CN113678057B - Nanorods, methods of making the same, and light valves containing the same - Google Patents
Nanorods, methods of making the same, and light valves containing the same Download PDFInfo
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- CN113678057B CN113678057B CN201980093898.2A CN201980093898A CN113678057B CN 113678057 B CN113678057 B CN 113678057B CN 201980093898 A CN201980093898 A CN 201980093898A CN 113678057 B CN113678057 B CN 113678057B
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- alkaline earth
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- 239000002073 nanorod Substances 0.000 title claims abstract description 103
- 238000000034 method Methods 0.000 title claims description 23
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000011737 fluorine Substances 0.000 claims abstract description 64
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000002834 transmittance Methods 0.000 claims abstract description 25
- 239000002245 particle Substances 0.000 claims description 67
- -1 nitrogen-containing heterocyclic carboxylic acid Chemical class 0.000 claims description 38
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 claims description 34
- 239000006194 liquid suspension Substances 0.000 claims description 23
- 239000011810 insulating material Substances 0.000 claims description 22
- 229910001515 alkali metal fluoride Inorganic materials 0.000 claims description 19
- 229910001618 alkaline earth metal fluoride Inorganic materials 0.000 claims description 19
- 229910001615 alkaline earth metal halide Chemical group 0.000 claims description 18
- 229940117955 isoamyl acetate Drugs 0.000 claims description 17
- 229910001508 alkali metal halide Inorganic materials 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 229920002678 cellulose Polymers 0.000 claims description 14
- 239000001913 cellulose Substances 0.000 claims description 14
- 150000008045 alkali metal halides Chemical group 0.000 claims description 13
- 239000011630 iodine Substances 0.000 claims description 13
- 229910052740 iodine Inorganic materials 0.000 claims description 13
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 239000006228 supernatant Substances 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 9
- FJFYFBRNDHRTHL-UHFFFAOYSA-N tris(8-methylnonyl) benzene-1,2,4-tricarboxylate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC(C)C)C(C(=O)OCCCCCCCC(C)C)=C1 FJFYFBRNDHRTHL-UHFFFAOYSA-N 0.000 claims description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 8
- 239000000020 Nitrocellulose Substances 0.000 claims description 8
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 8
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 8
- 239000011707 mineral Substances 0.000 claims description 8
- 229920001220 nitrocellulos Polymers 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000003921 oil Substances 0.000 claims description 8
- 235000019198 oils Nutrition 0.000 claims description 8
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 8
- 239000008158 vegetable oil Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 6
- 239000001856 Ethyl cellulose Substances 0.000 claims description 6
- 229920001249 ethyl cellulose Polymers 0.000 claims description 6
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 125000001153 fluoro group Chemical group F* 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- SIXWIUJQBBANGK-UHFFFAOYSA-N 4-(4-fluorophenyl)-1h-pyrazol-5-amine Chemical compound N1N=CC(C=2C=CC(F)=CC=2)=C1N SIXWIUJQBBANGK-UHFFFAOYSA-N 0.000 claims description 4
- UNMYWSMUMWPJLR-UHFFFAOYSA-L Calcium iodide Chemical compound [Ca+2].[I-].[I-] UNMYWSMUMWPJLR-UHFFFAOYSA-L 0.000 claims description 4
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 4
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 4
- NKQIMNKPSDEDMO-UHFFFAOYSA-L barium bromide Chemical compound [Br-].[Br-].[Ba+2] NKQIMNKPSDEDMO-UHFFFAOYSA-L 0.000 claims description 4
- 229910001620 barium bromide Inorganic materials 0.000 claims description 4
- SGUXGJPBTNFBAD-UHFFFAOYSA-L barium iodide Chemical compound [I-].[I-].[Ba+2] SGUXGJPBTNFBAD-UHFFFAOYSA-L 0.000 claims description 4
- 229910001638 barium iodide Inorganic materials 0.000 claims description 4
- 229940075444 barium iodide Drugs 0.000 claims description 4
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 4
- 229910001622 calcium bromide Inorganic materials 0.000 claims description 4
- 229940059251 calcium bromide Drugs 0.000 claims description 4
- WGEFECGEFUFIQW-UHFFFAOYSA-L calcium dibromide Chemical compound [Ca+2].[Br-].[Br-] WGEFECGEFUFIQW-UHFFFAOYSA-L 0.000 claims description 4
- 229910001640 calcium iodide Inorganic materials 0.000 claims description 4
- 229940046413 calcium iodide Drugs 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 235000019438 castor oil Nutrition 0.000 claims description 4
- 239000004359 castor oil Substances 0.000 claims description 4
- 229920001727 cellulose butyrate Polymers 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- KWKXNDCHNDYVRT-UHFFFAOYSA-N dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 0.000 claims description 4
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 4
- 230000005484 gravity Effects 0.000 claims description 4
- 239000004014 plasticizer Substances 0.000 claims description 4
- 229920001083 polybutene Polymers 0.000 claims description 4
- 229920002545 silicone oil Polymers 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 235000012424 soybean oil Nutrition 0.000 claims description 4
- 239000003549 soybean oil Substances 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 2
- 229920002301 cellulose acetate Polymers 0.000 claims description 2
- 230000005855 radiation Effects 0.000 abstract description 11
- 230000007774 longterm Effects 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000000725 suspension Substances 0.000 description 12
- 102100035182 Plastin-2 Human genes 0.000 description 11
- 101710081231 Plastin-2 Proteins 0.000 description 11
- 239000002253 acid Substances 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 10
- 238000012512 characterization method Methods 0.000 description 9
- 230000005684 electric field Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 229910012513 LiSbF 6 Inorganic materials 0.000 description 4
- LOUPRKONTZGTKE-WZBLMQSHSA-N Quinine Chemical compound C([C@H]([C@H](C1)C=C)C2)C[N@@]1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-WZBLMQSHSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- PDWBGRKARJFJGI-UHFFFAOYSA-N 2-phenylcyclohexa-2,4-dien-1-one Chemical compound O=C1CC=CC=C1C1=CC=CC=C1 PDWBGRKARJFJGI-UHFFFAOYSA-N 0.000 description 3
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- 230000005653 Brownian motion process Effects 0.000 description 2
- 235000001258 Cinchona calisaya Nutrition 0.000 description 2
- 229910013063 LiBF 4 Inorganic materials 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000004983 Polymer Dispersed Liquid Crystal Substances 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 238000005537 brownian motion Methods 0.000 description 2
- LOUPRKONTZGTKE-UHFFFAOYSA-N cinchonine Natural products C1C(C(C2)C=C)CCN2C1C(O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000004673 fluoride salts Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- KOUKXHPPRFNWPP-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid;hydrate Chemical compound O.OC(=O)C1=CN=C(C(O)=O)C=N1 KOUKXHPPRFNWPP-UHFFFAOYSA-N 0.000 description 2
- 229960000948 quinine Drugs 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- OCLTZILENWBWIY-HKPQTANOSA-N (r)-[(2s,4s,5r)-5-ethenyl-1-azabicyclo[2.2.2]octan-2-yl]-(6-methoxyquinolin-4-yl)methanol;molecular iodine;sulfuric acid;dihydroiodide Chemical compound I.I.II.II.OS(O)(=O)=O.OS(O)(=O)=O.OS(O)(=O)=O.C([C@H]([C@H](C1)C=C)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OC)C=C21.C([C@H]([C@H](C1)C=C)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OC)C=C21.C([C@H]([C@H](C1)C=C)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OC)C=C21.C([C@H]([C@H](C1)C=C)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OC)C=C21 OCLTZILENWBWIY-HKPQTANOSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- IKRJEDLJNOBPDW-UHFFFAOYSA-N bismuth manganese(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Bi+3] IKRJEDLJNOBPDW-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229960002050 hydrofluoric acid Drugs 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000004028 organic sulfates Chemical class 0.000 description 1
- NIPZZXUFJPQHNH-UHFFFAOYSA-N pyrazine-2-carboxylic acid Chemical compound OC(=O)C1=CN=CC=N1 NIPZZXUFJPQHNH-UHFFFAOYSA-N 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- SMYKBXMWXCZOLU-UHFFFAOYSA-N tris-decyl benzene-1,2,4-tricarboxylate Chemical compound CCCCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCCCC)C(C(=O)OCCCCCCCCCC)=C1 SMYKBXMWXCZOLU-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B26/00—Optical devices or arrangements for the control of light using movable or deformable optical elements
- G02B26/02—Optical devices or arrangements for the control of light using movable or deformable optical elements for controlling the intensity of light
-
- 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
- G02F1/17—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 variable-absorption elements not provided for in groups G02F1/015 - G02F1/169
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Optics & Photonics (AREA)
- General Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biophysics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Composite Materials (AREA)
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
Abstract
The nanorod is an inorganic-organic hybridized fluorine-containing nanorod, the light valve containing the inorganic-organic hybridized fluorine-containing nanorod has higher total light transmittance, and can enhance the stability of the light valve to water and ultraviolet radiation, better protect the light valve from being damaged and is very important for improving the long-term stability of a light valve device.
Description
Technical Field
The present invention relates to a nanorod, a method of manufacturing the same, and a light valve including the same, and more particularly, to an organic-inorganic hybrid fluorine-containing anion nanorod and a light valve including the same.
Background
A light valve is a device that can regulate the transmittance of light passing through itself. As one of the light valves, a device capable of controlling light transmittance by adjusting a voltage applied thereto is also called an electrochromic device. According to the operating principle of electrochromic devices, it can be classified into Polymer Dispersed Liquid Crystal (PDLC), electrochemical devices (EC) and Suspended Particle Devices (SPD). Specifically, a light valve (hereinafter, abbreviated as LV) refers to a device that can control light transmittance through a medium by adjusting the level of Alternating Current (AC) voltage applied to the medium.
Eighty five years ago, light valve devices comprising nanoparticles were invented. Later on, suspended Particle Device (SPD) films were further developed, comprising a light modulating unit of a suspension, which unit consists of a suspension containing mixed metal oxides, such as bismuth manganese oxide rod-like particles. Needle-like quinine iodisulfate (HERAPATHITE) was the multi-iodide used for SPD at the earliest, however quinine iodisulfate is thermally unstable and unstable to some chemicals, such as methanol, ethylene glycol monoethyl ether, etc., even in trace amounts. Poor stability is a fatal problem for SPD light valve devices. To address the stability problem, other types of polyhalides have been investigated and used in SPD light valves. However, the prior art is relatively sensitive to ultraviolet radiation and water vapor erosion, and is used for manufacturing SPD light valve devices, and long-term stability is a problem which needs to be solved. Thus, a challenge is to prepare rod-shaped particles that are more stable and useful in SPD light valve devices.
Organic lithium ion batteries are one of the determining factors for recent market of electric vehicles, and electrolytes are one of the five key factors of organic lithium ion batteries. The electrolyte must be both soluble in suitable organic solvents and ionically conductive and must also have high stability. These requirements for organic lithium ion battery electrolytes are just as basic as the metal compounds for the preparation of rod-like particles for SPD light valve devices. Therefore, the rod-shaped particles of the SPD light valve device can be prepared stably by referring to electrolyte salt of the organic lithium ion battery.
The earliest organic lithium ion battery electrolyte salts were lithium perchlorate, and many of them currently used are lithium tetrafluoroborate, lithium hexafluorophosphate, lithium hexafluoroantimonate, and the like, and organic silicates, organic sulfates, and the like, have been studied.
It can be seen that the rod-shaped particles of the SPD light valve device have the problem of low stability in the prior art. Therefore, there is a need to develop a better material that can have more stable performance by adjusting the voltage, with a wider range of control light transmittance.
Disclosure of Invention
In order to solve the technical problems, the invention provides a nano rod which comprises an inorganic-organic complex containing fluorine atoms, carbon atoms and nitrogen atoms.
Preferably, the components of the inorganic-organic complex comprise a component A, B, C, D, E, wherein the component A is iodine, the component B is alkali metal halide or alkaline earth metal halide, the component C is alkali metal fluoride or alkaline earth metal fluoride, the component D is nitrogen-containing heterocyclic carboxylic acid or nitrogen-containing heterocyclic carboxylic ester, the component E is modified cellulose, and the mass ratio of the components is A: b: c: d: e is 0.3 to 3:1:0.1 to 1:0.5 to 4:0.2 to 3.
In addition, the particle length of the nano rod is 50-800 nm, and the aspect ratio between the particle length and the particle width is 2-30.
Preferably, the nanorods have a particle length of 200 to 500nm and an aspect ratio between the particle length and the particle width of preferably 5 to 15.
Preferably, the purity of the iodine is not less than 98%.
Preferably, the alkaline earth metal halide is at least one of calcium iodide, barium iodide, calcium bromide, and barium bromide.
Preferably, the purity of the alkali metal halide or alkaline earth metal halide is not less than 99%.
Preferably, the fluoride containing acid radical in the alkali metal fluoride containing acid salt or alkaline earth metal fluoride containing acid salt is at least one of BF 4 -,PF6 -,SbF6 -.
Preferably, the metal ion in the alkali metal fluoride or alkaline earth metal fluoride is at least one of Li +,Na+,K+,Ca2+,Sr2+,Ba2+.
Preferably, the alkali metal fluoride or alkaline earth metal fluoride has a purity of not less than 99%.
Preferably, the modified cellulose is at least one of nitrocellulose, ethylcellulose, cellulose acetate and cellulose butyrate.
Preferably, the nitrogen-containing heterocyclic carboxylic acid or nitrogen-containing heterocyclic carboxylic acid ester is at least one of the following compounds:
n is 1-4; /(I) N is 1-3;
n is 1-2; /(I) N is 1-5;
n is 1-4; /(I)
N is 1-4; /(I)N is 1-7;
n is 1-7; /(I) N is 1-6;
The present application also provides a light valve capable of controlling light transmittance, preferably comprising two transparent electrodes (i.e. a first transparent electrode and a second transparent electrode) and a liquid suspension medium sandwiched between the two transparent electrodes, wherein: the nano rods are uniformly dispersed in the liquid suspension medium, and the buoyancy and gravity of the nano rods in the liquid suspension medium are balanced, so that the nano rods can be stably suspended in the liquid suspension medium and can move freely; when the LED lamp works, the two transparent electrodes can be connected with alternating current with adjustable voltage.
Preferably, the liquid suspension medium is a non-conductive liquid, which is at least one of a mineral insulating material, a synthetic insulating material, and a vegetable oil.
Preferably, wherein the mineral insulating material comprises transformer oil.
Preferably, the synthetic insulating material is at least one of silicone oil, fluorocarbon organic compound, plasticizer (dioctyl phthalate, dibutyl phthalate, diisooctyl phthalate and triisodecyl trimellitate (TDTM)), dodecylbenzene, polybutene oil.
Preferably, the vegetable oil is at least one of castor oil, soybean oil and rapeseed oil.
Preferably, each of the transparent electrodes includes at least one of ITO conductive glass, ITO/PET conductive film, nano Ag wire/PET conductive film, nano Cu wire/PET conductive film.
Preferably, the peripheries of the two transparent electrodes are sealed by an insulating material, and the insulating material is epoxy resin.
Preferably, the voltage regulation range of the alternating current is 5-500V alternating current.
Here, the value of the alternating current refers to the effective value.
In addition, the application also provides a film comprising one of the above light valves.
In addition, the application also provides a method for synthesizing the inorganic-organic hybrid fluorine-containing nanorod, which takes isoamyl acetate as a solvent, takes low-carbon alcohol with the carbon number less than 8 and distilled water as charge balancing agents, and comprises the following components in percentage by mass: and the component B comprises the following components: and C, component: and D, a component: and E component: lower alcohols: water: isoamyl acetate 0.2-5: 1:0.1 to 1:0.4 to 3:0.5 to 5:0.1 to 8:0.01 to 5: 5-100, the method comprises the following steps:
a. Adding E component modified cellulose, A component iodine, isoamyl acetate, B component alkali metal halide or alkaline earth metal halide, C component alkali metal fluoride or alkaline earth metal fluoride, heating to 5-150 ℃, adding low carbon alcohol, distilled water and D component nitrogen heterocyclic carboxylic acid or nitrogen heterocyclic carboxylic ester after iodine is dissolved, continuously heating to maintain the temperature, stirring for reacting for 0.1-20 hours, and naturally cooling;
b. centrifuging the reaction solution for 0.2-2 hours under the condition of not more than 5000G to remove large-particle products, centrifuging supernatant for 0.5-20 hours under the condition of not less than 10000G, and discarding supernatant to obtain light-operated particles, thereby obtaining the inorganic-organic hybridized fluorine-containing nanorods.
The invention provides an inorganic-organic hybrid fluorine-containing nano rod, the main body of which is an inorganic-organic complex comprising fluoric acid radicals. Wherein the metal atom in the alkali metal or alkaline earth metal compound (component B and C) forms a chemical bond with the nitrogen atom in the nitrogen-containing heterocyclic carboxylic acid or ester (component D). Iodine (component a) also forms a multi-iodine complex with the metal atoms in the alkali or alkaline earth metal compounds (components B and C). The fluoride-containing acid radical also participates in the formation of the polyiodine complex. The selected modified cellulose can inhibit the aggregation of the inorganic-organic hybridized fluorine-containing nanorods, control the production speed of different crystal planes, and promote the rapid growth of one crystal plane in preference to other crystal planes, thereby generating a rod-like morphology.
The water and the low-carbon alcohol added in the preparation method balance the inorganic-organic complex in a hydrogen bond or coordination bond mode, play roles in balancing charges and the like, and enable the structure of the inorganic-organic complex to be more stable.
When no electric field is applied (in a closed state), the inorganic-organic hybrid fluorine-containing nanorods in the liquid suspension are randomly dispersed due to Brownian motion, and light beams entering the light valve are absorbed and/or scattered at the moment, so that the light valve has poor light transmittance and is relatively dark. When an electric field is applied (on state), the nanorods are polarized by the electric field and are aligned in a direction in which the electric fields are parallel to each other, so that most of the light can pass through the light valve, and the light valve has effectively enhanced light transmittance and is relatively transparent.
Experiments show that the total light transmittance of the light valve reaches 68.1%, the defect that the light valve has a small light transmittance adjusting range in the prior art is overcome, the light transmittance can be adjusted in a wider range, the stability of rod-shaped particles is obviously improved, a better technical effect is obtained, and the light valve has a good application prospect.
The inorganic-organic hybridized fluorine-containing nanorod and the light valve containing the nanorod are synthesized by a one-step method, and the nanorod takes advantages of fluorine-containing materials, nano materials and the like into consideration, has a plurality of characteristics and coordinated actions, so that the material has unique performance, and the light valve prepared from the material has excellent performance, can adjust light transmittance in a wider range, has higher stability and has good application prospect.
Drawings
FIG. 1 is a schematic diagram of a light valve of the present invention prior to power-up;
FIG. 2 is a schematic diagram of the structure of the light valve of the present invention after power-on.
Detailed Description
According to one embodiment of the present invention, there is provided a nanorod including an inorganic-organic complex containing fluorine atoms, carbon atoms, nitrogen atoms.
The nanorod is an inorganic-organic complex, the composition of the nanorod comprises A, B, C, D, E components, wherein the component A is iodine, the component B is alkali metal halide or alkaline earth metal halide, the component C is alkali metal fluoride or alkaline earth metal fluoride, the component D is nitrogen-containing heterocyclic carboxylic acid or nitrogen-containing heterocyclic carboxylic ester, the component E is modified cellulose, and the mass ratio of the components is A: b: c: d: e is 0.3 to 3:1:0.1 to 1:0.5 to 4:0.2 to 3.
The purity of the iodine is not less than 98%. Iodine has a large atomic diameter and is easily polarized, and its dipole moment is large, and thus is used to produce light polarizing particles.
The alkali metal halide or alkaline earth metal halide may be selected from commercial compounds purchased directly, such as calcium iodide, barium iodide, calcium bromide, barium bromide, etc., and preferably the purity of the alkali metal halide or alkaline earth metal halide selected is not less than 99%.
The fluoride containing acid radical in the alkali metal fluoride containing acid salt or alkaline earth metal fluoride containing acid salt is at least one of BF 4 -,PF6 -,SbF6 -.
The alkali metal fluoride-containing salt or alkaline earth metal fluoride-containing salt may be selected from commercial compounds such as lithium tetrafluoroborate, lithium hexafluorophosphate, lithium hexafluoroantimonate and the like, which are directly purchased. Preferably, the alkali metal or alkaline earth metal fluoride salt is selected to have a purity of not less than 99%.
The nitrogen-containing heterocyclic carboxylic acid or nitrogen-containing heterocyclic carboxylic acid ester is exemplified by the compounds listed in the following table, but is not limited to the compounds in table 1.
Table 1:
The modified cellulose is at least one of nitrocellulose, ethyl cellulose, cellulose acetate and cellulose butyrate.
The nanorods have a particle length of 50 to 800nm, more preferably 200 to 500nm, and an aspect ratio between the particle length and the particle width of 2 to 30, more preferably 5 to 15.
The body of the fluorine-containing nano rod is an inorganic-organic complex. The metal atom in the alkali metal or alkaline earth metal halide (component B) forms a chemical bond with the nitrogen atom in the nitrogen-containing heterocyclic carboxylic acid or ester (component D). Iodine (component a), iodide ion (component B), fluoride-containing acid radical (component C) also form a fluorine-containing multi-iodine complex with the metal atom in the alkali metal or alkaline earth metal halide (component B). The selected modified cellulose can inhibit the agglomeration of the formed fluorine-containing nanorods, control the production speed of different crystal planes, and promote the rapid growth of one crystal plane in preference to other crystal planes, thereby generating a rod-like morphology.
Here, in order to realize the production of the inorganic-organic hybrid fluorine-containing nanorods of the present invention, the present invention provides a method for synthesizing the inorganic-organic hybrid fluorine-containing nanorods: the method takes isoamyl acetate as a solvent, low-carbon alcohol with the carbon number less than 8 and distilled water as charge balancing agents, and the mass ratio of each component is that A component: and the component B comprises the following components: and C, component: and D, a component: and E component: lower alcohols: water: isoamyl acetate 0.2-5: 1:0.1 to 1:0.4 to 3:0.5 to 5:0.1 to 8:0.01 to 5: 5-100, the specific preparation steps comprise:
a. Adding E component modified cellulose, A component iodine, isoamyl acetate, B component alkali metal halide or alkaline earth metal halide, C component alkali metal fluoric acid salt or alkaline earth metal fluoric acid salt in corresponding mass component proportion into a glass flask, heating to 5-150 ℃, adding low-carbon alcohol, distilled water and D component nitrogen heterocyclic carboxylic acid or nitrogen heterocyclic carboxylic acid ester after iodine dissolution, continuously heating to maintain the temperature, stirring for reacting for 0.1-20 hours, and naturally cooling;
b. Centrifuging the reaction solution at a temperature of not more than 5000G for 0.2-2 hours to remove large-particle products, centrifuging supernatant at a temperature of not less than 10000G for 0.5-20 hours, and discarding supernatant to obtain light-operated particles, thereby obtaining the inorganic-organic hybridized fluorine-containing nanorods.
The water and the low-carbon alcohol added in the method balance the shell inorganic-organic complex in a hydrogen bond or coordination bond mode, play roles of balancing charges and the like, and enable the structure of the inorganic-organic complex to be more stable.
The light valve capable of controlling light transmittance comprises two transparent electrodes 100 and a liquid suspension medium 300 sandwiched between the electrodes, wherein the inorganic-organic hybrid fluorine-containing nanorods 200 are uniformly dispersed in the liquid suspension medium 300, and the buoyancy and gravity of the nanorods 200 in the liquid suspension medium 300 are balanced, so that the nanorods can stably suspend in the liquid suspension medium 300 and can freely move; an alternating current with adjustable voltage is connected to the two transparent electrodes 300.
The liquid suspension medium 300 is a non-conductive liquid, which is at least one of a mineral insulating material, a synthetic insulating material, and a vegetable oil. The mineral insulating material is transformer oil, etc. The synthetic insulating material is at least one of organic silicone oil, fluorocarbon organic compound, plasticizer (dioctyl phthalate, dibutyl phthalate, diisooctyl phthalate and triisodecyl trimellitate (TDTM)), dodecylbenzene, polybutene oil and the like. The vegetable oil is at least one of castor oil, soybean oil and rapeseed oil. Here, the liquid suspension medium 300 for the light valve of the present invention is not limited to the above, and may be any liquid light valve suspension known in the art, and may be formulated according to techniques well known to those skilled in the art.
The transparent electrode 100 is at least one of ITO conductive glass, ITO/PET conductive film, nano Ag wire/PET conductive film, nano Cu wire/PET conductive film.
The two transparent electrodes 100 are sealed with an insulating material, which is epoxy resin.
The light valve adopts alternating current to drive and adjust the light transmittance, and preferably 5-500V alternating current; preferably, 20-300V ac; more preferably, 50 to 150V ac power is preferred.
When no electric field is applied (in a closed state), the inorganic-organic hybrid fluorine-containing nanorods 200 in the liquid suspension medium 300 are randomly dispersed due to Brownian motion, and at the moment, light beams entering the light valve are absorbed and/or scattered, the light valve has poor light transmittance and is relatively dark, and the structure is shown in figure 1. When an electric field is applied (on state), the inorganic-organic hybrid fluorine-containing nanorods 200 are polarized by the electric field so as to be aligned in a direction in which the electric fields are parallel to each other, thereby allowing most of light to pass through the light valve, which is effectively enhanced in light transmittance and relatively transparent, and has a structure as shown in fig. 2.
The following methods were used to evaluate the stability of inorganic-organic hybrid fluorine-containing nanorods to water and to ultraviolet radiation.
Method of assessing stability to water:
The stability to water reflects the resistance of light valve devices using inorganic-organic hybrid fluorine-containing nanorods to water vapor. The test method is to place the light valve device in an environment box with 95% relative humidity and 60 ℃ air temperature and no xenon lamp irradiation, and compare the time required for different light valve devices to turn colorless. The shorter the time required, the poorer the stability to water.
A method of assessing stability to ultraviolet radiation:
The stability to uv radiation reflects the resistance of light valve devices using inorganic-organic hybrid fluorine-containing nanorods to uv radiation. The test method is to place the light valve device in an environment box under the irradiation of a 500W/m 2 xenon lamp with 15% relative humidity and air temperature of 60 ℃ and compare the time required by different light valve devices to turn colorless. The shorter the time required, the poorer the stability to ultraviolet radiation.
The invention is further illustrated by the following examples.
Example 1 preparation of inorganic-organic hybrid fluorine-containing nanorods
The mass ratio of the feed of each component is A: and the component B comprises the following components: and C, component: and D, a component: and E component: 1.5:0.875:0.125:1.0:1.6
To a 500 ml three neck round bottom glass flask was added 90 g of an isoamyl acetate solution containing 21.2 wt.% nitrocellulose, 6 g of I 2, 70 g of isoamyl acetate, 3.5 g of anhydrous CaI 2 and 0.5 g of LiSbF 6 and heated to 42 ℃. After I 2 was dissolved, 6 g of absolute methanol, 0.8 g of distilled water and 4g of 2,5-PDA xH 2 O (2, 5-pyrazinedicarboxylic acid hydrate) were added to a three-necked round bottom glass flask. The reaction was heated at 42℃with stirring for 4 hours and then cooled naturally.
The reaction solution was centrifuged at 1350G for 0.5 hours to remove large particle products. Centrifuging the supernatant at 18000G for 5 hours, discarding the supernatant to obtain light-operated particles, and obtaining the fluorine-containing nanorods, namely the inorganic-organic hybrid fluorine-containing nanorods, wherein the inorganic-organic hybrid fluorine-containing nanorods are fully dispersed by using 250 milliliters of isoamyl acetate.
SEM characterization results show that the inorganic-organic hybrid fluorine-containing nanorod has a particle length of 300nm, a particle width of 50nm, and a particle aspect ratio of 6.
Into a 250 ml round bottom glass flask was added 40 g of TDTM (tridecyl trimellitate) and the above prepared isoamyl acetate dispersion of inorganic-organic hybrid fluorine-containing nanorods was added in portions, the isoamyl acetate was removed by a rotary evaporator, and finally the treatment was continued at 80℃for 3 hours using a rotary evaporator. A suspension containing inorganic-organic hybrid fluorine-containing nanorods (referred to as LCP-1) was obtained.
Example 2 preparation of inorganic-organic hybrid fluorine-containing nanorods
Following the procedure of [ example 1 ], except substituting 3.9 g of anhydrous CaI 2 and 0.1 g of LiBF 4 for 3.5 g of anhydrous CaI 2 and 0.5 g of LiSbF 6, the components were heated and stirred at 42 ℃ for 2 hours, and the mass ratio of the components was: and the component B comprises the following components: and C, component: and D, a component: the E component is 1.5:0.975:0.025:1.0: SEM characterization results showed that the inorganic-organic hybrid fluorine-containing nanorod particles had a length of 378nm, a particle width of 53nm, and a particle aspect ratio of 7.1. The resulting suspension containing inorganic-organic hybrid fluorine-containing nanorods (referred to as LCP-2).
Example 3 preparation of inorganic-organic hybrid fluorine-containing nanorods
Following the procedure of [ example 1], except substituting 3.8 g of anhydrous CaI 2 and 0.2 g of LiBF 4 for 3.5 g of anhydrous CaI 2 and 0.5 g of LiSbF 6, the components were heated and stirred at 42 ℃ for 1 hour, and the mass ratio of the components was: and the component B comprises the following components: and C, component: and D, a component: the E component is 1.5:0.95:0.05:1.0:1.6.SEM characterization results show that the inorganic-organic hybrid fluorine-containing nanorod has a particle length of 338nm, a particle width of 40nm, and a particle aspect ratio of 8.45. The resulting suspension containing inorganic-organic hybrid fluorine-containing nanorods (referred to as LCP-3).
Example 4 preparation of inorganic-organic hybrid fluorine-containing nanorods
According to the method of [ example 1 ], except that 0.5 g of LiPF 6 is used instead of 3.5 g of anhydrous CaI 2 and 0.5 g of LiSbF 6, the reaction is heated and stirred at 42 ℃ for 1 hour, and the mass ratio of each component is A: and the component B comprises the following components: and C, component: and D, a component: the E component is 1.5:0.875:0.125:1.0:1.6.SEM characterization results showed that the inorganic-organic hybrid fluorine-containing nanorod particles had a length of 448nm, a particle width of 71nm, and a particle aspect ratio of 6.3. The resulting suspension containing inorganic-organic hybrid fluorine-containing nanorods (referred to as LCP-4).
Example 5 preparation of inorganic-organic hybrid fluorine-containing nanorods
According to the method of [ example 2 ], except that 2-pyrazinecarboxylic acid is used instead of 2, 5-pyrazinedicarboxylic acid hydrate, the mixture is heated and stirred at 50 ℃ for reaction for 6 hours, and the mass ratio of the components is that of the component A: and the component B comprises the following components: and C, component: and D, a component: the E component is 1.2:0.9:0.2:1.0:2.SEM characterization results show that the inorganic-organic hybrid fluorine-containing nanorod has a particle length of 150nm, a particle width of 30nm, and a particle aspect ratio of 5. The resulting suspension containing inorganic-organic hybrid fluorine-containing nanorods (referred to as LCP-5).
Example 6 preparation of inorganic-organic hybrid fluorine-containing nanorods
According to the method of [ example 1 ], except that n-propanol is used for replacing absolute methanol, ethyl cellulose is used for replacing nitrocellulose, and the mixture is heated and stirred at 50 ℃ for reaction for 1 hour, the mass ratio of the components is that the component A: and the component B comprises the following components: and C, component: and D, a component: the E component is 2.5:2:0.5:1.0:1.6.SEM characterization results show that the inorganic-organic hybrid fluorine-containing nanorod has a particle length of 600nm, a particle width of 50nm, and a particle aspect ratio of 12. The resulting suspension containing inorganic-organic hybrid fluorine-containing nanorods (referred to as LCP-6).
Example 7 preparation of inorganic-organic hybrid fluorine-containing nanorods
According to the method of [ example 1], except that KI is used for replacing anhydrous CaI 2, ethylcellulose is used for replacing nitrocellulose, and the mixture is heated and stirred at 50 ℃ for 2 hours, and the mass ratio of the components is that of the component A: and the component B comprises the following components: and C, component: and D, a component: the E component is 2.5:1.5:0.6:1.0:1.6.SEM characterization results show that the inorganic-organic hybrid fluorine-containing nanorod has a particle length of 800nm, a particle width of 30nm, and a particle aspect ratio of 26.6. The resulting suspension containing inorganic-organic hybrid fluorine-containing nanorods (referred to as LCP-7).
Example 8 preparation of inorganic-organic hybrid fluorine-containing nanorods
According to the method of [ example 1], except that n-butanol is used for replacing absolute methanol, cellulose acetate is used for replacing nitrocellulose, and the mixture is heated and stirred at 45 ℃ for reaction for 1 hour, the mass ratio of the components is that the component A: and the component B comprises the following components: and C, component: and D, a component: the E component is 1:1:0.1:1.0:1.6.SEM characterization results show that the inorganic-organic hybrid fluorine-containing nanorod has a particle length of 250nm, a particle width of 40nm, and a particle aspect ratio of 6.3. The resulting suspension containing inorganic-organic hybrid fluorine-containing nanorods (referred to as LCP-8).
Example 9 LV-1 light valve manufactured from LCP-1
The LCP-1 fabricated in [ example 1] was sealed between two transparent ITO conductive glass electrodes using epoxy to form a 200 micron thick LV light valve (referred to as LV-1). When no voltage is applied (off state), LV-1 shows a blue hue and the total light transmittance is 1.0%. When a 110 volt alternating current (on state) at 50 hz was applied, LV-1 became clear and the total light transmittance was 68.1%.
In the present application, the voltage value of the alternating current refers to the effective value.
Furthermore, the reversibility and stability of LV-1 were evaluated by periodically alternating between the off state and the on state, each state being maintained for 2 minutes to constitute an on-off cycle. After 5000 on-off cycles, the contrast of this LV-1 was kept at 105, corresponding to 95.5% reversibility, with specific results shown in Table 2.
Example 10 LV-2 light valve made from LCP-2
Manufactured and tested according to [ example 9 ], except that LCP-2 was used instead of LCP-1, referred to as LV-2, with specific results shown in Table 2.
Example 11 LV-3 light valve manufacture from LCP-3
Manufactured and tested according to [ example 9 ], except that LCP-3 was used instead of LCP-1, referred to as LV-3, with specific results shown in Table 2.
Example 12 LV-4 light valve manufacture from LCP-4
Manufactured and tested according to [ example 9 ], except that LCP-4 was used instead of LCP-1, referred to as LV-4, with specific results shown in Table 2.
Example 13 manufacture of LV-5 light valves from LCP-5
Manufactured and tested according to [ example 9 ], except that LCP-5 was used instead of LCP-1, referred to as LV-5, with specific results shown in Table 2.
Example 14 manufacture of LV-6 light valves from LCP-6
Manufactured and tested according to [ example 9 ], except that LCP-6 was used instead of LCP-1, referred to as LV-6, with specific results shown in Table 2.
Example 15 LV-7 light valve made from LCP-7
Manufactured and tested as per [ example 9 ], except that LCP-7 was used instead of LCP-1, referred to as LV-7, with specific results shown in Table 2.
Example 16 LV-8 light valve manufacture from LCP-8
Manufactured and tested according to [ example 9 ], except that LCP-8 was used instead of LCP-1, referred to as LV-8, with specific results shown in Table 2.
Preparation of inorganic-organic Complex (comparative example 1)
Comparative LCP samples were prepared following the procedure of [ example 1], except that no fluoride-containing salt was added. SEM characterization results showed that the inorganic-organic complex without added fluoride had a particle length of 400nm, a particle width of 50nm, and a particle aspect ratio of 8. The resulting suspension of inorganic-organic hybrid nanorods without added fluoride salt (referred to as LCP-comparative example-1).
Comparative example 2 LV-9 light valve made from LCP-comparative example-1
Manufactured and tested as per [ example 9 ], except that LCP-comparative example-1 was used instead of LCP-1, referred to as LV-9. The light transmittance measurements for LV-9 were 0.8% (off state) and 53.5% (on state), respectively. In addition, after 5000 on-off cycles, the contrast of LV-9 became 46, corresponding to 89% reversibility, with specific results shown in Table 2.
The comparison of LV-1 and LV-9 proves that the inorganic-organic hybrid fluorine-containing nano rod greatly improves the light control performance of the light valve.
Table 2:
Experiments show that the total light transmittance of the light valve reaches about 69.1%, the defect that the light valve has a small light transmittance adjusting range in the prior art is effectively overcome, a better technical effect is achieved, the light transmittance can be adjusted in a wider range, and the light valve has a good application prospect.
Evaluation of inorganic-organic hybrid fluorine-containing nanorods
LV light valve devices were prepared by using the fluorine-containing nanorods prepared in examples 1 to 8 and comparative example 1, respectively, and were placed in an environmental chamber at 95% relative humidity and air temperature of 60℃without xenon lamp irradiation, and the time required for the different light valve devices to become colorless was measured, and the results are shown in Table 3:
The fluorine-containing nanorods prepared in examples 1 to 8 and comparative example 1 were also respectively prepared into LV light valve devices, which were numbered LV-1a to 9a, and were placed in an environmental chamber under irradiation of a 500W/m 2 xenon lamp at a relative humidity of 15% and an air temperature of 60℃to measure the time required for the different light valve devices to become colorless, and the results are shown in Table 4:
Table 3 comparison of stability to water for each sample
Table 4 comparison of stability of samples to uv radiation
Stability to water: the comparative sample LV-9 became colorless after 312 hours at 95% relative humidity, 60℃and no xenon lamp irradiation. In contrast, all example samples required at least double the time to fade to colorless. It is therefore evident that the inorganic-organic hybrid fluorine-containing nanorods have good stability to water.
Stability to ultraviolet radiation: under irradiation of 15% relative humidity, 60℃and 500W/m 2 xenon lamp, the comparative sample LV-9 became colorless after 532 hours. In contrast, all example samples required at least double the time to fade to colorless. It is therefore evident that the inorganic-organic hybrid fluorine-containing nanorods have good stability to ultraviolet radiation.
In summary, the inorganic-organic hybrid fluorine-containing nanorod can enhance the stability of the light valve device to water and ultraviolet radiation, and better protect the light valve from damage. This has important significance for improving the long-term stability of the light valve device and prolonging its service life.
An inorganic-organic hybrid fluorine-containing nanorod, wherein: comprising a nanorod composed of a fluorine-containing anion, the nanorod comprising an inorganic-organic complex containing fluorine atoms, carbon atoms, nitrogen atoms, etc.; the fluorine atoms are provided by BF 4 -,PF6 -,SbF6 - plasma.
Preferably, the nanorod is an inorganic-organic complex, the composition of the nanorod comprises a composition A, B, C, D, E, wherein the composition A is iodine, the composition B is alkali metal halide or alkaline earth metal halide, the composition C is alkali metal fluoride or alkaline earth metal fluoride, the composition D is nitrogen-containing heterocyclic carboxylic acid or nitrogen-containing heterocyclic carboxylic ester, the composition E is modified cellulose, and the mass ratio of the compositions A is: b: c: d: e is 0.3 to 3:1:0.1 to 1:0.5 to 4:0.2 to 3. Preferably, the nanorods have a particle length of 50 to 800nm and an aspect ratio of 2 to 30 between the particle length and the particle width.
Preferably, the particle length of the nanorods is preferably 200 to 500nm, and the aspect ratio between the particle length and the particle width is preferably 5 to 15.
Preferably, the purity of the iodine is not less than 98%.
Preferably, the alkaline earth metal halide is at least one of calcium iodide, barium iodide, calcium bromide, and barium bromide.
Preferably, the purity of the above alkali metal halide or alkaline earth metal halide is not less than 99%.
Preferably, the fluoride-containing acid group in the alkali metal fluoride-containing acid salt or alkaline earth metal fluoride-containing acid salt is at least one of BF 4 -,PF6 -,SbF6 -.
Preferably, the metal ion in the alkali metal fluoride or alkaline earth metal fluoride is at least one of Li +,Na+,K+,Ca2+,Sr2+,Ba2+ and the like.
Preferably, the purity of the alkali metal fluoride or alkaline earth metal fluoride is not less than 99%.
Preferably, the above-mentioned nitrogen-containing heterocyclic carboxylic acid or nitrogen-containing heterocyclic carboxylic acid ester is the following compound
N is 1-4; /(I)N is 1-3;
n is 1-2; /(I) N is 1-5;
n is 1-4; /(I)
N is 1-4; /(I)N is 1-7;
n is 1-7; /(I) N is 1-6;
/>
At least one of them.
Preferably, the modified cellulose is at least one of nitrocellulose, ethylcellulose, cellulose acetate, and cellulose butyrate.
A method for synthesizing inorganic-organic hybrid fluorine-containing nanorods uses isoamyl acetate as a solvent, low-carbon alcohol with the carbon number less than 8 and distilled water as charge balancing agents, and the mass ratio of the components is that A: and the component B comprises the following components: and C, component: and D, a component: and E component: lower alcohols: water: isoamyl acetate 0.2-5: 1:0.1 to 1:0.4 to 3:0.5 to 5:0.1 to 8:0.01 to 5: 5-100, the specific preparation steps comprise:
a. providing E component modified cellulose, A component iodine, isoamyl acetate, B component alkali metal halide or alkaline earth metal halide, C component alkali metal fluoride or alkaline earth metal fluoride, heating to 5-150 ℃, adding low carbon alcohol, distilled water and D component nitrogen heterocyclic carboxylic acid or nitrogen heterocyclic carboxylic ester after iodine dissolution, continuously heating to maintain the temperature, stirring for reacting for 0.1-20 hours, and naturally cooling;
b. Centrifuging the reaction solution for 0.2-2 hours under the condition of not more than 5000G to remove large-particle products, centrifuging supernatant for 0.5-20 hours under the condition of not less than 10000G, discarding supernatant to obtain light-operated particles, and obtaining the inorganic-organic hybridized fluorine-containing nanorods.
The light valve capable of controlling light transmittance comprises two transparent electrodes and a liquid suspension medium clamped between the electrodes, wherein the inorganic-organic hybrid fluorine-containing nanorods are uniformly dispersed in the liquid suspension medium, and the buoyancy and gravity of the nanorods in the liquid suspension medium are balanced and can stably suspend in the liquid suspension medium and freely move; when in operation, the two transparent electrodes are connected with alternating current with adjustable voltage.
Preferably, the liquid suspension medium is a non-conductive liquid, and is at least one of a mineral insulating material, a synthetic insulating material and vegetable oil.
Preferably, the mineral insulating material is transformer oil.
Preferably, the synthetic insulating material is at least one of silicone oil, fluorocarbon organic compound, plasticizer (dioctyl phthalate, dibutyl phthalate, diisooctyl phthalate and triisodecyl trimellitate (TDTM)), dodecylbenzene, polybutene oil.
Preferably, the vegetable oil is at least one of castor oil, soybean oil and rapeseed oil.
Preferably, the transparent electrode is at least one of ITO conductive glass, ITO/PET conductive film, nano Ag wire/PET conductive film and nano Cu wire/PET conductive film.
Preferably, the two transparent electrodes between which the liquid suspension is sandwiched are sealed with an insulating material, which is an epoxy resin.
Preferably, the alternating current is 5 to 500V alternating current.
The above examples are for illustration only and do not limit the scope of the invention. All chemicals used in the examples were purchased from SIGMA ALDRICH, unless otherwise indicated. In all of these examples, all parts and percentages are by weight unless otherwise indicated. The transmittance of the LV light valve was measured with Oceanview spectrometer.
Claims (21)
1. A nanorod comprising an inorganic-organic complex containing fluorine atoms, carbon atoms and nitrogen atoms,
Wherein: the inorganic-organic complex comprises components A and B, C, D, E, wherein the component A is iodine, the component B is alkali metal halide or alkaline earth metal halide, the component C is alkali metal fluoride or alkaline earth metal fluoride, the component D is nitrogen-containing heterocyclic carboxylic acid or nitrogen-containing heterocyclic carboxylic ester, the component E is modified cellulose, and the mass ratio of the components A is as follows: b: c: d: e is 0.3 to 3:1:0.1 to 1:0.5 to 4:0.2 to 3.
2. The nanorod according to claim 1, wherein the nanorod has a particle length of 50 to 800nm and an aspect ratio between the particle length and the particle width of 2 to 30.
3. A nanorod according to claim 2, wherein the particle length of the nanorod is between 200 and 500nm, and the aspect ratio between particle length and particle width is preferably between 5 and 15.
4. The nanorod according to claim 1, wherein the purity of the iodine is not less than 98%.
5. The nanorod according to claim 1, wherein the alkaline earth metal halide is at least one of calcium iodide, barium iodide, calcium bromide, barium bromide.
6. The nanorod according to claim 1, wherein the purity of the alkali metal halide or alkaline earth metal halide is not less than 99%.
7. The nanorod according to claim 1, wherein the fluoride in the alkali metal fluoride or alkaline earth metal fluoride is at least one of BF 4 -,PF6 -,SbF6 -.
8. The nanorod of claim 1, wherein: the metal ion in the alkali metal fluoride or alkaline earth metal fluoride is at least one of Li +,Na+,K+,Ca2+,Sr2+,Ba2+.
9. The nanorod according to claim 1, wherein the alkali metal or alkaline earth metal fluoride has a purity of not less than 99%.
10. The nanorod according to claim 1, wherein the modified cellulose is at least one of nitrocellulose, ethylcellulose, cellulose acetate, cellulose butyrate.
11. The nanorod according to claim 1, wherein the nitrogen-containing heterocyclic carboxylic acid or nitrogen-containing heterocyclic carboxylic acid ester is at least one of the following compounds:
n is 1-4; /(I) N is 1-3;
n is 1-2; /(I) N is 1-5;
n is 1-4; /(I)
N is 1-4; /(I)N is 1-7;
n is 1-7; /(I) N is 1-6;
12. A light valve for controlling light transmittance comprising a first transparent electrode and a second transparent electrode, and a liquid suspension medium sandwiched between the first transparent electrode and the second transparent electrode, wherein: the nanorods according to any one of claims 1 to 11 are dispersed in the liquid suspension medium, and the buoyancy and gravity of the nanorods in the liquid suspension medium are balanced, can be stably suspended in the liquid suspension medium and can move freely; when the LED lamp works, the first transparent electrode and the second transparent electrode are connected with alternating current with adjustable voltage.
13. The light valve of claim 12, wherein: the liquid suspending medium is non-conductive liquid, and is at least one of mineral insulating material, synthetic insulating material and vegetable oil.
14. The light valve of claim 13, wherein the mineral insulating material comprises transformer oil.
15. The light valve of claim 13, wherein: the synthetic insulating material is at least one of organic silicone oil, fluorocarbon organic compound, plasticizer (dioctyl phthalate, dibutyl phthalate, diisooctyl phthalate and triisodecyl trimellitate (TDTM)), dodecylbenzene and polybutene oil.
16. The light valve of claim 13, wherein: the vegetable oil is at least one of castor oil, soybean oil and rapeseed oil.
17. The light valve of claim 13, wherein: each of the first transparent electrode and the second transparent electrode includes at least one of an ITO conductive glass, an ITO/PET conductive film, a nano Ag wire/PET conductive film, and a nano Cu wire/PET conductive film.
18. The light valve of claim 12, wherein the first transparent electrode and the second transparent electrode are sealed around with an insulating material.
19. The light valve of claim 18, wherein the insulating material is an epoxy.
20. The light valve of claim 12, wherein the ac voltage adjustment range is 5-500V ac.
21. A method for synthesizing inorganic-organic hybrid fluorine-containing nanorods uses isoamyl acetate as a solvent, low-carbon alcohol with the carbon number less than 8 and distilled water as charge balancing agents, and the mass ratio of the components is that A: and the component B comprises the following components: and C, component: and D, a component: and E component: lower alcohols: water: isoamyl acetate 0.2-5: 1:0.1 to 1:0.4 to 3:0.5 to 5:0.1 to 8:0.01 to 5: 5-100, the method comprises the following steps:
a. providing E component modified cellulose, A component iodine, isoamyl acetate, B component alkali metal halide or alkaline earth metal halide, C component alkali metal fluoride or alkaline earth metal fluoride, heating to 5-150 ℃, adding low carbon alcohol, distilled water and D component nitrogen heterocyclic carboxylic acid or nitrogen heterocyclic carboxylic ester after iodine is dissolved, continuously heating to maintain the temperature, stirring for reacting for 0.1-20 hours, and naturally cooling;
b. centrifuging the reaction solution for 0.2-2 hours under the condition of not more than 5000G to remove large-particle products, centrifuging supernatant for 0.5-20 hours under the condition of not less than 10000G, and discarding supernatant to obtain light-operated particles, thereby obtaining the inorganic-organic hybridized fluorine-containing nanorods.
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| PCT/CN2019/119862 WO2021097740A1 (en) | 2019-11-21 | 2019-11-21 | Nanorod and method for manufacturing same, and light valve containing nanorod |
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| CN113759627A (en) * | 2021-09-08 | 2021-12-07 | 浙江精一新材料科技有限公司 | Light valve device, light-controlled particles and preparation method thereof |
| CN115536052B (en) * | 2022-09-29 | 2023-11-03 | 深圳市华科创智技术有限公司 | Fluoride nano rod, preparation method thereof and application thereof in liquid light valve |
| CN115327831B (en) * | 2022-10-14 | 2023-02-17 | 江苏集萃智能液晶科技有限公司 | Multicolor dimming device and application thereof |
| CN115356882B (en) * | 2022-10-21 | 2023-03-31 | 合肥精卓光电有限责任公司 | Light valve device and preparation method thereof |
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| CA3079571A1 (en) * | 2017-10-18 | 2019-04-25 | The Government Of The United States Of America, As Represented By The Secretary Of The Navy | Plasmonic nanoparticles as pixels and sub-microsecond switches |
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| US4407565A (en) * | 1981-01-16 | 1983-10-04 | Research Frontiers Incorporated | Light valve suspension containing fluorocarbon liquid |
| CN103429668A (en) * | 2011-05-19 | 2013-12-04 | Dic株式会社 | Phthalocyanine nanorods and photoelectric conversion element |
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