WO2012112491A1 - Conversion d'énergie par effet thermoélectrique basée sur du czts (cuivre-zinc-étain-soufre) nanostructuré - Google Patents

Conversion d'énergie par effet thermoélectrique basée sur du czts (cuivre-zinc-étain-soufre) nanostructuré Download PDF

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Publication number
WO2012112491A1
WO2012112491A1 PCT/US2012/024973 US2012024973W WO2012112491A1 WO 2012112491 A1 WO2012112491 A1 WO 2012112491A1 US 2012024973 W US2012024973 W US 2012024973W WO 2012112491 A1 WO2012112491 A1 WO 2012112491A1
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WIPO (PCT)
Prior art keywords
tin sulfide
zinc tin
copper zinc
nanocrystals
copper
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PCT/US2012/024973
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English (en)
Inventor
Yue Wu
Haoran YANG
Genquiang ZHANG
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Purdue Research Foundation
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Publication of WO2012112491A1 publication Critical patent/WO2012112491A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G19/00—Compounds of tin
    • C01G19/006—Compounds containing, besides tin, two or more other elements, with the exception of oxygen or hydrogen
    • 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
    • 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
    • H10N10/852—Thermoelectric active materials comprising inorganic compositions comprising tellurium, selenium or sulfur
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
    • 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
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/32—Thermal properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties

Definitions

  • thermoelectric materials and, more specifically, to nanostructured thermoelectric materials and methods of utilizing nanostructured materials including, without limitation, copper zinc tin sulfide-based materials.
  • Thermoelectric materials directly convert temperature difference into electric voltage and vice versa.
  • Thermoelectric materials can be used to generate electricity from waste heat or used as a heater or cooler when electrically powered.
  • the performance of a thermoelectric material is evaluated by a quantity called the dimensionless figure of merit, ZT.
  • the dimensionless figure of merit can be expressed as an equation:
  • thermoelectric material ⁇ is the electrical conductivity of the thermoelectric material
  • T is the temperature
  • K is the thermal conductivity
  • a novel technique has been developed to use nanostructured copper zinc tin sulfide (CZTS) as a high efficient thermoelectric material.
  • CZTS copper zinc tin sulfide
  • This novel nanostructured material is advantageous because it comprises relatively inexpensive, abundant, and non-toxic elements.
  • DOS enhanced electron density of states
  • ⁇ thermal conductivity
  • a Seebeck coefficient is greater than 65 ⁇ / ⁇ and less than 301 ⁇ ⁇ within a temperature range of 300 K to 700 K.
  • an electrical conductivity is greater than 409 S/m and less than 1388 S/m within a temperature range of 300 K to 700 K.
  • a thermal conductivity is greater than 0.645 W/mK and less than 0.695 W/mK within a temperature range of 300 K to 700 K.
  • a dimensionless figure of merit is greater than 0.0008 and less than 0.14 within the temperature range of 300 K to 700 K.
  • the method further includes drying the refined product to create dried copper zinc tin sulfide nanocrystals, and grinding the dried copper zinc tin sulfide nanocrystals into a copper zinc tin sulfide nanocrystal powder.
  • the method further includes hot pressing the dried copper zinc tin sulfide nanocrystals.
  • the copper precursor comprises copper
  • the zinc precursor comprises zinc acetate dihydrate.
  • the tin precursor comprises tin acetate dihydrate.
  • the reactant mixture is purged with an inert gas.
  • the reactant mixture is heated to 300 °C upon the injection of a sulfur precursor and then reacted for one hour at 300 °C.
  • the precipitating step includes mixing the product mixture with ethanol, followed by centrifugation.
  • the refining step includes dispersing the intermediate in chloroform, followed by centrifugation, to create a supernatant comprising copper zinc tin sulfide nanocrystals.
  • the method further includes dispersing the intermediate in a dispersing agent to create a suspension, and processing the suspension to retain a supernatant that includes copper zinc tin sulfide nanocrystals.
  • the method further includes precipitating a portion of the supernatant to form a refined product comprising a higher percentage of copper zinc tin sulfide nanocrystals than in the intermediate, and at least one of centrifuging, drying, and pressing the refined product.
  • FIG. 1 is an X-ray diffraction on the synthesized exemplary material of the instant disclosure, with the diffraction pattern being indexed to tetragonal CZTS.
  • FIG. 2 is a transmission electron microscopy analysis on the synthesized exemplary material of the instant disclosure.
  • FIG. 3 is a UV-Vis spectrum of the synthesized exemplary material of the instant disclosure.
  • FIG. 4 is a magnification image from a scanning electron microscope of a bulk sample of synthesized exemplary material of the instant disclosure after hot press.
  • FIG. 5 is a plot of thermoelectric properties of the synthesized exemplary material of the instant disclosure as a function of temperature.
  • thermoelectric materials and, more specifically, to nanostructured thermoelectric materials and methods of utilizing and creating nanostructured materials including, without limitation, copper zinc tin sulfide-based materials.
  • nanostructured thermoelectric materials including, without limitation, copper zinc tin sulfide-based materials.
  • the preferred embodiments discussed below are exemplary in nature and may be reconfigured without departing from the scope and spirit of the present invention.
  • the exemplary embodiments as discussed below may include optional steps, methods, and features that one of ordinary skill should recognize as not being a requisite to fall within the scope of the present invention.
  • a novel nanostructure thermoelectric energy conversion material fabricated in accordance with the instant disclosure is believed to have the following chemical formula: Cu 2 ZnSnS (abbreviated hereafter as CZTS).
  • CZTS Cu 2 ZnSnS
  • An exemplary synthesis of CZTS in the form of nanocrystals includes adding 0.98 g of copper acetylacetonate (97%), 0.295 g of zinc acetate dihydrate (reagent grade), and 0.355 g of tin chloride (98%) to 55 mL of oleylamine in a 100 mL three-neck flask on a Schlenk line.
  • reaction mixture is thereafter degassed under vacuum at 80 °C for one hour, then purged with nitrogen for thirty minutes at 1 10 °C, and then heated 2012/024973
  • CZTS nanocrystals may be created simply by multiplying the amount of each ingredient by a predetermined factor.
  • the contents are then combined with ethanol, followed by centrifugation, in order to precipitate the CZTS nanocrystals.
  • the precipitated CZTS nanocrystals are further refined to remove solid reaction by products and aggregates of poorly capped nanocrystals by dispersing the nanocrystals in chloroform, followed by centrifugation conducted for two minutes at 8000 rpm. The resulting precipitation is discarded, while the CZTS nanocrystals comprise a supernatant.
  • the CZTS nanocrystals are thereafter collected by centrifugation, dried in vacuum, and ground into powder.
  • a hot press (HP) process is thereafter carried out on the CZTS nanocrystals to form a bulk material while preserving the nanostructure.
  • the CZTS nanocrystals are consolidated at 523 K for 15 minutes under an axial pressure of 120 MPa.
  • X-ray diffraction was performed on the as-synthesized CZTS nanocrystals and the hot pressed CZTS bulk, where the diffraction pattern was indexed to tetragonal CZTS.
  • nanocrystals were in the range of 5 to 30 nanometers. [0024] Referring to FIG. 3, a UV-Vis spectrum indicated that the band gap of the CZTS nanocrystals was 1.5 eV. The relative density of the final CZTS nanocrystals is 89%, which indicates a porous structure.
  • thermoelectric properties for the CZTS nanocrystals were investigated from 300 to 700 K.
  • Seebeck coefficients for the CZTS nanocrystals were measured using MMR Technologies' MMR SB 100 Seebeck Measurement System (www.mmr.com). Comparing the measured Seebeck coefficients for the CZTS nanocrystals with bulk CZTS, it was observed that the Seebeck coefficient was enhanced with the CZTS nanostructure at high temperature.
  • the Seebeck coefficient for CZTS nanocrystals increases from 65 ⁇ / ⁇ at room temperature to 301 ⁇ / ⁇ at 700 K, which is 43% higher than the Seebeck coefficient of the CZTS bulk crystals.
  • a positive Seebeck coefficient indicates that the conduction in CZTS nanocrystals is p-type.
  • electrical conductivity of the CZTS nanocrystals were measured with a home-made electrical measurement system.
  • the electrical conductivity of the CZTS nanocrystals increases from 409 S/m at 300 K to 1388 S/m at 700 K.
  • the thermal conductivity of the Cu-doped CZTS nanocrystals remains low between 300 and 700 K and reaches a minimum of 0.645 W/(m-K) at 700 K, which corresponds to a 28.3% decrease compared to the Cu-doped CZTS bulk crystals (0.9 W/m-K at 700 K).
  • the power factor and figure of merit (ZT) is calculated with the aforementioned thermoelectric properties.
  • the power factor and overall ZT for the CZTS nanocrystal samples reach to their peak values of 125 ⁇ /m-K 2 and 0.14 at 700 K, respectively.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

La présente invention concerne un matériau thermoélectrique et plus spécifiquement des matériaux thermoélectriques nanostructurés ainsi que des procédés pour utiliser et créer ces matériaux nanostructurés comprenant, sans s'y limiter, les matériaux à base de CZTS.
PCT/US2012/024973 2011-02-15 2012-02-14 Conversion d'énergie par effet thermoélectrique basée sur du czts (cuivre-zinc-étain-soufre) nanostructuré WO2012112491A1 (fr)

Applications Claiming Priority (2)

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US201161442947P 2011-02-15 2011-02-15
US61/442,947 2011-02-15

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104031459A (zh) * 2014-06-09 2014-09-10 京东方科技集团股份有限公司 一种Cu2Zn0.14Sn0.25Te2.34纳米晶溶液及制备方法、光敏树脂溶液、黑矩阵的制备方法、彩膜基板
CN105482700A (zh) * 2015-12-15 2016-04-13 吴振宇 一种用于选矿摇床的易固化耐磨生漆涂料及其制备方法
US9618841B2 (en) 2014-06-09 2017-04-11 Boe Technology Group Co., Ltd. Cu2Zn0.14Sn0.25Te2.34 nanocrystalline solution, its preparation method, photosensitive resin solution, method for forming black matrix, and color filter substrate
JP2018088458A (ja) * 2016-11-28 2018-06-07 株式会社日本触媒 熱電変換材料
CN114940618A (zh) * 2022-05-31 2022-08-26 南京理工大学 亚稳态立方相铜锡基硫属化物高熵热电材料及其制备方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010135622A1 (fr) * 2009-05-21 2010-11-25 E. I. Du Pont De Nemours And Company Nanoparticules de chalcogénure de cuivre, de zinc et d'étain

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010135622A1 (fr) * 2009-05-21 2010-11-25 E. I. Du Pont De Nemours And Company Nanoparticules de chalcogénure de cuivre, de zinc et d'étain

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
LIU ET AL.: "Improved Thermoelectric Properties of Cu-Doped Quaternary Chalcogenides of Cu2CdSnSe4", ADV. MATER., vol. 21, no. 37, 5 October 2009 (2009-10-05), pages 3808 - 3812 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104031459A (zh) * 2014-06-09 2014-09-10 京东方科技集团股份有限公司 一种Cu2Zn0.14Sn0.25Te2.34纳米晶溶液及制备方法、光敏树脂溶液、黑矩阵的制备方法、彩膜基板
US9618841B2 (en) 2014-06-09 2017-04-11 Boe Technology Group Co., Ltd. Cu2Zn0.14Sn0.25Te2.34 nanocrystalline solution, its preparation method, photosensitive resin solution, method for forming black matrix, and color filter substrate
CN105482700A (zh) * 2015-12-15 2016-04-13 吴振宇 一种用于选矿摇床的易固化耐磨生漆涂料及其制备方法
JP2018088458A (ja) * 2016-11-28 2018-06-07 株式会社日本触媒 熱電変換材料
CN114940618A (zh) * 2022-05-31 2022-08-26 南京理工大学 亚稳态立方相铜锡基硫属化物高熵热电材料及其制备方法
CN114940618B (zh) * 2022-05-31 2023-05-05 南京理工大学 亚稳态立方相铜锡基硫属化物高熵热电材料及其制备方法

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