CN111592874A - Composition, electrochromic device, housing assembly, and electronic apparatus - Google Patents

Composition, electrochromic device, housing assembly, and electronic apparatus Download PDF

Info

Publication number
CN111592874A
CN111592874A CN202010562768.3A CN202010562768A CN111592874A CN 111592874 A CN111592874 A CN 111592874A CN 202010562768 A CN202010562768 A CN 202010562768A CN 111592874 A CN111592874 A CN 111592874A
Authority
CN
China
Prior art keywords
composition
electrochromic material
electrochromic
anode
electrolyte
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.)
Pending
Application number
CN202010562768.3A
Other languages
Chinese (zh)
Inventor
曹贞虎
彭明镇
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.)
Ningbo Ninuo Electronic Technology Co ltd
Guangdong Oppo Mobile Telecommunications Corp Ltd
Original Assignee
Ningbo Ninuo Electronic Technology Co ltd
Guangdong Oppo Mobile Telecommunications Corp 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 Ningbo Ninuo Electronic Technology Co ltd, Guangdong Oppo Mobile Telecommunications Corp Ltd filed Critical Ningbo Ninuo Electronic Technology Co ltd
Priority to CN202010562768.3A priority Critical patent/CN111592874A/en
Publication of CN111592874A publication Critical patent/CN111592874A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • 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
    • G02F1/1516—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 organic material
    • G02F1/15165—Polymers
    • 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
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems
    • 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
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom

Landscapes

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

Abstract

Disclosed are compositions, electrochromic devices, housing assemblies, and electronic devices. The composition comprises: the composition comprises an anode electrochromic material, a cathode electrochromic material, an electrolyte, an antioxidant and a solvent, wherein the molar ratio of the anode electrochromic material to the cathode electrochromic material in the composition is (0.35:1) - (2:1), the water content in the composition is less than 400ppm, the oxygen content in the composition is less than 400ppm, the purity of the anode electrochromic material is more than 99.97%, the purity of the cathode electrochromic material is more than 99.95%, the purities of the electrolyte, the antioxidant and the solvent are respectively and independently more than 99.5%, and the anode electrochromic material has a structural formula shown as a formula (I):
Figure DDA0002546518740000011
wherein R is1、R2、R3、R4Are respectively independentAnd is independently hydrogen, halogen, alkyl, haloalkyl or an oxygen-containing hydrocarbon functional group; y is methyl, ethyl or a bond; r6 and R7 are each independently hydrogen, methoxy, methyl or trifluoromethyl. The electrochromic device prepared by the composition has good durability, high contrast of a colored state and a transparent state and high response speed, and is suitable for electronic equipment with high requirements on color change/fading, such as mobile phones, mobile terminals or camera equipment.

Description

Composition, electrochromic device, housing assembly, and electronic apparatus
Technical Field
The present application relates to the field, in particular, to compositions, electrochromic devices, housing assemblies, and electronic devices.
Background
The optical property of the electrochromic material can be reversibly changed, so that the electrochromic material can show reversible change of color and transparency in appearance property. When a voltage with a certain polarity is applied to the electrochromic material, the visible light transmittance of the material is increased along with the voltage, so that the material is faded, and when the polarity of the voltage is opposite, the light transmittance of the material is reduced along with the voltage, so that the material is darkened and colored. Electrochromic materials can be roughly classified into organic electrochromic materials and inorganic electrochromic materials according to chemical compositions, and the organic electrochromic materials are further classified into anode electrochromic materials and cathode electrochromic materials. However, although electrochromic materials have been used to prepare devices including color-changing windows, the color-changing speed, the contrast between the colored state and the transparent state, the durability of the devices, etc. of electrochromic compositions still have difficulty in meeting the requirements of electronic devices with complex functions, for example, the current electrochromic compositions have difficulty in being popularized to most electronic devices due to the problems of low contrast between the colored state and the transparent state, the discoloration of the device as a whole, or the slow coloring speed (response speed).
Therefore, the composition of electrochromic materials, electrochromic devices, housing components, and electronic devices are still in need of improvement.
Disclosure of Invention
The present application is based on the discovery and recognition by the inventors of the following facts and problems:
the inventor finds that the common aging resistance of the current electrochromic material is poor, and the requirement of electronic equipment such as a mobile phone and the like on the aging resistance cannot be met. In particular, since the current electrochromic materials are mostly used for forming parts used indoors such as automobile rearview mirrors, the requirement on aging resistance, especially the aging resistance caused by ultraviolet irradiation, is not high. In contrast, for the application scenario of the housing assembly of electronic equipment such as a mobile phone, the electrochromic module in the housing assembly of the mobile phone is easily yellowed when the mobile phone is exposed to sunlight for a long time in the outdoor use scenario, especially in hot summer when the ultraviolet light is strong, thereby affecting the aesthetic degree and the shielding function of the overall appearance of the mobile phone. In addition, the current electrochromic materials are difficult to meet the requirements of electronic equipment such as mobile phones and the like on the contrast and the response speed of the color-changing device. Therefore, if a composition with excellent performance can be provided, and the electrochromic device prepared from the composition can have better contrast and response speed, and meanwhile, the material has better aging resistance, the technical problems can be greatly alleviated and even solved.
In one aspect of the present application, a composition for use in the preparation of an electrochromic device is presented. The composition comprises: the anode electrochromic material and the cathode electrochromic material in the composition have a molar ratio of (0.35:1) - (2:1), the water content of the composition is less than 400ppm, the oxygen content of the composition is less than 400ppm, the purity of the anode electrochromic material is more than 99.97%, the purity of the cathode electrochromic material is more than 99.95%, and the purities of the electrolyte, the antioxidant and the solvent are respectively and independently more than 99.5%,
the anode electrochromic material has a structural formula shown as a formula (I):
Figure BDA0002546518720000021
wherein R is1、R2、R3、R4Each independently is hydrogen, halogen, alkyl, halogenated alkyl or oxygen-containing carbon hydrogen functional group; y is methyl, ethyl or a bond; r6 and R7 are each independently hydrogen, methoxy, methyl or trifluoromethyl. The electrochromic device prepared by the composition has good durability, high contrast of a colored state and a transparent state and high response speed, and is suitable for electronic equipment with high requirements on color change/fading, such as mobile phones, mobile terminals or camera equipment.
In yet another aspect of the present application, a method of making an electrochromic device utilizing the composition set forth above is presented. The method comprises the following steps: mixing the anodic electrochromic material, the cathodic electrochromic material, the electrolyte, the antioxidant, and the solvent to obtain the electrochromic material; and a filling space is defined between the first substrate and the second substrate, the electrochromic material is filled in the filling space, and sealing treatment is carried out to obtain the electrochromic device. Thereby, an electrochromic device having the aforementioned electrochromic material can be obtained simply.
In yet another aspect of the present application, an electrochromic device is presented. The electrochromic device has the composition described previously. Thus, the electrochromic device has all the features and advantages of the composition described above, and will not be described herein again. In general, the electrochromic device has at least one of advantages of better durability, rapid discoloration/fading, higher contrast in colored and transparent states, and the like.
In yet another aspect of the present application, a housing assembly is presented. The housing assembly includes: a transparent substrate and the electrochromic device described earlier, said electrochromic device being located on one side of said transparent substrate. Therefore, the shell component can obtain richer appearance effects by utilizing the electrochromic device and has at least one of the advantages of better durability, rapid color change/fading, higher contrast of a colored state and a transparent state and the like.
In yet another aspect of the present application, an electronic device is presented. The electronic device includes: the housing assembly as described above, the housing assembly having an accommodating space; display screen and mainboard, the display screen with the mainboard is located inside the accommodation space, the display screen with the mainboard electricity is connected. Therefore, the electronic equipment has at least one of the advantages of richer appearance, better durability, rapid color change/fading, higher contrast between a colored state and a transparent state and the like.
Drawings
The above and/or additional aspects and advantages of the present application will become apparent and readily appreciated from the following description of the examples taken in conjunction with the accompanying drawings, in which:
FIG. 1 shows a schematic structural diagram of an electrochromic device according to one example of the present application;
FIG. 2 shows a schematic structural diagram of an electronic device according to an example of the present application;
fig. 3 shows a graph of the performance of electrochemical tests of an electrochromic device obtained according to example 1 of the present application;
fig. 4 shows a graph of the performance of electrochemical tests of the electrochromic device obtained according to comparative example 1 of the present application.
Detailed Description
Reference will now be made in detail to examples of the present application, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The examples described below with reference to the drawings are illustrative only for the purpose of explaining the present application and are not to be construed as limiting the present application.
In one aspect of the present application, a composition for use in the preparation of an electrochromic device is presented. Specifically, the composition comprises an anode electrochromic material, a cathode electrochromic material, an electrolyte, an antioxidant and a solvent, wherein the molar ratio of the anode electrochromic material to the cathode electrochromic material in the composition is (0.35:1) - (2: 1).
Specifically, the anode electrochromic material has a structural formula shown as a formula (I):
Figure BDA0002546518720000031
wherein R is1、R2、R3、R4Are respectively and independently hydrogen, halogen, alkyl or oxygen-containing hydrocarbon functional groups, Y is methyl, ethyl or a bond, and R6 and R7 are respectively and independently hydrogen, methoxy, methyl or trifluoromethyl.
The inventor finds that the aniline compound with the O-containing six-membered heterocyclic ring has stronger intermolecular interaction between N atoms in a pyran ring and a diphenylamine group and has larger steric hindrance as a whole, so that the contrast and the color change response speed of the aniline compound as an electrochromic material can be improved compared with linear or linear modified diphenylamine compounds. And, the anode electrochromic material has higher electron cloud density, so that the color change depth is deeper when performing electrochromism, thereby providing better color change/fading contrast. Specifically, when the N atom is positioned at a position para to the O atom position on the pyran ring in tetrahydropyran and derivatives thereof, it is more favorable to disperse the electron cloud of the O atom, thereby facilitating the formation of intermolecular forces between the O atom and the N atom. And, the N atom is located at the para position of the O atom, which is also beneficial to reducing the production cost: the difficulty of synthesizing the compound is low when the N atom is located at the para position relative to the O atom in other positions (e.g., ortho or meta). Therefore, the anode electrochromic material has lower production cost and better color change effect.
According to specific embodiments of the present application, the specific type of the cathodic electrochromic material is not particularly limited. For example, viologen compounds can be used as the cathode electrochromic material. After the anode electrochromic material of the aniline compound containing the oxygen six-membered heterocyclic ring and the viologen cathode electrochromic material are combined and compounded, the color change range of the electrochromic material can be prolonged, and the contrast of an electrochromic device prepared from the composition can be improved.
In some embodiments of the present application, R1、R2、R3、R4Can be the same or different alkyl groups. In particular, alkyl groups having 1 to 10 carbon atoms are possible. In another embodiment, the alkyl group may contain 1 to 8 carbon atoms; in yet another embodiment, the alkyl group contains 1 to 6 carbon atoms; in yet another embodiment, the alkyl group contains 1 to 3 carbon atoms. The inventors found that when the number of alkyl groups is too high, undesirable phenomena such as crystallization of the anodic electrochromic material during use are easily caused, which affects the lifetime and performance of the electrochromic device obtained using the composition.
Specifically, examples of alkyl groups include, but are not limited to, methyl (Me, -CH)3) Ethyl group (Et, -CH)2CH3) N-propyl (n-Pr, -CH)2CH2CH3) Isopropyl group (i-Pr, -CH (CH)3)2) N-butyl (n-Bu, -CH)2CH2CH2CH3) Isobutyl (i-Bu, -CH)2CH(CH3)2) Sec-butyl (s-Bu, -CH (CH)3)CH2CH3) Tert-butyl (t-Bu, -C (CH)3)3) N-pentyl (-CH)2CH2CH2CH2CH3) 2-pentyl (-CH (CH)3)CH2CH2CH3) 3-pentyl (-CH (CH)2CH3)2) 2-methyl-2-butyl (-C (CH)3)2CH2CH3) 3-methyl-2-butyl (-CH (CH)3)CH(CH3)2) 3-methyl-1-butyl (-CH)2CH2CH(CH3)2) 2-methyl-1-butyl (-CH)2CH(CH3)CH2CH3) N-hexyl (-CH)2CH2CH2CH2CH2CH3) 2-hexyl (-CH (CH)3)CH2CH2CH2CH3) 3-hexyl (-CH (CH)2CH3)(CH2CH2CH3) 2-methyl-2-pentyl (-C (CH))3)2CH2CH2CH3) 3-methyl-2-pentyl (-CH (CH)3)CH(CH3)CH2CH3) 4-methyl-2-pentyl (-CH (CH)3)CH2CH(CH3)2) 3-methyl-3-pentyl (-C (CH)3)(CH2CH3)2) 2-methyl-3-pentyl (-CH (CH)2CH3)CH(CH3)2) 2, 3-dimethyl-2-butyl (-C (CH)3)2CH(CH3)2) 3, 3-dimethyl-2-butyl (-CH (CH)3)C(CH3)3) N-heptyl, n-octyl, and the like.
In the present application, the term "alkyl" shall meanIs to be understood in a broad sense. Namely: unless otherwise specified, the "alkyl" may be a saturated or unsaturated alkyl group, and the unsaturated alkyl group may have a degree of saturation of 2 or greater than 2, and may, for example, contain one or more triple carbon-carbon bonds, may also contain one or more double carbon-carbon bonds, and may also be a straight-chain or branched alkyl group. Provided that R is1、R2、R3、R4Contains only C atoms and H atoms, and the total number of C atoms is not more than 10, i.e., "alkyl" as defined herein.
In particular, the alkyl group may also have one or more carbon-carbon sp groups therein2A linear or branched hydrocarbon group of a double bond, which includes the positioning of "cis" and "tans", or the positioning of "E" and "Z". Examples of alkenyl groups include, but are not limited to, vinyl (-CH ═ CH)2) Allyl (-CH)2CH＝CH2) And so on.
According to further examples of the present application, the alkyl group may further comprise one or more carbon-carbon sp groups3A triple bonded linear or branched hydrocarbon group. In one embodiment, alkynyl groups may contain 2-8 carbon atoms; in yet another embodiment, alkynyl groups contain 2-6 carbon atoms. Examples of alkynyl groups include, but are not limited to, ethynyl (-C.ident.CH), propargyl (-CH)2C.ident.CH), 1-propynyl (-C.ident.C-CH)3) And so on.
In some embodiments of the present application, R1、R2、R3、R4May be the same or different haloalkyl. In particular, a haloalkyl group having 1 to 10 carbon atoms. The term "haloalkyl" denotes an alkyl group substituted with one or more halogen atoms, examples of which include, but are not limited to, trifluoromethyl, chloroethyl, and the like.
In some embodiments of the present application, R1、R2、R3、R4Can be the same or different oxygen-containing hydrocarbon functional groups. In particular, it may be a carbonyl or ester group. The carbonyl or ester group can contain 1-10 carbon atoms, and the oxygen-containing hydrocarbon functional group can be a branched or straight-chain carbonyl or ester group.
According to an example of the present application, the4 substituents (i.e., R) on the pyran ring in the anodic electrochromic material1、R2、R3、R4) May be the same or different, i.e., the pyran rings may be symmetrical or asymmetrical. Specifically, R1、R2、R3、R4May be both H, or a portion may be H and another portion may be an alkyl, haloalkyl, or oxygen-containing hydrocarbon functional group. For example, R1、R2、R3、R4R in (1)1、R3May be the same substituent, with R4、R2Are the same substituents; or, R1、R2、R3、R4R in (1)1、R4May be the same substituent, with R2、R3Are the same substituents; or, R1、R2May be the same substituent, with R4、R3Are the same substituents.
The inventor finds that the two phenyl groups (or substituted phenyl groups) of diphenylamine can make electrons on N more stable, thereby being beneficial to improving the performance of the anode electrochromic material. R6 and R7 on the phenyl (or substituted phenyl) group are not particularly limited and can be designed by those skilled in the art according to the actual circumstances as long as they are not acidic groups. For example, according to some examples herein, R6 and R7 may each independently be hydrogen, methoxy, methyl, or trifluoromethyl. That is, R6 and R7 may be the same or different. More specifically, the positions of R6 and R7 are not particularly limited as long as they are located on the two benzene rings of diphenylamine, respectively.
More specifically, the anodic electrochromic material may be at least one of the following compounds:
Figure BDA0002546518720000051
the inventors have found that an anodic electrochromic material satisfying the above requirements may have better activity, faster response speed (electrochromic speed and fading speed), and deeper color change, and that an electrochromic device composed of a mixture of materials has stronger color expression compared to an electrochromic device composed of a single type of electrochromic active material, in which the anodic electrochromic material and the cathodic electrochromic material are contained in the composition. Specifically, the anodic electrochromic material loses electrons when the device is energized, and the color-changing color of the anodic material is presented, and the cathodic electrochromic material obtains electrons and presents the color-changing color of the cathodic material. Thus, the color ultimately presented is a mixture of the discolored colors of the two materials. On the one hand, the color presented by the color change mixture of the two materials can have better visual effect than the single color change. On the other hand, it is also more convenient for the skilled person to adjust the color of the electrochromic component according to the needs, such as adjusting the mixing ratio of the cathode electrochromic active material and the anode electrochromic material, etc.
According to some examples of the invention, the molar ratio of the anodic electrochromic material to the cathodic electrochromic material in the composition may be (0.35:1) to (2:1), in particular (0.5: 1) to (0.95: 1). The inventor finds that if the addition amount of the aniline anode electrochromic material in the composition is too large, for example, the molar ratio of the aniline anode electrochromic material to the aniline anode electrochromic material is more than 2:1, the formed device is easy to oxidize under the conditions of ultraviolet irradiation and the environment that the electrochromic material contains a small amount of water and oxygen, so that the performance of the device is reduced, and the color of the device is changed or even fails. When the aniline compound, namely the anode electrochromic material, is added in an excessively small amount, for example, the molar ratio of the aniline compound to the anode electrochromic material is less than 0.35:1, specifically 0.3: 1 or less, the electrochromic device tends to have a problem of insufficient contrast due to an excessively small content of the aniline compound. The inventors have found that aniline compounds are more active than viologen compounds, and therefore when the two are mixed, the color of the colored state is more provided by the aniline compounds (the electrochromic color is darker). And the anode electrochromic material has larger steric hindrance and electron cloud density, so the content of the aniline compound has larger influence on the electrochromic performance of the composition. Therefore, by adjusting the molar ratio of the two, a more ideal coloring/fading speed, and a high-transmittance and high-contrast electrochromic device can be obtained.
It should be noted that in the present application, the term "contrast ratio" refers to the difference between the transmittance of the electrochromic material or device in the high transmittance state and the low transmittance state, respectively. Namely:
contrast ratio of TH(high transmittance) -TL(low transmittance).
According to some examples of the present application, the specific type of antioxidant in the composition is not particularly limited, and may be, for example, an ultraviolet antioxidant. Specifically, the compound may include at least one of 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole, 2- (2 '-hydroxy-3' -tert-butyl-5 '-methylphenyl) -5-chlorobenzotriazole, 2- (2' -hydroxy-3 ',5' -di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2 '-hydroxy-3', 5 '-dipentylphenyl) benzotriazole, 2- (2' -hydroxy-5 '-tert-octylphenyl) benzotriazole, bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate, and 2- (2' -hydroxy-3 ',5' -di-tert-butylphenyl) benzotriazole. Thus, the durability, i.e., service life, of the electrochromic device prepared from the composition can be improved.
According to some examples of the present application, the type of the electrolyte is not particularly limited as long as it can provide the composition with an ion-transporting effect. Specifically, the lithium fluoroborate compound comprises at least one of lithium trifluoromethanesulfonate and lithium fluoroborate. The electrolyte is well adapted to other components in the composition and has a high ion transmission rate. The specific components of the solvent are not particularly limited as long as the components such as the above-mentioned anodic electrochromic material, cathodic electrochromic material, and the like can be well dissolved and dispersed. For example, at least one of propylene carbonate, tetrahydropyran, acetonitrile, toluene, xylene, DMF, and ethyl acetate may be included.
According to some examples of the invention, the composition has an anti-delamination agent therein. Since the composition proposed in the present application has a mixture of anodic electrochromic material and cathodic electrochromic material, delamination is easily occurred during use. The anti-layering agent can be an ester-group-containing polymer, the ester-group-containing polymer can have good adaptability with the aniline anode electrochromic material with the pyran ring, a good state can be kept through an aging resistance test, the poor layering of an electrochromic device prepared from the composition is prevented, the response speed of the electrochromic device is improved, and particularly the fading response time can be shortened. Specifically, the delamination inhibitor may be PMMA.
In accordance with the examples herein, the compositions presented herein control the water content and oxygen content of the compositions. The inventors have found that when the water oxygen content of the composition is not controlled, it is liable to result in a reduction in the durability of electrochromic devices made from the composition. Specifically, the water oxygen content of the composition may be reduced by means including, but not limited to, purification treatments of the components of the composition. Alternatively, the process of preparing the composition may be controlled, for example, by allowing the mixing operation to be carried out in an atmosphere which is water and oxygen-free, such as a glove box. The composition has a water content of less than 400ppm and an oxygen content of less than 400 ppm. Specifically, the purity of the anode electrochromic material in the composition is more than 99.97%, the purity of the cathode electrochromic material is more than 99.95%, and the purities of the electrolyte, the antioxidant, the anti-layering agent and the solvent are respectively and independently more than 99.5%. When the purity of each component in the composition meets the requirements, the composition has better durability.
According to examples of the present application, the composition may specifically comprise the following components: 300-800ppm of the antioxidant, 0.1-5 wt% of the anode electrochromic material, 0.2-5 wt% of the cathode electrochromic material, 0.3-1.2 wt% of the electrolyte and the balance of solvent, wherein the water content of the composition is less than 100ppm, and the oxygen content is less than 100 ppm.
Alternatively, according to further examples herein, the composition may include 300-800ppm of an antioxidant, the concentration of the anodic electrochromic material in the composition is 50-150mmol/L, the concentration of the cathodic electrochromic material in the composition is 80-200mmol/L, the concentration of the electrolyte in the composition is 20-80mmol/L, and the balance of the solvent. The composition has a water content of less than 10ppm and an oxygen content of less than 10 ppm. The inventor finds that reasonably increasing the content of the anode electrochromic material can improve the response speed of the fading of the composition, but the high content of the anode electrochromic material can cause the durability of an electrochromic device prepared by the composition to be reduced.
In order to further alleviate the delamination of the electrochromic material caused by long-term use, the composition may further comprise PMMA, for example, 2-8 wt% of PMMA may be contained.
Specifically, the composition can comprise 400-600ppm of 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole, 60-150mmol/L of anode electrochromic material, 100-150mmol/L of cathode electrochromic material in the composition, 40-60mmol/L of electrolyte in the composition and the balance of propylene carbonate, wherein the water content of the composition is less than 50ppm, and the oxygen content of the composition is less than 20 ppm.
The application adopts the anode electrochromic material with better performance, and the pyran ring contained in the anode electrochromic material can better disperse the electron cloud of the anode electrochromic material and provide proper steric hindrance, so that the anode electrochromic material has better electrochromic depth and activity. The proportion of the anode electrochromic material and the cathode electrochromic material is regulated and controlled, so that the composition has good color-changing contrast (namely high contrast) and durability, and the color-changing time is short. And the composition further improves the aging resistance of the composition by controlling the water content and the oxygen content in the composition and adding an antioxidant. The composition is also added with an anti-layering agent composed of PMMA and the like, so that the layering phenomenon of the electrochromic material is improved, and the response speed of the electrochromic material is further improved. The response speed of the composition can be 0.6-0.8s during coloring and can reach 0.8-1.2s during fading. The response speed can meet the requirements of most electronic equipment, for example, when the electronic equipment is used for shielding a camera, the camera cannot be used immediately due to overlong fading time of the device. The electrochromic device prepared by the composition has no obvious aging sign after being irradiated by ultraviolet rays for 168 hours at the test temperature of 85 ℃ and under the condition of electrifying at 1.2V, and has better aging resistance.
In yet another aspect of the present application, a method of making an electrochromic device utilizing the composition set forth above is presented. The method comprises the following steps: mixing the anodic electrochromic material, the cathodic electrochromic material, the electrolyte, the antioxidant, and the solvent to obtain the electrochromic material; and a filling space is defined between the first substrate and the second substrate, the electrochromic material is filled in the filling space, and sealing treatment is carried out to obtain the electrochromic device. Thereby, an electrochromic device having the aforementioned electrochromic material can be obtained simply.
In yet another aspect of the present application, an electrochromic device is presented. Referring to fig. 1, an electrochromic device has the composition described previously. The above composition may be used to form the electrochromic layer 300 of the electrochromic device. Thus, the electrochromic device has all the features and advantages of the composition described above, and will not be described herein again. In general, the electrochromic device has at least one of advantages of better durability, rapid discoloration/fading, higher contrast in colored and transparent states, and the like.
According to some specific examples of the present application, the electrochromic device may have two lens substrates, i.e., a first substrate 100 and a second substrate 200. The first and second substrates 100 and 200 are disposed opposite to each other and define a space for containing an electrochromic material, so that the electrochromic material composed of the aforementioned composition is filled between the first and second substrates 100 and 200 by means including, but not limited to, filling and the like and forms the electrochromic layer 300. In order to provide an electric field for color change to the electrochromic layer 300, a side of the first substrate 100 facing the electrochromic layer 300 may have a first electrode layer 110, a side of the second substrate 200 facing the electrochromic layer 300 may have a second electrode layer 210, and both the first electrode layer 110 and the second electrode layer 210 may be formed of a transparent conductive material. In order to realize sealing, a sealant 10 may be further disposed between the first substrate 100 and the second substrate 200.
In yet another aspect of the present application, a housing assembly is presented. The housing assembly includes: a transparent substrate and the electrochromic device described earlier, said electrochromic device being located on one side of said transparent substrate. Therefore, the shell component can obtain richer appearance effects by utilizing the electrochromic device and has at least one of the advantages of better durability, rapid color change/fading, higher contrast of a colored state and a transparent state and the like.
It is specifically noted that the housing assembly includes a transparent substrate, which may constitute all or part of the substrate of the housing assembly. In particular, the transparent substrate may correspond to the electrochromic device, i.e. the area of the housing assembly having the electrochromic device has a transparent substrate. Thereby, the color-changing color of the electrochromic device can be observed by a user through the transparent substrate.
In yet another aspect of the present application, an electronic device is presented. Referring to fig. 2, the electronic apparatus 3000 includes: in the case of the housing assembly 1000, the housing assembly 1000 defines a containing space, and the display screen and the motherboard (not shown) are located in the containing space, and the display screen is electrically connected to the motherboard. Also, the motherboard is electrically connected to the electrochromic device (not shown) in the housing assembly 1000. Therefore, the electronic equipment has at least one of the advantages of richer appearance, better durability, rapid color change/fading, higher contrast between a colored state and a transparent state and the like.
For example, the housing assembly 1000 may include, but is not limited to, a rear cover, a side frame, or an integrated housing of the electronic device 3000, and may also include a cover glass of the camera module 2000. Thus, electrochromic in the housing assembly 1000 can be utilized to provide an electrochromic appearance to the housing assembly 1000, or the electrochromic assembly can be utilized to shade the camera of the camera 2000. Specifically, when the camera does not work, the mainboard is used for controlling the electrochromic component to display the color in the colored state, and when the camera needs to work, the electrochromic component is quickly changed into the transparent state. Therefore, a better integrated appearance effect can be provided for the electronic equipment.
The following embodiments are provided to illustrate the present application, and should not be construed as limiting the scope of the present application. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
Preparing an anode electrochromic material, wherein the structural formula of the anode electrochromic material is as follows:
Figure BDA0002546518720000091
dissolving 19.7g of 4,4' -dimethyldiphenylamine and 19.3g of 4- (2-bromoethyl) tetrahydro-2H-pyran in 500g of toluene, uniformly stirring and mixing to obtain a mixed solution, and then mixing according to the molar ratio of potassium carbonate to 4- (2-bromoethyl) tetrahydro-2H-pyran of 1: 1, adding potassium carbonate, then adding 2g of cuprous iodide, heating to 60-90 ℃, heating, condensing and refluxing for 4-96h to obtain a crude product of the anode electrochromic material shown in the structural formula (1); and recrystallizing the crude product with acetonitrile to obtain the refined anode electrochromic material.
Reaction products of the reaction1H-NMR and13C-NMR analysis confirms that the target product is obtained, and the analysis results are as follows:
1H-NMR(300MHz,CDCL3)：6.84(4H),6.31(4H),3.6(2H),3.06(1H),2.35(2H),1.59(1H),1.51(2H),1.48(1H)。
13C-NMR(75MHz,CDCL3):146.1,130,127.9,119,66.9,45.7,34.8,32.5,31.6,24.3。
example 2
Preparing an anode electrochromic material, wherein the structural formula of the anode electrochromic material is as follows:
Figure BDA0002546518720000101
dissolving 22.9g of 4,4' -dimethoxydiphenylamine and 16.5g of 4-bromotetrahydropyran in 500g of toluene, uniformly stirring and mixing to obtain a mixed solution, and then mixing the mixed solution according to a molar ratio of potassium carbonate to 4-bromotetrahydropyran of 1: 1, adding potassium carbonate, then adding 1.5g of cuprous iodide, heating to 60-90 ℃, heating, condensing and refluxing for 4-96h to obtain a crude product of the anode electrochromic material shown in the structural formula (2); and recrystallizing the crude product with acetonitrile or toluene to obtain the refined anode electrochromic material shown as the structural formula (2).
Reaction products of the reaction1H-NMR and13C-NMR analysis confirms that the target product is obtained, and the analysis results are as follows:
1H-NMR(300MHz,CDCL3)：6.55(4H),6.32(4H),3.73(2H),3.6(2H),2.73(1H),1.78(2H)。
13C-NMR(75MHz,CDCL3):150.2,141.4,120.1,115.2,64.6,55.9,34.1。
example 3
Preparing an anode electrochromic material, wherein the structural formula of the anode electrochromic material is as follows:
Figure BDA0002546518720000102
dissolving 23.7g of m-trifluoromethyl diphenylamine and 22.6g of 4- (iodomethyl) tetrahydropyran in 500g of toluene, uniformly stirring and mixing to obtain a mixed solution, and then mixing the mixed solution according to a molar ratio of potassium carbonate to 4- (iodomethyl) tetrahydropyran of 1: 1, adding potassium carbonate, then adding 1g of cuprous iodide, heating to 60-90 ℃, heating, condensing and refluxing for 4-96h to obtain a crude product of the anode electrochromic material shown in the structural formula (3); and recrystallizing the crude product with acetonitrile or toluene to obtain the refined anode electrochromic material shown as the structural formula (3).
The reaction product was confirmed to be the target product by 1H-NMR and 13C-NMR analyses, and the analysis results were as follows:
1H-NMR(300MHz,CDCL3)：7.04(2H),6.97(1H),6.77(1H),6.62(1H),6.58(1H),6.43(3H),3.6(2H),3.02(1H),1.83(1H)1.51(1H)。
13C-NMR(75MHz,CDCL3):149.2,131.9,129.8,124.2,122.4,119.1,118.3,114.8,66.6,62.8,29.6,29。
comparative examples 1 to 3:
the anode material obtained in example 3 was used as an anode material, and the remaining components and contents are shown in table 1 below.
Comparative example 4:
the anode electrochromic material adopts a compound with the following structure:
Figure BDA0002546518720000111
the remaining components and amounts are shown in table 1 below.
The materials of examples 1-3 and comparative examples 1-4 were used to prepare electrochromic compositions in glove boxes, which were poured into electrochromic devices, and then sealed with glue, to obtain devices with electrochromic function. And (3) carrying out an aging resistance test in an aging resistance box, carrying out ultraviolet irradiation for 168 hours at 85 ℃ under a 1.2V power-on state, and carrying out aging resistance evaluation by using contrast parameter changes before and after the test. Wherein the electrolyte is lithium trifluoromethanesulfonate, the solvent is propylene carbonate, the antioxidant is 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole, and the purity of each component in the electrochromic composition is consistent. The proportions of the components in the electrochromic composition and the test results are given in table 1 below. The structural formulas of the cathodic electrochromic materials in the compositions of examples 1-3 and comparative examples 1-4 are as follows:
Figure BDA0002546518720000112
wherein R is1And R2Is methyl, X-Is composed of
Figure BDA0002546518720000121
TABLE 1
Figure BDA0002546518720000122
The comparison shows that the aging resistance is reduced due to insufficient raw material purity and excessive water and oxygen content (such as comparative example 1), and the contrast is seriously attenuated after the test; the aging resistance was seriously deteriorated when the antioxidant was not added (comparative example 2), the molar ratio was too large (comparative example 3). And the structural formula of the present application has better aging resistance than the composition shown in comparative example 4.
Referring to fig. 3 and 4 specifically, from the performance graphs (setting the maximum value of the test voltage to be 1.5V, recording the current change condition of the device) of the electrochemical tests of the electrochromic devices obtained in example 1 and comparative example 1 under the same test conditions (85 ℃, 1.2V power-on state, and 72h of ultraviolet irradiation), it can be seen that the device in comparative example 1 cannot recover the initial functional state after being subjected to coloring and fading changes, and obvious performance attenuation phenomena (both the oxidation characteristic peak position and the reduction characteristic peak position of the CV curve shift) occur.
Various examples and features of different examples described in this specification can be combined and combined by one skilled in the art without contradiction.
In the description of the present application, the terms "upper", "lower", and the like indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience of describing the present application but do not require that the present application must be constructed and operated in a specific orientation, and thus, cannot be construed as limiting the present application.
Various examples and features of different examples described in this specification can be combined and combined by one skilled in the art without contradiction. In addition, it should be noted that the terms "first" and "second" are used in this specification for descriptive purposes only and are intended to visually distinguish between two adhesive layers and two release film layers in a decorative film sheet, and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated.
Although embodiments of the present application have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present application, and that variations, modifications, substitutions and alterations may be made to the above embodiments by those of ordinary skill in the art within the scope of the present application.

Claims (13)

1. A composition for use in the preparation of an electrochromic device, comprising:
the anode electrochromic material and the cathode electrochromic material in the composition have a molar ratio of (0.35:1) - (2:1), the water content of the composition is less than 400ppm, the oxygen content of the composition is less than 400ppm, the purity of the anode electrochromic material is more than 99.97%, the purity of the cathode electrochromic material is more than 99.95%, and the purities of the electrolyte, the antioxidant and the solvent are respectively and independently more than 99.5%,
the anode electrochromic material has a structural formula shown as a formula (I):
Figure FDA0002546518710000011
wherein R is1、R2、R3、R4Each independently is hydrogen, halogen, alkyl, halogenated alkyl or oxygen-containing carbon hydrogen functional group;
y is methyl, ethyl or a bond;
r6 and R7 are each independently hydrogen, methoxy, methyl or trifluoromethyl.
2. The composition of claim 1, wherein R is1、R2、R3、R4Are each independently C1～C8Saturated or unsaturated alkyl groups.
3. The composition of claim 1, wherein the oxygen-containing hydrocarbon functional groups comprise at least one of carbonyl groups and ester groups.
4. The composition of claim 1, wherein the anodic electrochromic material is at least one selected from the group consisting of:
Figure FDA0002546518710000012
5. the composition of claim 1, wherein the cathodic electrochromic material comprises a viologen-based compound.
6. The composition of claim 1, the antioxidant includes at least one of 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole, 2- (2 '-hydroxy-3' -tert-butyl-5 '-methylphenyl) -5-chlorobenzotriazole, 2- (2' -hydroxy-3 ',5' -di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2 '-hydroxy-3', 5 '-dipentylphenyl) benzotriazole, 2- (2' -hydroxy-5 '-tert-octylphenyl) benzotriazole, bis (2,2,6, 6-tetramethyl-4-piperidinyl) sebacate, 2- (2' -hydroxy-3 ',5' -di-tert-butylphenyl) benzotriazole;
optionally, the electrolyte comprises at least one of lithium trifluoromethanesulfonate and lithium fluoroborate;
optionally, the solvent comprises at least one of propylene carbonate, tetrahydropyran, acetonitrile, toluene, xylene, DMF, ethyl acetate.
7. The composition of claim 1, wherein the molar ratio of the anodic electrochromic material to the cathodic electrochromic material is from (0.5: 1) to (0.95: 1).
8. The composition of claim 1,
the composition contains the antioxidant with the concentration of 300-800ppm, the concentration of the anode electrochromic material in the composition is 50-150mmol/L, the concentration of the cathode electrochromic material in the composition is 80-200mmol/L, the concentration of the electrolyte in the composition is 20-80mmol/L, and the balance is the solvent,
the purity of each component in the composition is more than 99.5%, the water content is less than 100ppm, and the oxygen content is less than 100 ppm.
9. The composition of claim 8,
the composition comprises 400-600ppm of the antioxidant, the concentration of the anode electrochromic material in the composition is 60-150mmol/L, the concentration of the cathode electrochromic material in the composition is 100-150mmol/L, the concentration of the electrolyte in the composition is 40-60mmol/L, and the balance of the solvent,
said water content of said composition is less than 50ppm and said oxygen content is less than 20 ppm.
10. A method of making an electrochromic device using the composition of any of claims 1-9, comprising:
mixing an anodic electrochromic material, a cathodic electrochromic material, an electrolyte and a solvent to obtain the electrochromic material;
and a filling space is defined between the first substrate and the second substrate, the electrochromic material is filled in the filling space, and sealing treatment is carried out to obtain the electrochromic device.
11. An electrochromic device, characterized in that it has a composition according to any one of claims 1 to 9.
12. A housing assembly, comprising:
a transparent substrate and the electrochromic device of claim 11, said electrochromic device being located on one side of said transparent substrate.
13. An electronic device, comprising:
the housing assembly of claim 12, having a receiving space;
display screen and mainboard, the display screen with the mainboard is located inside the accommodation space, the display screen with the mainboard electricity is connected.
CN202010562768.3A 2020-06-18 2020-06-18 Composition, electrochromic device, housing assembly, and electronic apparatus Pending CN111592874A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010562768.3A CN111592874A (en) 2020-06-18 2020-06-18 Composition, electrochromic device, housing assembly, and electronic apparatus

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010562768.3A CN111592874A (en) 2020-06-18 2020-06-18 Composition, electrochromic device, housing assembly, and electronic apparatus

Publications (1)

Publication Number Publication Date
CN111592874A true CN111592874A (en) 2020-08-28

Family

ID=72181187

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010562768.3A Pending CN111592874A (en) 2020-06-18 2020-06-18 Composition, electrochromic device, housing assembly, and electronic apparatus

Country Status (1)

Country Link
CN (1) CN111592874A (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2992517B1 (en) * 1998-07-16 1999-12-20 コレア クムホ ぺトロケミカル シーオー エルティーディー Method for producing sulfonium salt
JP2007178858A (en) * 2005-12-28 2007-07-12 Fujifilm Corp Photosensitive composition and pattern forming method using the photosensitive composition
JP2018108959A (en) * 2016-12-29 2018-07-12 三洋化成工業株式会社 Method for producing halogenated sulfonium salt

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2992517B1 (en) * 1998-07-16 1999-12-20 コレア クムホ ぺトロケミカル シーオー エルティーディー Method for producing sulfonium salt
JP2007178858A (en) * 2005-12-28 2007-07-12 Fujifilm Corp Photosensitive composition and pattern forming method using the photosensitive composition
JP2018108959A (en) * 2016-12-29 2018-07-12 三洋化成工業株式会社 Method for producing halogenated sulfonium salt

Similar Documents

Publication Publication Date Title
JP3798980B2 (en) Color-stabilized electrochromic device
US10626133B2 (en) Electrochromic compound, electrochromic composition, and display element
JP4816069B2 (en) Electrochromic device
JP4929995B2 (en) Electrochromic device
KR101270862B1 (en) Light control material and light control film
CN107429158A (en) Electrochromic compounds, electrochromic compositions, electric driven color-changing part and electrochromism Light modulating device
KR102180373B1 (en) Electrochromic device comprising the electrochromic compound and method of preparing the same
CN111607386A (en) Electrochromic material, composition, preparation method, electrochromic device, shell assembly and electronic equipment
CN106916099A (en) A kind of cathodic electrochromic compound in electrochromic device and preparation method thereof
CN111592874A (en) Composition, electrochromic device, housing assembly, and electronic apparatus
CN111269710B (en) Mobile terminal, shell component, electrochromic material and preparation method thereof
CN111676009A (en) Composition, electrochromic device and preparation method thereof, shell assembly and electronic equipment
CN111607385A (en) Composition, electrochromic device and preparation method thereof, shell assembly and electronic equipment
KR20190037062A (en) Electrochromic complex, electrochromic device containing the same and manufacturing method of the electrochromic device
JP7359441B2 (en) electrochromic element
CN111718291A (en) Cathode electrochromic material and preparation and application thereof
JP2007279572A (en) Electrochromic device
CN106928129A (en) A kind of cathodic electrochromic compound in electrochromic device
CN106916582A (en) A kind of cathodic electrochromic compound and associated media and device
CN115448955A (en) Mononuclear metal complex and preparation method and application thereof
JP2012017265A (en) Electrochromic complex compound and electrochromic element using the same
JP2013250520A (en) Electrochromic compound, electrochromic composition, and display element

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination