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WO2019151643A1 - Znbi stratifié, nanofeuille de znbi et leurs procédés de préparation - Google Patents

Znbi stratifié, nanofeuille de znbi et leurs procédés de préparation Download PDF

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Publication number
WO2019151643A1
WO2019151643A1 PCT/KR2018/016084 KR2018016084W WO2019151643A1 WO 2019151643 A1 WO2019151643 A1 WO 2019151643A1 KR 2018016084 W KR2018016084 W KR 2018016084W WO 2019151643 A1 WO2019151643 A1 WO 2019151643A1
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Prior art keywords
layered
znbi
aznbi
peeling
solvent
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Ceased
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PCT/KR2018/016084
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English (en)
Korean (ko)
Inventor
김성웅
이규형
송준성
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Sungkyunkwan University
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Sungkyunkwan University
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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
    • C30B29/68—Crystals with laminate structure, e.g. "superlattices"
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/80—Constructional details
    • H10N10/85—Thermoelectric active materials
    • H10N10/851—Thermoelectric active materials comprising inorganic compositions

Definitions

  • the present invention is brought to, and more particularly, excellent thermal properties of the layered KZnBi, NaZnBi, LiZnBi, ZnBi, and the KZnBi, NaZnBi, LiZnBi, ZnBi nanosheets and methods for their preparation produced through these peeling Bi 2
  • the present invention relates to layered KZnBi, NaZnBi, LiZnBi and ZnBi, and KZnBi, NaZnBi, LiZnBi, and ZnBi nanosheets, which may be used as thermoelectric materials instead of Te 3 and PbTe materials.
  • Graphene and other ultra-thin two-dimensional (2D) materials are being actively studied in various fields based on new physical, chemical, mechanical and optical properties.
  • the inventors of the present invention intend to secure excellent low-dimensional materials having various physical properties by using ion implantation (alkali metal, alkaline earth metal, etc.) in order to overcome the limitation of the existing research, the parent structure is possible only two-dimensional material. .
  • KZnBi prepared by the present invention is a material having a p63 / mmc structure, and has a ZnBi layered structure that did not exist by K ion insertion.
  • ZnBi nanosheets with excellent physical properties can be obtained by removing and peeling K ions in the fabricated KZnBi structure.
  • NaZnBi prepared by the present invention is a material having a P4 / nmmz structure, and has a ZnBi layered structure that did not exist by Na ion insertion. It is possible to secure ZnBi nanosheets with excellent physical properties by removing and peeling Na ion of NaZnBi structure.
  • the LiZnBi produced by the present invention is a material having a p63mc structure, and has a ZnBi layered structure that did not exist by Li ion insertion. It is possible to secure ZnBi nanosheets with excellent physical properties by removing and removing Li ion of LiZnBi structure.
  • the problem to be solved by the present invention is to overcome the parent structure, which is a limitation of the existing two-dimensional material research, the present inventors intend to solve the above problems through the crystal structure transition using the ion insertion.
  • ZnBi layered structures and ZnBi nanosheets which do not exist in nature can be prepared.
  • the present invention provides a layered compound represented by the following formula (1) or (2), and a nanosheet represented by formula (1) or formula (2).
  • AZnBi (where A is any one of K, Na, Li)
  • layered KZnBi and layered ZnBi prepared by removing K ions therefrom have a layered structure as shown in FIGS. 3 to 5.
  • the compounds have a layered structure of p63 / mmc.
  • layered NaZnBi and layered ZnBi prepared by removing Na ions therefrom have a layered structure as shown in FIGS. 6 to 8.
  • the compound has a layered structure of P4 / nmmz.
  • layered LiZnBi and layered ZnBi prepared by removing Li ions therefrom have a layered structure as shown in FIGS. 9 to 11.
  • the compound has a layered structure of p63mc.
  • the present invention also provides
  • the melting step is preferably carried out at a temperature of 650 ⁇ 800 °C.
  • the cooling step may be achieved by quenching or slow cooling the mixture.
  • the slow cooling is a step of growing a crystal by cooling at a rate of 0.5-3 ° C. to a temperature of 300-500 ° C. to form a single crystal
  • the quenching is a step of rapidly cooling the slow cooling to form a polycrystal.
  • the present invention also provides
  • the A ions in the crystal may be removed using an organic solvent, water, or a mixture thereof.
  • the organic solvent may be a cyclic carbonate solvent, a chain carbonate solvent, an ester solvent, an ether solvent, a nitrile solvent, an amide solvent, or a mixture thereof.
  • the present invention also provides
  • the layered AZnBi (where A is any one of K, Na, and Li), ZnBi and ZnBi nanosheets of the present invention have excellent thermoelectric properties and effectively utilize as a thermoelectric material in place of Bi 2 Te 3 and PbTe materials. Can be.
  • 1 is a diagram schematically showing a synthesis process of KZnBi.
  • FIG. 2 is a diagram schematically illustrating a process for synthesizing NaZnBi.
  • FIG. 3 to 5 are diagrams showing the crystal structure (Fig. 3) and XRD diffraction (Fig. 4) of the synthesized KZnBi, comparing the XRD diffraction (Fig. 5) of KZnBi having a ZnBi three-dimensional structure and a two-dimensional ZnBi layer Drawing.
  • FIG. 6 to 8 show the crystal structure (Fig. 6) and XRD diffraction (Fig. 7) of the synthesized NaZnBi, and XRD diffraction of NaZnBi and Na-depleted layered ZnBi having a three-dimensional ZnBi, two-dimensional ZnBi layer (Fig. 6). 8) Comparison drawing.
  • FIGS. 9 to 11 are diagrams showing the crystal structure (Figs. 9 and 10) and XRD diffraction (Fig. 11) of the synthesized LiZnBi.
  • the present invention provides a layered compound represented by the following formula (1) or (2), and a nanosheet represented by the formula (2).
  • AZnBi (where A is any one of K, Na, Li)
  • the layered compound and the nanosheet may have excellent thermoelectric properties and may be used as a thermoelectric material in place of Bi 2 Te 3 based materials and PbTe based materials.
  • layered KZnBi and layered ZnBi prepared by removing K ions therefrom have a layered structure as shown in FIGS. 3 to 5.
  • the compounds have a layered structure of p63 / mmc.
  • layered NaZnBi and layered ZnBi prepared by removing Na ions therefrom have a layered structure as shown in FIGS. 6 to 8.
  • the compounds have a layered structure of P4 / nmmz.
  • layered LiZnBi and layered ZnBi prepared by removing Li ions therefrom have a layered structure as shown in FIGS. 9 to 11.
  • the compound has a layered structure of p63mc.
  • the present invention also provides a method for synthesizing layered AZnBi, where A is any one of K, Na, and Li.
  • reaction vessel does not react with the sample and does not break at a high temperature.
  • Representative examples include alumina crucibles, molybdenum crucibles and tungsten crucibles.
  • the melting step is preferably carried out at a temperature of 650 ⁇ 800 °C. If the upper limit of the temperature range is exceeded, the vapor pressure in the quartz tube encapsulated by evaporation of Alkali ions may increase, and if the temperature falls below the lower limit of the temperature range, the raw material may remain unreacted because the sintering reaction of the material is not completed. It is not desirable.
  • the cooling step may be achieved by quenching or slow cooling the mixture.
  • the slow cooling is a step of growing a crystal by cooling at a rate of 0.5-3 ° C. to a temperature of 300-500 ° C. to form a single crystal
  • the quenching is a step of rapidly cooling the slow cooling to form a polycrystal.
  • the composition may change due to vaporization of alkali ions.
  • the quenching may be performed by various methods such as quenching the temperature by putting a sample encapsulated in a low temperature solvent such as water or oil (quenching), or quenching to room temperature by removing a heat source.
  • a low temperature solvent such as water or oil
  • the present invention also provides
  • Removing A from the layered AZnBi may remove A ions in the crystal using an organic solvent, water, or a mixture thereof.
  • the organic solvent may be a cyclic carbonate solvent, a chain carbonate solvent, an ester solvent, an ether solvent, a nitrile solvent, an amide solvent, or a mixture thereof.
  • the present invention also provides
  • the peeling of the layered ZnBi may include peeling by energy using ultrasonic waves, peeling by invasion of a solvent, peeling by a salt and a reaction gas formed by an alkali metal such as a solvent and K, Na, Li, and peeling using a tape, and It can be made using one or two or more processes selected from the group consisting of peeling with a material having an adhesive surface.
  • the present invention also provides
  • the peeling of the layered ZnBi may include peeling by energy using ultrasonic waves, peeling by invasion of a solvent, peeling by a salt and a reaction gas formed by an alkali metal such as a solvent and K, Na, Li, and peeling using a tape, and It can be made using one or two or more processes selected from the group consisting of peeling with a material having an adhesive surface.
  • a well-mixed quantitative amount of Zn and Bi powders and a quantitative amount of K are inserted into the reaction vessel.
  • the inside of the quartz tube maintains an inert gas atmosphere such as Ar or prevents oxidation or deterioration of the sample by making a vacuum.
  • the present inventors used quartz enclosed in vacuum due to the fear of quartz damage due to volume expansion of the inert gas at high temperature. .
  • the quartz tube containing the sample was reacted in an electric furnace, and maintained at 650-800 ° C. for 12 hours at which the sample could be melted, and then slowly cooled to 0.5-3 ° C./hr for recrystallization. After reaching 300-500 ° C, the power to the furnace is cut off to allow the sample to cool. This secured high purity KZnBi crystals (FIG. 1).
  • a well mixed amount of Zn and Bi powder and a quantity of Na are inserted into the reaction vessel.
  • the sample inserted into the reaction vessel is encapsulated in a quartz tube.
  • the inside of the quartz tube maintains an inert gas atmosphere such as Ar or prevents oxidation or deterioration of the sample by making a vacuum.
  • the present inventors used quartz enclosed in vacuum due to the fear of quartz damage due to volume expansion of the inert gas at high temperature. .
  • the quartz tube containing the sample was reacted in an electric furnace, and maintained at 650-800 ° C. for 12 hours at which the sample could be melted, and then slowly cooled to 0.5-3 ° C./hr for recrystallization. After reaching 300-500 ° C, the power to the furnace is cut off to allow the sample to cool. This secured high purity NaZnBi crystals (FIG. 1).
  • the synthesized KZnBi samples were identified by X-ray diffraction patterns in FIGS. 3 to 5, and the calculated KZnBi samples corresponded to the p63 / mmc structures. Therefore, the synthesized KZnBi was a p63 / mmc crystal structure. It was confirmed (FIG. 3).
  • the synthesized NaZnBi samples were identified by X-ray diffraction patterns in FIGS. 6 to 8 and were found to be consistent with the p4 / nmmz structures through calculations. Thus, the synthesized NaZnBi is a p4 / nmmz crystal structure. It was confirmed (FIG. 6).

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

La présente invention concerne de l'AZnBi stratifié (A représentant l'un quelconque parmi du K, du Na et du Li), du ZnBi stratifié, une nanofeuille de ZnBi, et leurs procédés de préparation. L'objet de la présente invention est de surmonter la structure d'une phase parente, qui est une limite dans la recherche existante sur des matériaux bidimensionnels. Le KZnBi, le NaZnBi ou le LiZnBi stratifié peut être préparé par une transition de structure cristalline faisant appel à une insertion d'ions, et une structure stratifiée de ZnBi et une nanofeuille de ZnBi, qui ne sont pas présentes dans la nature, peuvent être préparées en faisant appel à du KZnBi, du NaZnBi ou du LiZnBi stratifié. Le composé stratifié et la nanofeuille selon la présente invention présentent d'excellentes caractéristiques thermoélectriques, et peuvent ainsi être utilisés comme matériau thermoélectrique à la place d'un matériau à base de Bi2Te3 et d'un matériau à base de PbTe, et peuvent également être appliqués comme semiconducteurs magnétiques en raison de leurs caractéristiques ferromagnétiques.
PCT/KR2018/016084 2017-11-16 2018-12-18 Znbi stratifié, nanofeuille de znbi et leurs procédés de préparation Ceased WO2019151643A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20170152726 2017-11-16
KR20170152724 2017-11-16
KR1020180011427A KR102124975B1 (ko) 2017-11-16 2018-01-30 층상형 ZnBi, ZnBi 나노시트 및 이들의 제조방법
KR10-2018-0011427 2018-01-30

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111719165A (zh) * 2020-06-24 2020-09-29 江南大学 一种电化学剥离法制备Bi纳米片的方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102263257B1 (ko) * 2018-11-21 2021-06-11 성균관대학교 산학협력단 신규 3차원 위상 디락 반금속 KZnBi 및 이의 제조방법

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101360839B1 (ko) * 2011-12-23 2014-02-12 성균관대학교산학협력단 2차원 산화아연 나노시트 기반 나노전력발전소자의 제조 방법 및 그 방법으로 제조된 발전 소자
KR20150044285A (ko) * 2013-10-16 2015-04-24 이화여자대학교 산학협력단 금속이 혼성화된 금속 산화물-함유 나노시트, 상기의 제조 방법, 및 상기를 포함하는 광촉매
KR20170039851A (ko) * 2015-10-02 2017-04-12 한국세라믹기술원 화학적 박리를 이용한 ZnSb 나노시트의 제조방법

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101360839B1 (ko) * 2011-12-23 2014-02-12 성균관대학교산학협력단 2차원 산화아연 나노시트 기반 나노전력발전소자의 제조 방법 및 그 방법으로 제조된 발전 소자
KR20150044285A (ko) * 2013-10-16 2015-04-24 이화여자대학교 산학협력단 금속이 혼성화된 금속 산화물-함유 나노시트, 상기의 제조 방법, 및 상기를 포함하는 광촉매
KR20170039851A (ko) * 2015-10-02 2017-04-12 한국세라믹기술원 화학적 박리를 이용한 ZnSb 나노시트의 제조방법

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
BRAGA, M. H. ET AL.: "The experimental study of the Bi-Sn, Bi-Zn and Bi-Sn-Zn systems", COMPUTER COUPLING OF PHASE DIAGRAMS AND THERMOCHEMISTRY, vol. 31, 2007, pages 468 - 478, XP022297006, doi:10.1016/j.calphad.2007.04.004 *
C AO, W. ET AL.: "Dirac semimetal phase in hexagonal LiZnBi", PHYSICAL REVIEW B., vol. 96, no. 115203, 11 September 2017 (2017-09-11), pages 1 - 7, XP055628549 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111719165A (zh) * 2020-06-24 2020-09-29 江南大学 一种电化学剥离法制备Bi纳米片的方法
CN111719165B (zh) * 2020-06-24 2021-04-30 江南大学 一种电化学剥离法制备Bi纳米片的方法

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KR102124975B1 (ko) 2020-06-22
KR20190056263A (ko) 2019-05-24

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