CN106025056A - Preparation method of tin-sulfur compound thermoelectric material - Google Patents

Preparation method of tin-sulfur compound thermoelectric material Download PDF

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Publication number
CN106025056A
CN106025056A CN201610410062.9A CN201610410062A CN106025056A CN 106025056 A CN106025056 A CN 106025056A CN 201610410062 A CN201610410062 A CN 201610410062A CN 106025056 A CN106025056 A CN 106025056A
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China
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thiostannate
tin
thermoelectric material
sulfur compound
preparation
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Inventor
王超
陈乙德
杨萍
栾春红
姜晶
梁莹林
伍思昕
张蕊
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University of Electronic Science and Technology of China
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University of Electronic Science and Technology of China
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    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10NELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/01Manufacture or treatment
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10NELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/80Constructional details
    • H10N10/85Thermoelectric active materials
    • H10N10/851Thermoelectric active materials comprising inorganic compositions
    • H10N10/852Thermoelectric active materials comprising inorganic compositions comprising tellurium, selenium or sulfur

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  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Powder Metallurgy (AREA)

Abstract

The invention provides a preparation method of a tin-sulfur compound thermoelectric material. The method comprises the steps of: preparing tin-sulfur compound powder by a coprecipitation method; carrying out multiple washing by deionized water and absolute ethyl alcohol, removing impurity ions to obtain solid powder, and carrying out vacuum drying to obtain the tin-sulfur compound powder; carrying out heating and annealing under an inert atmosphere and preparing the bulk tin-sulfur compound thermoelectric material from the obtained tin-sulfur compound powder in a pressure sintering manner. A soluble salt of tin ions (Sn<4+>) or stannum ions (Sn<2+>) and the soluble salt of sulfur ions (S<2->) are utilized as raw materials; the tin-sulfur compound powder is produced; and then the tin-sulfur compound powder is subjected to high-temperature sintering and recrystallization under an inert gas to obtain the tin-sulfur compound thermoelectric material. Compared with an existing preparation method, the preparation method has the advantages of being low in production cost, simple in equipment, high in safety, simple and convenient to operate and the like; mass production is easy to achieve; the prepared tin-sulfur compound thermoelectric material is low in thermal conductivity and relatively good in performance.

Description

A kind of preparation method of thiostannate thermoelectric material
Technical field
The present invention relates to thermoelectric material field, be specifically related to the preparation method of a kind of thiostannate thermoelectric material.
Background technology
Thermoelectric material is can be directly realized by heat energy and functional material that electric energy is mutually changed, has Seebeck effect and Peltier Effect.Seebeck effect will the metal wire of two unlike materials join end to end composition closed-loop path, is added by one of them junction point Heat is to high temperature, and another junction point keeps low temperature, electric current can be detected in the loop;When be made up of by different conductors electric current During loop, except producing in addition to irreversible Joule heat, in the joint of different conductor along with the difference of the sense of current can occur respectively heat absorption, Exothermic phenomenon, referred to as Peltier effect.The two phenomenon discloses the thermoelectric material application potential in field of energy conversion;Utilize Seebeck effect can realize thermo-electric generation, utilizes Peltier effect can realize static Refrigeration Technique, and both of which has pollution-free, nothing Machine driving, noiselessness, high reliability.
At present, thermoelectric material is in military affairs, Waste Heat Reuse, Aero-Space, automobile, household electrical appliance, medical treatment and extreme condition energy supply etc. The application in field has presented flourish trend, has great business potential.
The thermoelectricity capability of material can be assessed by dimensionless number ZT, and ZT value is the highest, and the thermoelectricity capability of material is the best.At present, ZT The thermoelectric material that value is higher has Skutterudite, Zintl alloy, Clathrate, Half-heusler alloy, metal-oxide, sulfur Compounds of group and β-Zn4Sb3、FeSb2、Mg2Si etc., carry out performance by means such as doping, alloying, Nanostructure fabrications Optimizing, the ZT value of these materials generally can reach more than 1.0.Thiostannate has that the element yield needed for production is big, becomes The advantages such as this relatively low, avirulence, wherein SnS has relatively low thermal conductivity (0.4~0.9W/m K), Seebeck coefficient up to 650 μ V/K, related article reports that it reaches 0.19 (DOI:10.1039/c4ta06955b) in the ZT value of 823K, and SnS2With Sample has relatively low thermal conductivity (0.4~0.7W/m K), and Seebeck coefficient is up to-700 μ V/K, and related article reports its ZT value Up to 0.96 (DOI:10.1039/c5cp03700), thiostannate shows good thermoelectricity capability.
Preparing the main method of thiostannate thermoelectric material at present is to use machine-alloying, by Sn and S element simple substance by mole Than Vacuum Package in ball grinder, high-energy ball milling obtains thiostannate.The method uses high-purity Sn and S simple substance, price Costly, and equipment and operation skill are all had higher requirements, be unfavorable for large-scale production, it is more difficult to popularization and application.For with Upper problem, in the urgent need to a kind of low cost, the thiostannate thermoelectric material preparation method that low technical requires.
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, it is provided that the preparation method of a kind of thiostannate thermoelectric material, with fall Low cost and technology requirement, it is achieved mass generates thiostannate thermoelectric material.
For realizing object above, the preparation method of thiostannate thermoelectric material of the present invention, it is characterised in that comprise the following steps:
Step 1: use coprecipitation, obtain the precipitate of thiostannate;
Step 2: clean thiostannate precipitate, removes impurity therein, and then vacuum drying obtains thiostannate powder;
Step 3: heating anneal thiostannate powder under an inert atmosphere;
Step 4: pressure sintering thiostannate under 430~800 DEG C of scopes, obtains thiostannate block thermoelectric material.
Further, in step 1, described employing coprecipitation presses ion mol ratio Sn4+: S2-=1:2 or Sn2+: S2-=1:1 The soluble salt of mixing tin ion or stannous ion and the soluble salt solution of sulphion, continuously stirred two kinds of solution of lower mixing, obtain stannum sulfur Compound precipitation thing.
Further, in step 2, described cleaning method is deionized water and dehydrated alcohol is cleaned multiple times thiostannate precipitation Thing, carries out vacuum drying treatment to sample after having cleaned, and wash number is 1~10 time, and vacuum drying temperature is 50~100 DEG C.
Further, in step 3, described being heated to be under an inert atmosphere: temperature is 300~800 DEG C, heat time heating time is 2~24h (hour), controlling inert gas flow is 30~200mL/min (ml/min).
Further, in step 4, described pressure sintering mode is hot pressed sintering or discharge plasma sintering, and sintering temperature is 430~800 DEG C, pressurize 50~65Mpa (MPa), sintering time 3~20min (minute).
The object of the present invention is achieved like this:
The preparation method of thiostannate thermoelectric material of the present invention, uses coprecipitation to prepare thiostannate powder, at inert atmosphere Under it carried out heating anneal make it crystallize more preferably, use pressure sintering mode to be fabricated to block thiostannate thermoelectric material.This Tin ion or the soluble salt of the soluble salt of stannous ion and sulphion that bright use is cheap are material, it is not necessary to expensive chemistry unit Material and the equipment such as element simple substance and high energy ball mill;Compared with existing preparation method, having production cost low, equipment is simple, peace Quan Xinggao, easy and simple to handle, it is easy to the advantages such as mass generation.Meanwhile, the thiostannate thermoelectric material thermal conductivity prepared is low, Thermoelectricity capability is preferable.
Accompanying drawing explanation
Fig. 1 is the preparation method one detailed description of the invention flow chart of SnS thermoelectric material of the present invention;
Fig. 2 is the X-ray diffractogram of embodiment 1,2 gained SnS thermoelectric material;
Fig. 3 is the electrical conductivity temperature characterisitic schematic diagram of embodiment 1,2 gained SnS thermoelectric material;
Fig. 4 is the Seebeck coefficient temperature characterisitic schematic diagram of embodiment 1,2 gained SnS thermoelectric material;
Fig. 5 is the thermal conductivity temperature characterisitic schematic diagram of embodiment 1,2 gained SnS thermoelectric material;
Fig. 6 is the ZT value temperature characterisitic schematic diagram of embodiment 1,2 gained SnS thermoelectric material.
Detailed description of the invention
Below in conjunction with the accompanying drawings the detailed description of the invention of the present invention is described, in order to those skilled in the art is more fully understood that this Bright.Requiring particular attention is that, in the following description, when perhaps the detailed description of known function and design can desalinate this During bright main contents, these are described in and will be left in the basket here.
Fig. 1 is a kind of concrete mode embodiment flow chart of preparation method of thiostannate thermoelectric material of the present invention.
In the present embodiment, as it is shown in figure 1, the preparation method of thiostannate thermoelectric material of the present invention comprises the following steps that
Step 1: by ion mol ratio Sn4+: S2-=1:2 or Sn2+: S2-=1:1 prepares the solvable of tin ion or stannous ion respectively Salt and the soluble salt solution of sulphion, continuously stirred two kinds of solution of lower mixing, obtain thiostannate precipitate;
Step 2: alternately clean thiostannate precipitate 1~10 times with deionized water and dehydrated alcohol, to remove foreign ion, Such as Na+Ion, Cl-Ion and SO4 2-Ions etc., obtain pure thiostannate precipitate, and then 50~80 DEG C of vacuum are dried Dry, obtain thiostannate powder;
Step 3: after thiostannate powder mull, under an inert atmosphere heating thiostannate powder.Heating-up temperature is 300~800 DEG C, heat time heating time is 2~24h, after heating terminates, cools to room temperature with the furnace under inert atmosphere protection;
Step 4: putting into graphite jig by after thiostannate powder mull, pressure sintering becomes block so that it is performance is more stable. Concrete employing plasma discharging or hot pressed sintering mode, pressure is 50~65Mpa, sinters 3~20min at 430~800 DEG C, To block thiostannate thermoelectric material.
Embodiment 1
By SnCl2(analytical pure) and Na2S2O3It is molten that (analytical pure) is dissolved in 100mL ethylenediaminetetraacetic acid respectively by 2:1 mol ratio Liquid and 100mL deionized water, to SnCl2Solution is sequentially added into 10mL triethanolamine and 90mL ammonia, handle after stirring Na2S2O3Solution adds SnCl2In solution, normal-temperature reaction 15min under magnetic stirring, obtain coffee-like precipitation;Use deionization Water and dehydrated alcohol alternately clean precipitation 6 times, then precipitate are put into vacuum drying oven, and 80 DEG C of vacuum drying 6h obtain SnS Powder;Ground SnS powder is put in tube furnace, is passed through nitrogen with 100mL/min, be warming up to 700 DEG C and keep 4h, It is cooled to room temperature under nitrogen protection;To insert in the graphite jig that internal diameter is 10~13mm after SnS powder mull, use electric discharge Plasma agglomeration mode, plus-pressure 65Mpa, sinter 3~20min at 650 DEG C, obtain block SnS thermoelectric material.
According to X-ray diffractogram shown in Fig. 2, it is known that the present embodiment is successfully prepared SnS thermoelectric material.
Prepared by the present embodiment shown in Fig. 3, SnS thermoelectric material has higher electrical conductivity, can reach about 14S/cm.
Fig. 4 shows that SnS thermoelectric material prepared by the present embodiment has bigger Seebeck coefficient.
Fig. 5 shows that the thermal conductivity under 500K~850K of SnS thermoelectric material prepared by the present embodiment raises with temperature and is gradually lowered, Mental retardation reaches 0.55W/m about K.
Fig. 6 shows that prepared by the present embodiment, SnS thermoelectric material has preferable thermoelectricity capability, and its ZT value is in measuring temperature range Keep ascendant trend, be issued to about ZT=0.31 measuring range limit 850K, show preferable performance.In sum, The preparation method of the present invention is suitable for application and large-scale production.
Embodiment 2
Heating anneal SnS powder under inert atmosphere, is warming up to 700 DEG C and 600 DEG C respectively, and remaining operation is all with embodiment 1, system The thing phase of the standby SnS thermoelectric material obtained and thermoelectricity capability are as shown in Figures 2 to 6.
Although above the detailed description of the invention of invention description being described, in order to those skilled in the art understand this Invention, it should be apparent that the invention is not restricted to the scope of detailed description of the invention, from the point of view of those skilled in the art, As long as various changes limit and in the spirit and scope of the present invention that determine, these changes are apparent from appended claim, All utilize the innovation and creation of present inventive concept all at the row of protection.

Claims (5)

1. the preparation method of a thiostannate thermoelectric material, it is characterised in that comprise the following steps:
Step 1: use coprecipitation, obtain the precipitate of thiostannate;
Step 2: clean thiostannate precipitate, removes impurity therein, and then vacuum drying obtains thiostannate powder;
Step 3: heating anneal thiostannate powder under an inert atmosphere;
Step 4: pressure sintering thiostannate under 430~800 DEG C of scopes, obtains thiostannate block thermoelectric material.
Preparation method the most according to claim 1, it is characterised in that use coprecipitation to press ion mol ratio in step 1 Sn4+: S2-=1:2 or Sn2+: S2-The soluble salt of=1:1 mixing tin ion or stannous ion and the soluble salt solution of sulphion, continue The lower two kinds of solution of mixing of stirring, obtain thiostannate precipitate.
Preparation method the most according to claim 1, it is characterised in that in step 2 is many with deionized water and dehydrated alcohol Secondary cleaning thiostannate precipitate, carries out vacuum drying treatment to sample after having cleaned, and wash number is 1~10 time, vacuum Baking temperature is 50~100 DEG C.
Preparation method the most according to claim 1, it is characterised in that in step 3, described under an inert atmosphere Being heated to be: temperature is 300~800 DEG C, heat time heating time is 2~24 hours, and controlling inert gas flow is 30~200mL/min.
Method the most according to claim 1, it is characterised in that in step 4, described pressure sintering mode is hot pressing Sintering or discharge plasma sintering, sintering temperature is 430~800 DEG C, pressurization 50~65Mpa, sintering time 3~20 minutes.
CN201610410062.9A 2016-06-12 2016-06-12 Preparation method of tin-sulfur compound thermoelectric material Pending CN106025056A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109628784A (en) * 2018-12-29 2019-04-16 六盘水师范学院 A kind of high-temperature solid phase reaction method preparation FeSb2Method
US11072530B2 (en) 2016-12-28 2021-07-27 Lg Chem, Ltd. Compound semiconductor and use thereof
CN112885948B (en) * 2021-01-14 2022-07-29 电子科技大学 Copper-selenium-based thermoelectric material with high structural stability and preparation method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120138870A1 (en) * 2010-11-02 2012-06-07 California Institute Of Technology HIGH THERMOELECTRIC PERFORMANCE BY CONVERGENCE OF BANDS IN IV-VI SEMICONDUCTORS, HEAVILY DOPED PbTe, AND ALLOYS/NANOCOMPOSITES
CN102612486A (en) * 2009-11-25 2012-07-25 E·I·内穆尔杜邦公司 Aqueous process for producing crystalline copper chalcogenide nanoparticles, the nanoparticles so-produced, and inks and coated substrates incorporating the nanoparticles
CN102623567A (en) * 2012-04-09 2012-08-01 上海大学 Water bath preparation method of Cu2FeSnS4 nano-crystal thin film
CN102897827A (en) * 2012-10-09 2013-01-30 东华大学 Method for phased synthesis of SnS, SnS2 or SnS/SnS2 heterojunction nanocrystalline material by one-step process
CN103818948A (en) * 2014-02-17 2014-05-28 河南理工大学 Preparation method of thermoelectric compound
CN104810465A (en) * 2015-04-21 2015-07-29 电子科技大学 Cu2-xS thermoelectric material preparation method

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102612486A (en) * 2009-11-25 2012-07-25 E·I·内穆尔杜邦公司 Aqueous process for producing crystalline copper chalcogenide nanoparticles, the nanoparticles so-produced, and inks and coated substrates incorporating the nanoparticles
US20120138870A1 (en) * 2010-11-02 2012-06-07 California Institute Of Technology HIGH THERMOELECTRIC PERFORMANCE BY CONVERGENCE OF BANDS IN IV-VI SEMICONDUCTORS, HEAVILY DOPED PbTe, AND ALLOYS/NANOCOMPOSITES
CN102623567A (en) * 2012-04-09 2012-08-01 上海大学 Water bath preparation method of Cu2FeSnS4 nano-crystal thin film
CN102897827A (en) * 2012-10-09 2013-01-30 东华大学 Method for phased synthesis of SnS, SnS2 or SnS/SnS2 heterojunction nanocrystalline material by one-step process
CN103818948A (en) * 2014-02-17 2014-05-28 河南理工大学 Preparation method of thermoelectric compound
CN104810465A (en) * 2015-04-21 2015-07-29 电子科技大学 Cu2-xS thermoelectric material preparation method

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
ZULKARNAIN ZAINAL等: "Properties of tin sulphide thin films electrodeposited in the presence of triethanolamine", 《JOURNAL OF MATERIALS SCIENCE MATERIALS IN ELECTRONICS》 *
胡永红等: "化学浴法沉积SnS薄膜的机理分析", 《西安理工大学学报》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11072530B2 (en) 2016-12-28 2021-07-27 Lg Chem, Ltd. Compound semiconductor and use thereof
CN109628784A (en) * 2018-12-29 2019-04-16 六盘水师范学院 A kind of high-temperature solid phase reaction method preparation FeSb2Method
CN112885948B (en) * 2021-01-14 2022-07-29 电子科技大学 Copper-selenium-based thermoelectric material with high structural stability and preparation method thereof

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Application publication date: 20161012