US20210103197A1 - ABX3 perovskite particles and their application in reverse mode controlling photo-flux - Google Patents

ABX3 perovskite particles and their application in reverse mode controlling photo-flux Download PDF

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US20210103197A1
US20210103197A1 US16/055,444 US201816055444A US2021103197A1 US 20210103197 A1 US20210103197 A1 US 20210103197A1 US 201816055444 A US201816055444 A US 201816055444A US 2021103197 A1 US2021103197 A1 US 2021103197A1
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abx
perovskite particles
perovskite
particles
light
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Yanan Li
Dawei Zhang
Shiyong Zhao
Shuyong Xiao
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Zhejiang Jingyi New Material Technology Co Ltd
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Zhejiang Jingyi New Material Technology Co Ltd
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Priority to US16/055,444 priority Critical patent/US20210103197A1/en
Assigned to 1-MATERIAL INC reassignment 1-MATERIAL INC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: LI, Yanan, XIAO, Shuyong, ZHANG, DAWEI, ZHAO, SHIYONG
Priority to US17/263,911 priority patent/US11353766B2/en
Priority to JP2020541495A priority patent/JP6921330B2/ja
Priority to CN201980003454.5A priority patent/CN111010879B/zh
Priority to EP19821429.8A priority patent/EP3685207B1/en
Priority to PCT/CN2019/096775 priority patent/WO2020029770A1/en
Assigned to ZHEJIANG JINGYI NEW MATERIAL TECHNOLOGY CO., LTD reassignment ZHEJIANG JINGYI NEW MATERIAL TECHNOLOGY CO., LTD ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: 1-MATERIAL INC
Publication of US20210103197A1 publication Critical patent/US20210103197A1/en
Abandoned legal-status Critical Current

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    • 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 
    • G02F1/169—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 orientable non-spherical particles having a common optical characteristic, e.g. suspended particles of reflective metal flakes
    • 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
    • G02B26/026—Optical devices or arrangements for the control of light using movable or deformable optical elements for controlling the intensity of light based on the rotation of particles under the influence of an external field, e.g. gyricons, twisting ball displays
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G21/00—Compounds of lead
    • C01G21/006—Compounds containing, besides lead, two or more other elements, with the exception of oxygen or hydrogen
    • 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
    • G02F1/172—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 based on a suspension of orientable dipolar particles, e.g. suspended particles displays
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/30—Three-dimensional structures
    • C01P2002/34—Three-dimensional structures perovskite-type (ABO3)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
    • C01P2004/24—Nanoplates, i.e. plate-like particles with a thickness from 1-100 nanometer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention is related to ABX 3 perovskite particles and a reverse mode light valve; more specifically is related to the halide ABX 3 perovskite particles and a reverse mode light control valve that can control the light transmission.
  • the light control valve has the property of higher light transmittance when the power is turned off (OFF state) and lower light transmittance when the power is turned on (ON state), and such a device is preferably used for windows, lenses, or a light shutter such as a sunroof.
  • the beautiful multifunctional smart windows exhibit promising features for a wide range of applications in buildings, airplanes, automobiles, etc.
  • the present invention provides a new use for ABX 3 perovskite material.
  • this reverse mode light valve has the advantages of high safety and low power consumption compared with the normal mode light valve.
  • a light valve is a device that can regulate the amount of light passing through a media like a water valve that can control the water flow. Window shade can be viewed as a light valve too.
  • the light valve is referred a device which can electronically control the light transmittance, and such a device is also scientifically referred as an electrochromic device.
  • electrochromic device Depending on science behind an electrochromic device, it can be further classified as polymer dispersed liquid crystal (PDLC) (U.S. Pat. No. 3,585,381), electrochemical device (EC) (U.S. Pat. No. 9,581,877) and suspension particles display (SPD) (U.S. Pat. No. 6,606,185).
  • PDLC polymer dispersed liquid crystal
  • EC electrochemical device
  • SPD suspension particles display
  • a typical light valve In a typical light valve, it is general dark color and transmits less light through when the power is turned off (OFF state), and it becomes light color and transmits more light through when the power is turned on (ON state); such an electrochromic device is thus referred to a normal mode light valve.
  • the reverse mode light valve manipulates the light in a reversed way as to that of the normal mode light valve, and it is light color and transmits more light through when the power is turned off (OFF state) and becomes dark color and transmits less light through when the power is turned on (ON state).
  • the normal mode light valve which is less transparent when power is off, implies that once the power supply system fails, there is less visibility between two sides of the device, this may cause an adverse situation in certain circumstances.
  • the passengers of the vehicle would be difficult to spot the hazard situation outside when the electrochromic window lose its electric power. Contrasting to a normal mode light valve, the reverse mode light valve is more transparent at an OFF state, this eventually avoids the visibility problem in case of a power failing. Furthermore, passengers in most time need visibility for driving and for sightseeing, so the light valves (electrochromic windows here specifically) need to be transparent. To maintain this long period transparency, a normal mode light valve would require to be powered ON all the time, but a reserve mode light valve would simply be in OFF state without the need of power supplying. Obviously, the reverse mode light valve would provide energy saving most time comparing to the normal mode light valve.
  • This invention presents the method to use ABX 3 perovskite particles to control the flux of light in a reverse mode electrochromic device, i.e., a reverse mode light valve (r-LV for short hereafter).
  • a reverse mode light valve i.e., a reverse mode light valve (r-LV for short hereafter).
  • the reverse mode light valve is referred a device that the light transmittance can be controlled by alternating current (AC).
  • AC alternating current
  • This reverse mode is more transparent when the power is turned off (OFF state) and becomes less transparent when the power is turned on (ON state).
  • Such a device with controllable light switching and energy-saving advantages can be used as smart windows for transportation vehicles, architect buildings and other places where the light transmittance to be electronically controlled.
  • Perovskite the name of the perovskite, originated from the Russian geologist Perovski and originally single-pointed the calcium titanate (CaTiO 3 ) mineral. Later, crystals with similar structures were collectively referred to as perovskites.
  • the cell structure of the halide ABX 3 perovskite referred to in this patent is shown in FIG. 4 .
  • B atom and 6 X atoms form octahedral units, and 8 octahedral units occupy the position of the hexahedral apex centered on the A atom.
  • This kind of material has a unique structure, giving it excellent optical, electrical, magnetic and thermodynamic properties, and is a new type of materials with attractive prospects.
  • the ABX 3 perovskite material has been explored in other potential applications, such as LED (Light Emitting Diodes) (Tan, Zhi-Kuang, et al., Nature Nanotechnology, 9: 687-692, 2014), Lasers (Haiming Zhu, et al., Nature Mater., 14: 636-642, 2015), Photodetectors (Zhenqian Yang, et al., Adv.
  • LED Light Emitting Diodes
  • Lasers Haiming Zhu, et al., Nature Mater., 14: 636-642, 2015
  • Photodetectors Zhenqian Yang, et al., Adv.
  • This invention presents the method to use ABX 3 perovskite particles to control the flux of light in a light control device (referred as a light valve).
  • a light valve a light control device
  • the present invention provides a new use of the ABX 3 perovskite material, and method to make such a material. More specifically, the present invention further provides a reverse mode light valve(r-LV).
  • This invented r-LV device comprises a liquid suspension having such a material of ABX 3 perovskite particles, which can electronically control transmission of light in such way that it allows more light transmitted through when the power is turned off (OFF state) and less light transmitted through when the power is turned on (ON state).
  • ABX 3 perovskite particles with a more specific chemical composition where A is at least one of Cs + , CH3NH 3 + , and Rb + , B is at least one of Pb 2+ , Ge 2+ , and Sn 2+ , and X is exclusively selected from one of halide anions including Cl ⁇ , Br ⁇ , or I ⁇ .
  • the said ABX 3 perovskite material is referred as halide ABX 3 perovskite material.
  • the referred halide ABX 3 perovskite material is to be used in a form of particles, thus more specifically these particles used are referred as halide ABX 3 perovskite particles.
  • these halide ABX 3 perovskite particles are characterized in that have a non-spherical morphology.
  • the halide ABX 3 perovskite particles morphology is at least one of a nanorod (one-dimensional); a nanosheet (two-dimensional); a cuboid, irregular (three-dimensional).
  • the liquid suspension which is used as a liquid medium to suspend the ABX 3 perovskite particles, comprises one or more a mineral resistive material, a synthetic resistive material, and a vegetable oil.
  • the said transparent electrode ( 100 ) can be made of the same material or different materials, where light can be transmitted through, preferably having a light transmittance equals to or greater than 80%.
  • FIG. 1 presents schematically the r-LV, wherein, a liquid suspension ( 300 ) is sandwiched between two transparent substrates ( 100 ) and ( 100 ).
  • the halide ABX 3 perovskite particles ( 200 ) are suspended in the liquid suspension ( 300 ).
  • FIG. 2 presents light transmittance of a r-LV device made according to this invention Example 6 before and after applying an electric voltage of 220V.
  • FIG. 3 presents SEM image of CsPbBr 3 nanosheets according to this invention Example 3.
  • FIG. 4 presents the cell structure of the ABX 3 perovskite.
  • the present invention provides a new use for halide ABX 3 perovskite particles to control the flux of light in a light control device in a reverse mode, thus referred as a reverse light valve (r-LV).
  • r-LV reverse light valve
  • FIG. 1 schematically illustrates a typical r-LV device, wherein, a liquid suspension ( 300 ) is sandwiched between two transparent substrates ( 100 ) and ( 100 ).
  • the halide ABX 3 perovskite particles ( 200 ) are suspended in the liquid suspension ( 300 ).
  • the halide ABX 3 perovskite particles in the liquid suspension assume random positions due to Brownian movement.
  • the beam of light passing into the light valve is partially absorbed/scattered, other part of light transmits through the light valve, so the light valve is thus relatively bright and transparent in the OFF state.
  • the light control halide ABX 3 perovskite particles When an electric field is applied thereto (ON state), the light control halide ABX 3 perovskite particles are polarized, that the effective maximum surface of the ABX 3 perovskite particles is perpendicular to the direction of the electric field. Hence, a major part of light going into the light valve is absorbed/scattered, and other smaller fraction of light is transmitted through, so the light valve is thus relatively darker and less transparent in the ON state.
  • the present invention provides a novel use of the ABX 3 perovskite particles in a reverse mode light control device (r-LV).
  • the invented r-LV comprises a liquid suspension having such a material of ABX 3 perovskite particles, which can electronically control transmission of light in such way that it allows more light transmitted through when the power is turned off (OFF state) and less light transmitted through when the power is turned on (ON state).
  • ABX 3 perovskite particles with a more specific chemical composition where A is at least one of Cs + , CH3NH 3 + , and Rb + , B is at least one of Pb 2+ , Ge 2+ , and Sn 2+ , and X is at least one of halide anions selected from Cl ⁇ , Br ⁇ , or I ⁇ .
  • the specified ABX 3 perovskite material is referred as halide ABX 3 perovskite material.
  • the referred halide ABX 3 perovskite material is to be used in a form of particles, thus more specifically these particles used are referred as halide ABX 3 perovskite particles.
  • these halide ABX 3 perovskite particles are characterized in that have a non-spherical morphology. Still further, the halide ABX 3 perovskite particles morphology is at least one of a nanorod (one-dimensional); a nanosheet (two-dimensional); a cuboid, irregular (three-dimensional).
  • the said ABX 3 perovskite particles ( 200 ) which are encapsulated inside the said liquid suspension ( 300 ) shall be capable of re-orientating themselves in an electronic field. Therefore, the geometric dimension of the said ABX 3 perovskite particles needs to be scientifically optimized.
  • the said ABX 3 perovskite particles preferably to be in a form of flakes and referred to nanosheets herein. Still the said nanosheets are preferably having a length of about 50 nm-2000 nm, more preferably 200 nm-500 nm, and a thickness of 5 nm-100 nm, more preferably 10 nm-50 nm.
  • the said ABX 3 perovskite particles shall have such a characteristic that the said ABX 3 perovskite particles are capable of being polarized under an electric field, and still the effective maximum surface of the polarized ABX 3 perovskite particles is perpendicular to direction of the electric field.
  • the said ABX 3 perovskite particles are nanosheets, after being polarized under an electric field, the surface of the large specific surface of the nanosheets is oriented to be perpendicular to the direction of the electric field.
  • the said liquid suspension ( 300 ), which is used as a liquid medium to suspend the ABX 3 perovskite particles, comprises one or more non-aqueous, electrically resistive liquids.
  • a liquid or a liquid mixture referring as the suspension medium, can maintain the suspended ABX 3 perovskite particles in gravitational equilibrium.
  • the liquid suspension ( 300 ) comprises one or more a mineral resistive material, a synthetic resistive material, a vegetable oil.
  • Mineral resistive materials such as transformer oils
  • synthetic resistive materials such as silicone oils, fluorocarbon organic compounds, plasticizers (such as Dioctyl phthalate, Dibutyl phthalate, Diisobutyl phthalate, Triisodecyl trimellitate (TDTM) etc.), dodecylbenzene, polybutene oil, etc.
  • vegetable oils such as castor oil, soybean oil, rapeseed oil, etc.
  • the liquid suspension medium used in the light valve of the present invention can be any liquid light valve suspension known in the art and can be formulated according to techniques well known to those skilled in the art.
  • the said both transparent electrodes ( 100 ) can be made of the same material or different materials, where light can be transmitted through, preferably having a light transmittance equals to or greater than 80%, more preferably 90%.
  • Either one or both the said transparent electrodes ( 100 ) can be ITO conductive glass, ITO/PET conductive film, Ag nanowire/PET conductive film, Cu nanowire/PET conductive film.
  • the transparent electrodes ( 100 ) are preferred to be of the same material for the simplicity of processing and for the same physical properties (such as flexibility and thermal expansion), important for device durability under certain conditions, such as thermal stress.
  • the liquid suspension containing the said halide ABX 3 perovskite particles sandwiched between the two transparent electrodes is preferably to be sealed with a resistive material, such as epoxy resin, etc.
  • An alternating current is thus applied through the transparent electrodes ( 110 ) to control the light transmittance through the assembled r-LV, and the voltage of such an alternating current is preferably in the range of 5-500 V, more preferably in a range of 30-220 V, which can be easily achieved by a common transformer.
  • Cesium carbonate (Cs 2 CO 3 , 4.07 g) was loaded into a 250 mL 3-neck flask along with octadecene (ODE, 50 mL) and oleic acid (11.088 g), and the mixture was dried for 1 h at 120° C. and then heated under Argon (Ar) to 150° C. until all Cs 2 CO 3 reacted with oleic acid.
  • the obtained Cs-Oleate may precipitate out of ODE at room temperature, and it can be preheated to make it soluble before further using.
  • N,N-dimethylformamide (DMF, 100 mL) and lead iodide (PbI 2 , 2.305 g) were charged into a 250 mL flask. Oleic acid (0.438 g) and octylamine (2.339 g) were added. After complete solubilization of PbI 2 , 5 mL Cs-Oleate solution was added (prepared as described in Example 1). Then, the resulted solution was added into a 5 L flask along with 4200 mL of toluene. Subsequently, the resulted solution was centrifuged at 5000 G for 1.5 hours and the supernatant was discarded to yield the light control CsPbI 3 nanosheets. Finally, the CsPbI 3 nanosheets were further dispersed with 500 mL of toluene, mixed well with shaking and sonication (referring as LCP-Example-2).
  • Example 3 presents SEM image of CsPbBr 3 nanosheets.
  • r-LV suspension containing CsPbI 3 nanosheets which is referred as r-LV Suspension Example-4.
  • r-LV Suspension Example-5 Into a 250 mL round bottom glass flask was weighted 10 g of silicone oil, then the LCP-Example-3 prepared in the Example 3 was added in portions. After thoroughly mixing the resulted suspension by shaking, toluene was subsequently removed by a rotary evaporator for 3 hours at 80° C. to yield a r-LV suspension containing CsPbBr 3 nanosheets, which is referred as r-LV Suspension Example-5.
  • r-LV Device-6 When no electric voltage was applied (OFF State), r-LV Device-6 exhibited an orange tint and light transmission was measured to be 19.4%.
  • OFF State When it was electrically activated using 220 Volts AC at 50 Hz (ON State), the r-LV Device-6 became darker and light transmission was measured to be 7.0% only. Table 1 summaries these results.
  • FIG. 2 presents the absorption spectrum of r-LV Device-6 at OFF state and ON state respectively.
  • r-LV Device-7 When no electric voltage was applied (OFF State), r-LV Device-7 exhibited an orange tint and light transmission was measured to be 25.1%.
  • OFF State When it was electrically activated using 220 Volts AC at 50 Hz (ON State), the r-LV Device-7 became darker and light transmission was measured to be 12.5% only as listed in Table 1.

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  • Physics & Mathematics (AREA)
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Application Number Priority Date Filing Date Title
US16/055,444 US20210103197A1 (en) 2018-08-06 2018-08-06 ABX3 perovskite particles and their application in reverse mode controlling photo-flux
US17/263,911 US11353766B2 (en) 2018-08-06 2019-07-19 ABX3 perovskite particles and their application in reverse mode controlling photo-flux
JP2020541495A JP6921330B2 (ja) 2018-08-06 2019-07-19 Ａｂｘ３ペロブスカイト粒子及びその光フラックスを制御するリバースモードでの用途
CN201980003454.5A CN111010879B (zh) 2018-08-06 2019-07-19 Abx3钙钛矿颗粒及其在反向模式控制光通量中的应用
EP19821429.8A EP3685207B1 (en) 2018-08-06 2019-07-19 Abx3 perovskite particles and their application in reverse mode controlling photo-flux
PCT/CN2019/096775 WO2020029770A1 (en) 2018-08-06 2019-07-19 Abx3 perovskite particles and their application in reverse mode controlling photo-flux

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CN116371452A (zh) * 2023-04-19 2023-07-04 上海应用技术大学 一种高效吸附和还原CO2的Cs2CuBr4光催化剂

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CN113980449A (zh) * 2021-10-13 2022-01-28 五邑大学 一种荧光材料及其制备方法与应用
CN116212904B (zh) * 2023-02-23 2024-03-22 昆明理工大学 一种四钙钛矿光催化材料及其应用

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