CN113678057A - Nanorod, manufacturing method thereof and light valve containing nanorod - Google Patents
Nanorod, manufacturing method thereof and light valve containing nanorod Download PDFInfo
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- CN113678057A CN113678057A CN201980093898.2A CN201980093898A CN113678057A CN 113678057 A CN113678057 A CN 113678057A CN 201980093898 A CN201980093898 A CN 201980093898A CN 113678057 A CN113678057 A CN 113678057A
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- nanorod
- light valve
- inorganic
- alkaline earth
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- 239000002073 nanorod Substances 0.000 title claims description 102
- 238000004519 manufacturing process Methods 0.000 title abstract description 17
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 67
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000011737 fluorine Substances 0.000 claims abstract description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 230000005540 biological transmission Effects 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims description 67
- -1 nitrogen-containing heterocyclic carboxylic acid Chemical class 0.000 claims description 40
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 claims description 34
- 150000003839 salts Chemical class 0.000 claims description 23
- 239000011810 insulating material Substances 0.000 claims description 22
- 239000006194 liquid suspension Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 22
- 229910052799 carbon Inorganic materials 0.000 claims description 21
- 229910001515 alkali metal fluoride Inorganic materials 0.000 claims description 18
- 229910001618 alkaline earth metal fluoride Inorganic materials 0.000 claims description 18
- 229910001615 alkaline earth metal halide Chemical group 0.000 claims description 17
- 229940117955 isoamyl acetate Drugs 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 229910001508 alkali metal halide Inorganic materials 0.000 claims description 14
- 229920002678 cellulose Polymers 0.000 claims description 14
- 239000001913 cellulose Substances 0.000 claims description 14
- 150000004673 fluoride salts Chemical class 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- 150000008045 alkali metal halides Chemical group 0.000 claims description 12
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 11
- 239000011630 iodine Substances 0.000 claims description 11
- 229910052740 iodine Inorganic materials 0.000 claims description 11
- 229910001640 calcium iodide 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
- 238000003756 stirring Methods 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 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
- 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
- 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
- 150000001721 carbon Chemical group 0.000 claims description 7
- 239000007788 liquid Substances 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
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229920001249 ethyl cellulose Polymers 0.000 claims description 6
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 6
- 229910018286 SbF 6 Inorganic materials 0.000 claims description 5
- 125000001153 fluoro group Chemical group F* 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000000047 product Substances 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
- 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
- 229940046413 calcium iodide Drugs 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
- 150000002148 esters Chemical class 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
- 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
- 239000003513 alkali Substances 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 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
- 150000004820 halides Chemical class 0.000 claims 1
- 229920002857 polybutadiene Polymers 0.000 claims 1
- 230000005855 radiation Effects 0.000 abstract description 10
- 230000007774 longterm Effects 0.000 abstract description 3
- 238000009396 hybridization Methods 0.000 abstract description 2
- 238000002834 transmittance Methods 0.000 description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000002360 preparation method Methods 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
- 238000012512 characterization method Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 230000005684 electric field Effects 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 229910052724 xenon Inorganic materials 0.000 description 6
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 6
- 229910012513 LiSbF 6 Inorganic materials 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 229910001547 lithium hexafluoroantimonate(V) Inorganic materials 0.000 description 4
- 229910001496 lithium tetrafluoroborate Inorganic materials 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
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 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 2
- 230000005653 Brownian motion process Effects 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
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229910052784 alkaline earth 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
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000012774 insulation material Substances 0.000 description 2
- 239000000203 mixture Substances 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
- 238000010998 test method Methods 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical class F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 230000033228 biological regulation Effects 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
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 229960002050 hydrofluoric acid Drugs 0.000 description 1
- 239000003446 ligand Substances 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
- 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
- 229920001083 polybutene Polymers 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
- 235000009566 rice Nutrition 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
- 229910009112 xH2O Inorganic materials 0.000 description 1
Images
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
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- 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)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biophysics (AREA)
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
Abstract
A nanometer stick and its manufacturing method and light valve containing the nanometer stick, the nanometer stick is inorganic-organic hybridization fluorine nanometer stick, the light valve using the nanometer stick has higher light transmission, at the same time, it can enhance the stability of the light valve to water and ultraviolet radiation, better protect the light valve from damage, it is very important to improve the long-term stability of the light valve device.
Description
The present invention relates to nanorods, a method for manufacturing the same, and a light valve including the same, and more particularly, to organic-inorganic hybrid fluoroanion-containing nanorods and a light valve including the same.
A light valve is a device that can adjust the transmittance of light passing through itself. As one type of light valve, 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 device (EC) and Suspended Particle Device (SPD). Specifically, a light valve (hereinafter, abbreviated as LV) refers to a device that can control the transmittance of light passing through a medium by adjusting the level of Alternating Current (AC) voltage applied to the medium.
Eighty-five years ago, light valve devices containing nanoparticles were invented. Later further developments have included Suspended Particle Device (SPD) films comprising a light modulating cell of a suspension consisting of a suspension containing rod-shaped particles of a mixed metal oxide, such as bismuth manganese oxide. Needle-like quinine iodosulfate (heraphathite) is the polyiodide first applied to SPD, however, quinine iodosulfate is not stable to heat, nor 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 issue, other types of polyhalides have been investigated and used in SPD light valves. However, the prior art is sensitive to ultraviolet irradiation and water vapor erosion, and the long-term stability of the SPD light valve device prepared by the prior art is a problem to be solved. Therefore, a challenge is how to prepare more stable rod-shaped particles that can be used in SPD light valve devices.
The organic lithium ion battery is a determining factor for the recent market of electric vehicles, and the electrolyte is one of five key factors of the organic lithium ion battery. The electrolyte must be soluble in a suitable organic solvent, ionically conductive, and have high stability. These requirements for the electrolyte of the organic lithium ion battery are just the basic requirements for the metal compound used for preparing the rod-shaped particles of the SPD light valve device. Therefore, the stable rod-shaped particles of the SPD light valve device can be prepared by taking the electrolyte salt of the organic lithium ion battery as a reference.
The earliest used electrolyte salt for an organic lithium ion battery was lithium perchlorate, and many of the currently used electrolyte salts include lithium tetrafluoroborate, lithium hexafluorophosphate, lithium hexafluoroantimonate, and the like, and further, 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 in the prior art have the problem of low stability. Therefore, there is a need to invent a better material which can have more stable performance on the basis of wider control light transmittance range by adjusting voltage.
Disclosure of Invention
In order to solve the above technical problems, the present invention provides a nanorod comprising an inorganic-organic complex including a fluorine atom, a carbon atom, and a nitrogen atom.
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-containing salt or alkaline earth metal fluoride-containing salt, 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 0.3-3: 1: 0.1-1: 0.5-4: 0.2 to 3.
In addition, the nanorod has a particle length of 50-800 nm and an aspect ratio of 2-30 between the particle length and the particle width.
Preferably, the nanorod has a particle length of 200-500 nm, and an aspect ratio between the particle length and the particle width of 5-15 is preferred.
Preferably, the iodine has a purity of 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 alkali metal halide or alkaline earth metal halide has a purity of not less than 99%.
Preferably, the fluoride-containing acid salt in the alkali metal fluoride-containing acid salt or the alkaline earth metal fluoride-containing acid salt is BF4 -，PF 6 -，SbF 6 -At least one of (1).
Preferably, the metal ion in the alkali metal fluoride salt or the alkaline earth metal fluoride salt is Li+，Na +，K +，Ca 2+，Sr 2+，Ba 2+At least one of (1).
Preferably, the alkali metal fluoride salt or alkaline earth metal fluoride salt has a purity of not less than 99%.
Preferably, the modified cellulose is at least one of nitrocellulose, ethyl cellulose, cellulose acetate, and cellulose butyrate.
Preferably, the nitrogen-containing heterocyclic carboxylic acid or nitrogen-containing heterocyclic carboxylic ester is at least one of the following compounds:
the present application also provides a light valve for controlling the transmittance of light, preferably comprising two transparent electrodes (i.e. a first transparent electrode and a second transparent electrode) and a liquid suspending 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 keep balance, so that the nano rods can be stably suspended in the liquid suspension medium and can freely move; when the device works, alternating current with adjustable voltage can be connected to the two transparent electrodes.
Preferably, the liquid suspension medium is a non-conductive liquid, which is at least one of a mineral insulation material, a synthetic insulation material, 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 and polybutylen 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 an ITO conductive glass, an ITO/PET conductive film, a nano Ag wire/PET conductive film, a nano Cu wire/PET conductive film.
Preferably, the two transparent electrodes are sealed with 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 means an effective value.
Further, the present application provides a film comprising one of the above light valves.
In addition, the application also provides a method for synthesizing inorganic-organic hybrid fluorine-containing nanorods, wherein isoamyl acetate is used as a solvent, low-carbon alcohol with the carbon atom number less than 8 and distilled water are used as charge balancing agents, and the feeding mass ratio of the components is component A: and B component: and C, component C: and (D) component: and E, component (E): low carbon alcohol: water: the content of the isoamyl acetate is 0.2-5: 1: 0.1-1: 0.4-3: 0.5-5: 0.1-8: 0.01-5: 5-100, the method comprises the following steps:
a. adding component E modified cellulose, component A iodine, isoamyl acetate, component B alkali metal halide or alkaline earth metal halide and component C alkali metal fluoride or alkaline earth metal fluoride in corresponding mass component proportion, heating to 5-150 ℃, adding low carbon alcohol, distilled water and component D nitrogen-containing heterocyclic carboxylic acid or nitrogen-containing heterocyclic carboxylic ester after iodine is dissolved, continuously heating and keeping the temperature, stirring and reacting for 0.1-20 hours, and then naturally cooling;
b. centrifuging the reaction solution for 0.2-2 hours under the condition of not higher than 5000G to remove large-particle products, centrifuging the supernatant for 0.5-20 hours under the condition of not lower than 10000G, and discarding the supernatant to obtain light-controlled particles, thereby obtaining the inorganic-organic hybrid fluorine-containing nanorod.
The main body of the inorganic-organic hybrid fluorine-containing nanorod provided by the invention is an inorganic-organic complex comprising a fluoride acid radical. Wherein the metal atom of the alkali metal or alkaline earth metal compound (components B and C) forms a chemical bond with the nitrogen atom of the nitrogen-containing heterocyclic carboxylic acid or ester (component D). Iodine (component A) also forms polyiodide complexes with the metal atoms of the alkali metal or alkaline earth metal compounds (components B and C). Fluoride-containing acid radicals also participate in the formation of polyiodide complexes. The selected modified cellulose can inhibit the agglomeration of the formed inorganic-organic hybrid fluorine-containing nanorods, control the production speed of different crystal faces, and promote the rapid growth of a certain crystal face in preference to other crystal faces, thereby generating a rod-shaped appearance.
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 the roles of 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 an off 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, so that the light valve has poor light transmission and is relatively dark. When an electric field is applied (on state), the nanorods are polarized by the electric field and are thus aligned in a direction in which the electric fields are parallel to each other, so that most of light can pass through the light valve, which effectively enhances light transmittance and is relatively transparent.
Experiments show that the total light transmittance of the light valve reaches 68.1 percent, the defect of small light transmittance adjusting range of the light valve in the prior art is overcome, the light transmittance can be adjusted in a wider range, the stability of the rod-shaped particles is obviously improved, a better technical effect is obtained, and the light valve has a good application prospect.
The inorganic-organic hybrid fluorine-containing nanorod and the light valve containing the nanorod are synthesized by a one-step method, the nanorod taking fluorine-containing anions as ligands is synthesized by the nanorod, the nanorod takes the advantages of fluorine-containing materials, nano materials and the like into consideration, and multiple characteristics are coordinated, so that the material has unique performance, the light valve made of the material has excellent performance, the light transmittance can be adjusted in a wider range, the stability is high, and the application prospect is good.
FIG. 1 is a schematic diagram of a light valve according to the present invention before power is applied;
fig. 2 is a schematic diagram of a light valve according to the present invention after being powered on.
According to an embodiment of the present invention, there is provided a nanorod including an inorganic-organic complex including a fluorine atom, a carbon atom, and a nitrogen atom.
The nanorod is an inorganic-organic complex and comprises A, B, C, D, E five 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-containing salt or alkaline earth metal fluoride-containing salt, 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 0.3-3: 1: 0.1-1: 0.5-4: 0.2 to 3.
The purity of the iodine is not lower than 98%. Iodine has a large atomic diameter and is easily polarized, and its dipole moment is large, and thus is used to manufacture light polarizing particles.
The alkali metal halide or alkaline earth metal halide may be selected from commercially available compounds such as calcium iodide, barium iodide, calcium bromide, barium bromide, etc., and preferably, the purity of the selected alkali metal halide or alkaline earth metal halide is not less than 99%.
The fluoric acid radical in the alkali metal fluoric acid salt or the alkali earth metal fluoric acid salt is BF4 -，PF 6 -，SbF 6 -At least one of (1).
The alkali metal fluoride salt or the alkaline earth metal fluoride salt may be selected from commercially available compounds such as lithium tetrafluoroborate, lithium hexafluorophosphate, lithium hexafluoroantimonate and the like. Preferably, the alkali or alkaline earth metal fluoride-containing 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 a compound listed in the following table, but is not limited to the compound in table 1.
Table 1:
the modified cellulose is at least one of nitrocellulose, ethyl cellulose, cellulose acetate and cellulose butyrate.
The nanorod has the particle length of 50-800 nm, more preferably 200-500 nm, and the aspect ratio between the particle length and the particle width is 2-30, more preferably 5-15.
The fluorine-containing nanorod has an inorganic-organic complex as a main body. The metal atom in the alkali metal or alkaline earth metal halide (B component) forms a chemical bond with the nitrogen atom in the nitrogen-containing heterocyclic carboxylic acid or ester (D component). Iodine (component A), iodide ions (component B) and fluoride-containing acid radicals (component C) also form a fluorine-containing polyiodide complex with metal atoms in the alkali metal or alkaline earth metal halide (component B). The selected modified cellulose can inhibit the agglomeration of the formed fluorine-containing nano-rods, control the production speed of different crystal faces and promote a certain crystal face to grow quickly in preference to other crystal faces, thereby generating a rod-shaped appearance.
Here, in order to realize the production of the inorganic-organic hybrid fluorine-containing nanorod of the present invention, the present invention provides a method for synthesizing the inorganic-organic hybrid fluorine-containing nanorod: the method takes isoamyl acetate as a solvent, low-carbon alcohol with the carbon atom number less than 8 and distilled water as a charge balancing agent, and the feeding mass ratio of the components is component A: and B component: and C, component C: and (D) component: and E, component (E): low carbon alcohol: water: the content of the isoamyl acetate is 0.2-5: 1: 0.1-1: 0.4-3: 0.5-5: 0.1-8: 0.01-5: 5-100, and 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 and 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-containing heterocyclic carboxylic acid or nitrogen-containing heterocyclic carboxylic ester after iodine is dissolved, continuously heating and keeping the temperature, stirring for reaction for 0.1-20 hours, and then naturally cooling;
b. centrifuging the reaction solution for 0.2-2 hours under the condition that the temperature is not higher than 5000G to remove large-particle products, centrifuging the supernatant for 0.5-20 hours under the condition that the temperature is not lower than 10000G, and discarding the supernatant to obtain light-operated particles, thereby obtaining the inorganic-organic hybrid fluorine-containing nanorods.
The water and the low-carbon alcohol added in the method balance the inorganic-organic complex of the shell in a hydrogen bond or coordination bond mode, play a role in balancing charges and the like, and enable the structure of the inorganic-organic complex to be more stable.
A 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 nanorods 200 are balanced in buoyancy and gravity in the liquid suspension medium 300, can be stably suspended in the liquid suspension medium 300 and can freely move; the two transparent electrodes 300 are connected with an alternating current with adjustable voltage.
The liquid suspension medium 300 is a non-conductive liquid, and is at least one of a mineral insulating material, a synthetic insulating material, and vegetable oil. The mineral insulating material is transformer oil. 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)), dodecyl benzene, polybutene oil, etc. The vegetable oil is at least one of castor oil, soybean oil and rapeseed oil. The liquid suspension medium 300 used in the light valves of the present invention is not limited to the above, and may be any liquid light valve suspension known in the art and 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, and nano Cu wire/PET conductive film.
The peripheries of the two transparent electrodes 100 are sealed by an insulating material, and the insulating material is epoxy resin.
The light valve adopts alternating current to drive and adjust the light transmittance, and preferably, alternating current of 5-500V is adopted; preferably, the alternating current is preferably 20-300V; more preferably, the alternating current is 50-150V.
When no electric field is applied (in an off state), the inorganic-organic hybrid fluorine-containing nanorods 200 in the liquid suspension medium 300 are randomly dispersed due to brownian motion, and light beams entering the light valve are absorbed and/or scattered, so that the light valve has poor light transmittance and is relatively dark, and the structure of the light valve is shown in fig. 1. When an electric field is applied (on state), the inorganic-organic hybrid fluorine-containing nanorods 200 are polarized by the electric field to be aligned in a direction in which the electric fields are parallel to each other, so that most of light can pass through the light valve, which has effectively enhanced light transmittance and is relatively transparent, and has a structure as shown in fig. 2.
The following method was used to evaluate the stability of inorganic-organic hybrid fluorine-containing nanorods to water and to ultraviolet radiation.
Method for evaluating stability to water:
the stability to water reflects the resistance of the light valve device using inorganic-organic hybrid fluorine-containing nanorods to water vapor. The test method is that the light valve device is placed in an environment box with 95% relative humidity and 60 ℃ of air temperature and without xenon lamp irradiation, and the time required for different light valve devices to become colorless is compared. The shorter the time required, the less stable it is to water.
Method for assessing stability to ultraviolet radiation:
the stability against ultraviolet radiation reflects the resistance of the light valve device using inorganic-organic hybrid fluorine-containing nanorods against ultraviolet radiation. The test method comprises placing the light valve device at 15% relative humidity, air temperature of 60 deg.C, and 500W/m2In the environment box under the irradiation of the xenon lamp, the time required for different light valve devices to become colorless was compared. The shorter the time required, the less stable it is to ultraviolet radiation.
The invention is further illustrated by the following examples.
Example 1 preparation of inorganic-organic hybrid fluorine-containing nanorods
The feeding mass ratio of each component is component A: and B component: and C, component C: and (D) component: and E, component (E): 1.5: 0.875: 0.125: 1.0: 1.6
Into a 500 ml three-neck round bottom glass flask was added 90 g of isoamyl acetate solution containing 21.2 wt% nitrocellulose, 6 g of I270 g of isoamyl acetate, 3.5 g of anhydrous CaI2And 0.5 g LiSbF6And heated to 42 ℃. Etc. I2After dissolution, 6 g of anhydrous methanol, 0.8 g of distilled water and 4 g of 2, 5-PDA. xH2O (2, 5-pyrazine dicarboxylic acid hydrate) was charged into a three-necked round bottom glass flask. The reaction was stirred with heating at 42 ℃ for 4 hours and then allowed to cool naturally.
The reaction solution was centrifuged at 1350G for 0.5 hours to remove large particle product. Centrifuging the supernatant for 5 hours at 18000G, discarding the supernatant to obtain light-controlled particles, and then obtaining fluorine-containing nanorods, namely inorganic-organic hybrid fluorine-containing nanorods, and fully dispersing the inorganic-organic hybrid fluorine-containing nanorods by using 250 ml 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.
40 g of TDTM (tridecyl trimellitate) was added to a 250 ml round bottom glass flask, and the dispersion of isoamyl acetate of inorganic-organic hybrid fluorine-containing nanorods prepared above was added in portions, and the isoamyl acetate was removed by a rotary evaporator, and finally the treatment was continued at 80 ℃ for 3 hours using the rotary evaporator. To obtain the suspension (called LCP-1) containing inorganic-organic hybrid fluorine-containing nano-rods.
Example 2 preparation of inorganic-organic hybrid fluorine-containing nanorods
Following the procedure as in [ example 1 ] except that 3.9 g of anhydrous CaI2And 0.1 g LiBF4Instead of 3.5 g of anhydrous CaI2And 0.5 g LiSbF6Heating and stirring at 42 ℃ for reaction for 2 hours, wherein the feeding mass ratio of each component is component A: and B component: and C, component C: and (D) component: the E component is 1.5: 0.975: 0.025: 1.0: SEM characterization results show that the inorganic-organic hybrid fluorine-containing nanorod particles have the length of 378nm, the particle width of 53nm and the particle aspect ratio of 7.1. The obtained inorganic-organic hybrid fluorine-containing nanorod suspension (LCP-2) is obtained.
Example 3 preparation of inorganic-organic hybrid fluorine-containing nanorods
Following the procedure as in [ example 1 ] except that 3.8 g of anhydrous CaI2And 0.2 g LiBF4Instead of 3.5 g of anhydrous CaI2And 0.5 g LiSbF6Heating and stirring at 42 ℃ for reaction for 1 hour, wherein the feeding mass ratio of the components is component A: and B component: and C, component C: and (D) 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 obtained inorganic-organic hybrid fluorine-containing nanorod suspension (LCP-3) is obtained.
Example 4 preparation of inorganic-organic hybrid fluorine-containing nanorods
Following the procedure as in [ example 1 ] except that 0.5 g LiPF6Instead of 3.5 g of anhydrous CaI 2And 0.5 g LiSbF6Heating and stirring at 42 ℃ for reaction for 1 hour, wherein the feeding mass ratio of the components is component A: and B component: and C, component C: and (D) component: the E component is 1.5: 0.875: 0.125: 1.0: 1.6.SEM characterization results show that the inorganic-organic hybrid fluorine-containing nanorod has a particle length of 448nm, a particle width of 71nm and a particle aspect ratio of 6.3. The obtained inorganic-organic hybrid fluorine-containing nanorod suspension (LCP-4) is obtained.
Example 5 preparation of inorganic-organic hybrid fluorine-containing nanorods
According to the method of example 2, 2-pyrazinecarboxylic acid is used to replace 2, 5-pyrazinedicarboxylic acid hydrate, and the mixture is heated and stirred at 50 ℃ for reaction for 6 hours, wherein the feeding mass ratio of the components is A: and B component: and C, component C: and (D) 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 obtained inorganic-organic hybrid fluorine-containing nanorod suspension (LCP-5) is obtained.
Example 6 preparation of inorganic-organic hybrid fluorine-containing nanorods
According to the method of [ example 1 ], only 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, wherein the feeding mass ratio of the components is A: and B component: and C, component C: and (D) 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 obtained inorganic-organic hybrid fluorine-containing nanorod suspension (LCP-6) is obtained.
Example 7 preparation of inorganic-organic hybrid fluorine-containing nanorods
According to the method of [ example 1 ], except that KI was used instead of anhydrous CaI2Replacing nitrocellulose with ethyl cellulose, heating and stirring at 50 ℃ for reaction for 2 hours, wherein the feeding mass ratio of each component is component A: and B component: and C, component C: and (D) component: the E component is 2.5: 1.5: 0.6: 1.0: 1.6.SEM characterization result shows that the inorganic-organic hybrid fluorine-containing nanoThe length of the rice stick particles is 800nm, the width of the particles is 30nm, and the aspect ratio of the particles is 26.6. The obtained inorganic-organic hybrid fluorine-containing nanorod suspension (LCP-7) is obtained.
Example 8 preparation of inorganic-organic hybrid fluorine-containing nanorods
According to the method of [ example 1 ], but n-butanol is used for replacing absolute methanol, cellulose acetate is used for replacing nitrocellulose, and the reaction is carried out for 1 hour by heating and stirring at 45 ℃, wherein the feeding mass ratio of each component is A: and B component: and C, component C: and (D) component: the component E 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 obtained inorganic-organic hybrid fluorine-containing nanorod suspension (LCP-8) is obtained.
EXAMPLE 9 fabrication of LV-1 light valves from LCP-1
LCP-1 made 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 exhibits a blue hue and a total light transmittance of 1.0%. When 50 Hz 110V AC was applied (on state), LV-1 became clear and the total light transmittance was 68.1%.
In this application, the voltage value of the alternating current refers to the effective value.
Furthermore, LV-1 was evaluated for reversibility and stability by periodically alternating between an off state and an on state, each of which was held for 2 minutes to constitute an on-off cycle. After 5000 on-off cycles, the contrast of this LV-1 remained 105, corresponding to 95.5% reversibility, as shown in Table 2.
EXAMPLE 10 fabrication of LV-2 light valves from LCP-2
Manufactured and tested as per [ example 9 ] except that LCP-2 was used instead of LCP-1, designated as LV-2, with specific results as shown in table 2.
EXAMPLE 11 manufacture of LV-3 light valves from LCP-3
Manufactured and tested as per [ example 9 ] except that LCP-3 was used instead of LCP-1, designated as LV-3, with specific results as shown in table 2.
EXAMPLE 12 manufacture of LV-4 light valves from LCP-4
Manufactured and tested as per [ example 9 ] except that LCP-4 was used instead of LCP-1, designated as LV-4, with specific results as shown in table 2.
EXAMPLE 13 manufacture of LV-5 light valves from LCP-5
Manufactured and tested as per [ example 9 ] except that LCP-5 was used instead of LCP-1, designated as LV-5, with specific results as shown in table 2.
EXAMPLE 14 manufacture of LV-6 light valves from LCP-6
Manufactured and tested as per [ example 9 ] except that LCP-6 was used instead of LCP-1, designated as LV-6, with specific results as shown in table 2.
EXAMPLE 15 manufacture of LV-7 light valves from LCP-7
Manufactured and tested as per [ example 9 ] except that LCP-7 was used instead of LCP-1, designated as LV-7, with specific results as shown in table 2.
EXAMPLE 16 manufacture of LV-8 light valves from LCP-8
Manufactured and tested as per [ example 9 ] except that LCP-8 was used instead of LCP-1, designated as LV-8, with specific results as shown in table 2.
[ COMPARATIVE EXAMPLE 1 ] preparation of inorganic-organic Complex
Comparative LCP samples were prepared according to the method of [ example 1 ] except that no fluoride containing salt was added. SEM characterization results show that the inorganic-organic complex without fluoride salt has 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 fluoride salt addition (referred to as LCP-comparative example-1).
COMPARATIVE EXAMPLE 2 fabrication of LV-9 light valves 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 of LV-9 was measured at 0.8% (off state) and 53.5% (on state), respectively. In addition, after 5000 on-off cycles, the contrast of this LV-9 became 46, corresponding to 89% reversibility, the results are shown in Table 2.
Comparing LV-1 and LV-9, it is proved that the inorganic-organic hybridization 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 percent, the defect of small light transmittance adjusting range of the light valve in the prior art is effectively overcome, better technical effects are obtained, the light transmittance can be adjusted in a wider range, and the light valve has good application prospects.
Evaluation of inorganic-organic hybrid fluorine-containing nanorods
The fluorine-containing nanorods prepared in examples 1 to 8 and comparative example 1 were respectively fabricated into LV light valve devices, which were numbered as LV-1 to 9, and placed in an environmental chamber at 95% relative humidity and an 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:
furthermore, the fluorine-containing nanorods prepared in examples 1 to 8 and comparative example 1 were respectively fabricated into LV light valve devices, which were numbered as LV-1a-9a, and were placed at 15% relative humidity, 60 ℃ air temperature, and 500W/m2The time required for the different light valve devices to become colorless was measured in an environmental chamber under xenon lamp illumination, and the results are shown in table 4:
TABLE 3 comparison of stability to Water for each sample
| Examples | Fluoride-containing acid salt | Light valve numbering | Stability to water |
| (time/hour until colorless) | |||
| Example 9 | 0.5 g LiSbF 6 | LV-1 | 658 |
| Example 10 | 0.1 g LiBF 4 | LV-2 | 629 |
| Example 11 | 0.2 g LiBF 4 | LV-3 | 702 |
| Example 12 | 0.5 g LiPF 6 | LV-4 | 611 |
| Example 13 | 0.5 g LiSbF 6 | LV-5 | 665 |
| Example 14 | 0.5 g LiSbF 6 | LV-6 | 681 |
| Example 15 | 0.5 g LiSbF 6 | LV-7 | 683 |
| Example 16 | 0.5 g LiSbF 6 | LV-8 | 690 |
| Comparative example 2 | Is free of | LV-9 | 312 |
TABLE 4 comparison of stability to UV radiation for each sample
Stability to water: comparative sample LV-9 turned colorless after 312 hours at 95% relative humidity, 60 degrees Celsius, and no xenon lamp exposure. By contrast, all example samples took at least double the time to fade to colorless. Therefore, it is obvious that the inorganic-organic hybrid fluorine-containing nanorod has good stability to water.
Stability to ultraviolet radiation: at 15% relative humidity, 60 ℃ and 500W/m2The comparative sample LV-9 turned colorless after 532 hours under xenon illumination. By contrast, all example samples took at least double the time to fade to colorless. Therefore, it is obvious that the inorganic-organic hybrid fluorine-containing nanorod has good stability to ultraviolet radiation.
In conclusion, the inorganic-organic hybrid fluorine-containing nanorod can enhance the stability of a light valve device to water and ultraviolet radiation and better protect the light valve from being damaged. This is of great significance in improving the long-term stability of the light valve device and prolonging the service life of the light valve device.
Inorganic-organic hybrid fluorine-containing nanorod, wherein: nanorods comprising fluorine-containing anions, the nanorods comprising an inorganic-organic complex containing fluorine atoms, carbon atoms, nitrogen atoms, etc.; the fluorine atom is represented by BF4 -，PF 6 -，SbF 6 -Plasma is provided.
Preferably, the nanorod is an inorganic-organic complex, and the component of the nanorod comprises 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-containing salt or alkaline earth metal fluoride-containing salt, 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 0.3-3: 1: 0.1-1: 0.5-4: 0.2 to 3. Preferably, the nanorod has a particle length of 50-800 nm and an aspect ratio of 2-30 between the particle length and the particle width.
Preferably, the nanorod has a particle length of preferably 200-500 nm, and an aspect ratio between the particle length and the particle width of preferably 5-15.
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-mentioned 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 the alkaline earth metal fluoride-containing acid salt is BF4 -，PF 6 -，SbF 6 -At least one of (1).
Preferably, the metal ion in the alkali metal fluoride salt or the alkaline earth metal fluoride salt is Li+，Na +，K +，Ca 2+，Sr 2+，Ba 2+And the like.
Preferably, the above alkali metal fluoride salt or alkaline earth metal fluoride salt has a purity of not less than 99%.
Preferably, the nitrogen-containing heterocyclic carboxylic acid or ester is the following compound
n is 1 to 4;
n is 1 to 3;
n is 1-2;
n is 1 to 5;
n is 1 to 4;
n is 1 to 4;
n is 1 to 7;
n is 1 to 7;
n is 1 to 6;
at least one of (1).
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 nano-rods takes isoamyl acetate as a solvent, low-carbon alcohol with the carbon atom number less than 8 and distilled water as a charge balancing agent, and the feeding mass ratio of the components is A: and B component: and C, component C: and (D) component: and E, component (E): low carbon alcohol: water: the content of the isoamyl acetate is 0.2-5: 1: 0.1-1: 0.4-3: 0.5-5: 0.1-8: 0.01-5: 5-100, and the specific preparation steps comprise:
a. providing component E modified cellulose, component A iodine, isoamyl acetate, component B alkali metal halide or alkaline earth metal halide and component C alkali metal fluoride or alkaline earth metal fluoride, heating to 5-150 ℃, adding low carbon alcohol, distilled water and component D nitrogen-containing heterocyclic carboxylic acid or nitrogen-containing heterocyclic carboxylic ester after iodine is dissolved, continuously heating and keeping the temperature, stirring and reacting for 0.1-20 hours, and then naturally cooling;
b. centrifuging the reaction solution for 0.2-2 hours under the condition of not higher than 5000G to remove large-particle products, centrifuging the supernatant for 0.5-20 hours under the condition of not lower than 10000G, and discarding the supernatant to obtain light-controlled particles, thereby obtaining the inorganic-organic hybrid fluorine-containing nanorod.
A 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 nanorods are balanced in buoyancy and gravity in the liquid suspension medium, can be stably suspended in the liquid suspension medium and can freely move; when the device works, alternating current with adjustable voltage is connected to the two transparent electrodes.
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 and polybutylen 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, an ITO/PET conductive film, a nano Ag wire/PET conductive film, and a nano Cu wire/PET conductive film.
Preferably, the two transparent electrodes sandwiching the liquid suspension are sealed with an insulating material, and the insulating material is epoxy resin.
Preferably, the alternating current is 5-500V alternating current.
The above examples are for illustrative purposes only and do not limit the scope of the present 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 an ocerview spectrometer.
Claims (22)
- A nanorod comprising an inorganic-organic complex including a fluorine atom, a carbon atom, and a nitrogen atom.
- The nanorod of claim 1, wherein: the inorganic-organic complex comprises a component 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-containing salt or alkaline earth metal fluoride-containing salt, 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 0.3-3: 1: 0.1-1: 0.5-4: 0.2 to 3.
- The nanorod of claim 1, wherein the nanorod has a particle length of 50-800 nm and an aspect ratio between the particle length and the particle width of 2-30.
- The nanorod according to claim 3, wherein the nanorod has a particle length of 200-500 nm, and an aspect ratio between the particle length and the particle width is preferably 5-15.
- The nanorod of claim 2, wherein the iodine is not less than 98% pure.
- The nanorod of claim 2, wherein the alkaline earth metal halide is at least one of calcium iodide, barium iodide, calcium bromide, barium bromide.
- The nanorod of claim 2, wherein the alkali or alkaline earth halide has a purity of not less than 99%.
- The nanorod of claim 2, wherein the fluoride-containing acid salt in the alkali metal fluoride-containing acid salt or the alkaline earth metal fluoride-containing acid salt is BF4 -，PF 6 -，SbF 6 -At least one of (1).
- The nanorod of claim 2, wherein: the metal ion in the alkali metal fluoride salt or the alkaline earth metal fluoride salt is Li+，Na +，K +，Ca 2+，Sr 2+，Ba 2+At least one of (1).
- The nanorod of claim 2, wherein the alkali or alkaline earth metal fluoride-containing salt has a purity of not less than 99%.
- The nanorod of claim 2, wherein the modified cellulose is at least one of nitrocellulose, ethylcellulose, cellulose acetate, cellulose butyrate.
- The nanorod of claim 2, wherein the nitrogen-containing heterocyclic carboxylic acid or ester is at least one of the following compounds:n is 1 to 4;
n is 1 to 3;
n is 1-2;
n is 1 to 5;
n is 1 to 4;
n is 1 to 4;
n is 1 to 7;
n is 1 to 7;
n is 1 to 6;
- a light valve for controlling the transmission of light comprising a first transparent electrode and a second transparent electrode, and a liquid suspending medium sandwiched between said first transparent electrode and said second transparent electrode, wherein: the nano-rods of any one of claims 1 to 11 are dispersed in the liquid suspension medium, and the nano-rods can be stably suspended in the liquid suspension medium and can freely move because of the balance of buoyancy and gravity in the liquid suspension medium; when the device works, alternating current with adjustable voltage is connected to the first transparent electrode and the second transparent electrode.
- The light valve of claim 13, wherein: the liquid suspension medium is a non-conductive liquid which is at least one of a mineral insulating material, a synthetic insulating material and vegetable oil.
- A light valve as claimed in claim 14, wherein the mineral insulating material comprises transformer oil.
- The light valve of claim 14, wherein: the synthetic insulating material is at least one of organic silicone oil, fluorocarbon organic compounds, plasticizers (dioctyl phthalate, dibutyl phthalate, diisooctyl phthalate and triisodecyl trimellitate (TDTM)), dodecyl benzene and polybutadienes oil.
- The light valve of claim 14, wherein: the vegetable oil is at least one of castor oil, soybean oil and rapeseed oil.
- The light valve of claim 14, wherein: each of the first and second transparent electrodes includes at least one of an ITO conductive glass, an ITO/PET conductive film, a nano Ag wire/PET conductive film, a nano Cu wire/PET conductive film.
- The light valve of claim 13, wherein the first transparent electrode and the second transparent electrode are sealed around with an insulating material.
- The light valve of claim 19, wherein the insulating material is an epoxy.
- The light valve as claimed in claim 13, wherein the alternating current has a voltage adjusting range of 5-500V alternating current.
- A method for synthesizing inorganic-organic hybrid fluorine-containing nano-rods takes isoamyl acetate as a solvent, low-carbon alcohol with the carbon atom number less than 8 and distilled water as a charge balancing agent, and the feeding mass ratio of the components is A: and B component: and C, component C: and (D) component: and E, component (E): low carbon alcohol: water: the content of the isoamyl acetate is 0.2-5: 1: 0.1-1: 0.4-3: 0.5-5: 0.1-8: 0.01-5: 5-100, the method comprises the following steps:a. providing component E modified cellulose, component A iodine, isoamyl acetate, component B alkali metal halide or alkaline earth metal halide and component C alkali metal fluoride or alkaline earth metal fluoride, heating to 5-150 ℃, adding low carbon alcohol, distilled water and component D nitrogen-containing heterocyclic carboxylic acid or nitrogen-containing heterocyclic carboxylic ester after iodine is dissolved, continuously heating and keeping the temperature, stirring and reacting for 0.1-20 hours, and then naturally cooling;b. centrifuging the reaction solution for 0.2-2 hours under the condition of not higher than 5000G to remove large-particle products, centrifuging the supernatant for 0.5-20 hours under the condition of not lower than 10000G, and discarding the supernatant to obtain light-controlled particles, thereby obtaining the inorganic-organic hybrid fluorine-containing nanorod.
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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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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115327831A (en) * | 2022-10-14 | 2022-11-11 | 江苏集萃智能液晶科技有限公司 | Multicolor dimming device and application thereof |
| CN115356882A (en) * | 2022-10-21 | 2022-11-18 | 合肥精卓光电有限责任公司 | Light valve device and preparation method thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| KR101736096B1 (en) * | 2016-01-22 | 2017-05-16 | 영남대학교 산학협력단 | Preparation method of mesoporous NiCo2O4 nanostructures |
| CN108659229A (en) * | 2017-04-01 | 2018-10-16 | 香港大学 | A kind of activity supermolecule polymer and preparation method thereof |
| CN109491174A (en) * | 2018-11-19 | 2019-03-19 | 浙江精新材料科技有限公司 | A kind of inorganic-organic hybridization core-shell type nano stick and the light valve with the nanometer rods |
| US20190113824A1 (en) * | 2017-10-18 | 2019-04-18 | The Government Of The United States Of America, As Represented By The Secretary Of The Navy | Plasmonic Nanoparticles as Pixels and Sub-Microsecond Switches |
| CN109856884A (en) * | 2018-11-19 | 2019-06-07 | 浙江精一新材料科技有限公司 | A kind of preparation method of the controllable light valve of suspended particles |
-
2019
- 2019-11-21 WO PCT/CN2019/119862 patent/WO2021097740A1/en active Application Filing
- 2019-11-21 CN CN201980093898.2A patent/CN113678057B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| KR101736096B1 (en) * | 2016-01-22 | 2017-05-16 | 영남대학교 산학협력단 | Preparation method of mesoporous NiCo2O4 nanostructures |
| CN108659229A (en) * | 2017-04-01 | 2018-10-16 | 香港大学 | A kind of activity supermolecule polymer and preparation method thereof |
| US20190113824A1 (en) * | 2017-10-18 | 2019-04-18 | The Government Of The United States Of America, As Represented By The Secretary Of The Navy | Plasmonic Nanoparticles as Pixels and Sub-Microsecond Switches |
| CN109491174A (en) * | 2018-11-19 | 2019-03-19 | 浙江精新材料科技有限公司 | A kind of inorganic-organic hybridization core-shell type nano stick and the light valve with the nanometer rods |
| CN109856884A (en) * | 2018-11-19 | 2019-06-07 | 浙江精一新材料科技有限公司 | A kind of preparation method of the controllable light valve of suspended particles |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115327831A (en) * | 2022-10-14 | 2022-11-11 | 江苏集萃智能液晶科技有限公司 | Multicolor dimming device and application thereof |
| 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 |
| CN115356882A (en) * | 2022-10-21 | 2022-11-18 | 合肥精卓光电有限责任公司 | Light valve device and preparation method thereof |
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