijke Philips N.V. Control unit for controlling the color of a window

Also Published As

Publication number Publication date
GB9115423D0 (en) 1991-09-04
JPH05158078A (en) 1993-06-25
GB9016009D0 (en) 1990-09-05

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