CN102280570B - Trace Cu-doped Bi2S3-based thermoelectric material - Google Patents

Trace Cu-doped Bi2S3-based thermoelectric material Download PDF

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Publication number
CN102280570B
CN102280570B CN 201110218183 CN201110218183A CN102280570B CN 102280570 B CN102280570 B CN 102280570B CN 201110218183 CN201110218183 CN 201110218183 CN 201110218183 A CN201110218183 A CN 201110218183A CN 102280570 B CN102280570 B CN 102280570B
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thermoelectric material
powder
thermal conductivity
power factor
bi2s3
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CN102280570A (en
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张波萍
葛振华
于昭新
刘勇
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University of Science and Technology Beijing USTB
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University of Science and Technology Beijing USTB
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Abstract

The invention belongs to the technical field of energy materials and in particular relates to a trace Cu-doped Bi2S3-based thermoelectric material. In the thermoelectric material, metal simple substance Bi and Cu powder with the purity of 99.99 percent and simple substance S powder serve as raw materials, the thermoelectric material is prepared according to a chemical general formula of CuxBi2-xS3, wherein x is mole fraction of a Cu component and x is more than or equal to 0.001 and less than or equal to 0.05, and the thermoelectric material is prepared into a block material by combining a discharge plasma sintering technology and a mechanical alloying method. By the method, the trace Cu-doped Bi2S3-based block thermoelectric material can be easy and convenient to prepare, trace Cu is introduced into a Bi2S3 lattice, the carrier concentration of a sample is improved, a power factor is optimized, a Cu-S nano deposition coherent with a substrate structure is formed, and the thermal conductivity is greatly reduced; therefore, the thermoelectric performance of the Bi2S3-based block material can be greatly improved.

Description

A kind of micro Cu doping Bi 2S 3Base thermoelectricity material
Technical field
The invention belongs to the energy and material technical field, particularly a kind of micro Cu doping Bi 2S 3Base thermoelectricity material.
Background technology
Along with socioeconomic development, environment and energy problem are more and more paid attention to by the mankind.Thermoelectric material can directly be realized the mutual conversion of heat energy and electric energy, and thermoelectric device is pollution-free, zero discharge and structure is light, volume is little, the life-span is long, day by day receives people's concern.Electrothermal module take thermoelectric device as core parts has a wide range of applications at aspects such as semiconductor refrigerating, thermoelectric cells.With the competition of the refrigeration modes of routine and conventional power source in, thermoelectric device realizes that the key of extensive use is to improve the efficient of thermoelectric cooling and thermoelectric power generation.Thermoelectricity capability characterizes ZT=TS with dimensionless thermoelectric figure of merit ZT 2σ/κ, S are Seebeck coefficients, and σ is conductivity, and κ is thermal conductivity, and T is absolute temperature; S 2σ is called power factor, is used for characterizing the electrical transmission performance of thermoelectric material, and thermal conductivity κ is charge carrier thermal conductivity κ eWith lattice thermal conductivity κ LSum.Well behaved thermoelectric material need to have high power factor and low thermal conductivity.But above-mentioned each physical quantity is interrelated, all relevant with carrier concentration, high carrier concentration is conducive to obtain high power factor, but the charge carrier thermal conductivity is risen, therefore the thermoelectricity capability that improves material must be controlled suitable carrier concentration, and reduces lattice thermal conductivity.The method that improves the block materials thermoelectricity capability has doping, texture, Composition Control etc.These methods are when improving power factor, and thermal conductivity slightly increases; When perhaps power factor descended slightly, thermal conductivity declined to a great extent, the lifting of combined influence thermoelectric figure of merit.
Cu is a kind of good conductor, has and appraises at the current rate, although be a kind of doped chemical commonly used, yet there are no relevant Cu doping Bi 2S 3The relevant report of base thermoelectricity material.Cu is different from other doped chemicals simultaneously, and Cu and S very easily form available general formula Cu 2-xS(0≤x≤1) a series of compounds of expression.If therefore at Bi 2S 3In carry out Cu when mixing experiment, can the part degree optimize carrier concentration although Cu mixes, this and other element doping effect is similar, is conducive to improve its power factor.But when the Cu doping large or control not at that time, Cu and S form second-phase impurity easily, will cause the resistivity of system significantly to increase, and compare pure Bi under the room temperature 2S 3Resistivity increase severely 3 more than the order of magnitude, be unfavorable for the lifting of thermoelectricity capability.The application's patent utilizes Cu and S very easily to form Cu exactly 2-xS(0≤x≤1) characteristic of series compound, with the second-phase Control of Impurities at nanoscale, make it in matrix, form the Cu-S nanometer precipitate of a large amount of and matrix phase structure coherence, when optimizing its power factor, significantly reduce its lattice thermal conductivity, reach the purpose that promotes thermoelectricity capability.
Summary of the invention
The objective of the invention is in order simply, conveniently, accurately to prepare the Bi that micro Cu is mixed 2S 3Matrix body material solves in the pyroelectric material performance optimizing process, and the problem that is difficult to improve simultaneously power factor and reduces thermal conductivity significantly improves Bi 2S 3The thermoelectricity capability of matrix body material.
Technical scheme of the present invention is: a kind of micro Cu doping Bi 2S 3Base thermoelectricity material, this thermoelectric material take purity as 99.99% metal simple-substance Bi, Cu powder and simple substance S powder be as raw material, according to chemical general formula Cu x Bi 2- x S 3(wherein xBe the molar fraction of Cu component, xSpan is 0.001≤ x≤ 0.05) configuration mixes, and adopts mechanical alloying method to be prepared into block materials in conjunction with discharge plasma sintering technique.
Principle of the present invention is: cross the addition of controlling various raw materials, accurately control the stoichiometric proportion of each element, so that the Cu of trace enters Bi in ma process and discharge plasma sintering process 2S 3In the lattice, regulate carrier concentration, improve the Cu-S nanometer precipitate of power factor and formation and matrix phase structure coherence, in the situation that does not affect conductivity, significantly reduce its lattice thermal conductivity.
The invention has the beneficial effects as follows: the method can simply, conveniently, accurately be prepared the Bi that micro Cu is mixed 2S 3Matrix body heat electric material is by the thermal conductivity that not only improves the power factor of sample but also significantly reduce sample of mixing of micro Cu.
Description of drawings
Fig. 1: the fracture stereoscan photograph of a kind of micro Cu doping of the present invention bismuth sulfide base thermoelectricity material block.
Fig. 2: the TEM photo of a kind of micro Cu doping of the present invention bismuth sulfide base thermoelectricity material.
Embodiment
Example 1
Press Cu:Bi: S mol ratio 0.001:1.999:3 is high-purity (99.99%) Cu powder, Bi powder and the S powder of weighing respectively, mixes, and puts into ball grinder, is filled with Ar gas after vacuumizing, and circulates three times, makes Ar gas be full of ball grinder, and ball grinder is airtight.Then ball grinder is put into ball mill, 400 rpm ball milling 10h take out ball grinder after complete, inject 100 ml absolute ethyl alcohols in ball grinder, in this process, keep the Ar air-flow logical, so as not to the destruction inert protective atmosphere, 250 rpm wet-millings 30 minutes.Powder is taken out, put into the drying box drying, temperature is 80 ℃, and the time is 2 h.Dried powder becomes block with discharge plasma sintering, and mould diameter is 20 mm, and programming rate is 100 ℃/min, 300 ℃ of temperature, and pressure 20Pa, temperature retention time is 5 min.Obtain at last the Cu that trace copper mixes 0.001Bi 1.999S 3Thermoelectric material, its power factor is 200 μ Wm during through test, calculating 573 K -1K -2, thermal conductivity is 0.6 Wm -1K -1
Example 2
Press Cu:Bi: S mol ratio 0.002:1.998:3 is high-purity (99.99%) Cu powder, Bi powder and the S powder of weighing respectively, mixes, and puts into ball grinder, is filled with Ar gas after vacuumizing, and circulates three times, makes Ar gas be full of ball grinder, and ball grinder is airtight.Then ball grinder is put into ball mill, 450 rpm ball millings, 15 h take out ball grinder after complete, inject the 100ml absolute ethyl alcohol in ball grinder, in this process, keep the Ar air-flow logical, so as not to the destruction inert protective atmosphere, 300 rpm wet-millings, 1 h.Powder is taken out, put into the drying box drying, temperature is 80 ℃, and the time is 12 h.The powder of drying is become block with discharge plasma sintering, and mould diameter is 10 mm, and programming rate is 100 ℃/min, 550 ℃ of temperature, and pressure 60 Pa temperature retention times are 5 min.Obtain at last the Cu that trace copper mixes 0.002Bi 1.998S 3Thermoelectric material, its power factor is 240 μ Wm during through test, calculating 573 K -1K -2, thermal conductivity is 0.54 Wm -1K -1
Example 3
Press Cu:Bi: S mol ratio 0.007:1.995:3 is high-purity (99.99%) Cu powder, Bi powder and the S powder of weighing respectively, mixes, and puts into ball grinder, is filled with Ar gas after vacuumizing, and circulates three times, makes Ar gas be full of ball grinder, and ball grinder is airtight.Then ball grinder is put into ball mill, 300 rpm ball millings, 20 h take out ball grinder after complete, inject 100 ml absolute ethyl alcohols in ball grinder, in this process, keep the Ar air-flow logical, so as not to the destruction inert protective atmosphere, 425 rpm wet-millings, 3 h.Powder is taken out, put into the drying box drying, temperature is 80 ℃, and the time is 8 h.The powder of drying is become block with discharge plasma sintering, and mould diameter is 25 mm, and programming rate is 100 ℃/min, 400 ℃ of temperature, and pressure 40 Pa, temperature retention time is 5 min.Obtain at last the Cu that trace copper mixes 0.007Bi 1.993S 3Thermoelectric material, its power factor is 303 μ Wm during through test, calculating 573 K -1K -2, thermal conductivity is 0.3 Wm -1K -1
Example 4
Press Cu:Bi: S mol ratio 0.01:1.993:3 is high-purity (99.99%) Cu powder, Bi powder and the S powder of weighing respectively, mixes, and puts into ball grinder, is filled with Ar gas after vacuumizing, and circulates three times, makes Ar gas be full of ball grinder, and ball grinder is airtight.Then ball grinder is put into ball mill, 450 rpm ball millings, 15 h take out ball grinder after complete, inject 100 ml absolute ethyl alcohols in ball grinder, in this process, keep the Ar air-flow logical, so as not to the destruction inert protective atmosphere, 200 rpm wet-millings, 3 h.Powder is taken out, put into the drying box drying, temperature is 80 ℃, and the time is 2 h.The powder of drying is carried out discharge plasma sintering become block, mould diameter is 15 mm, and programming rate is 100 ℃/min, 580 ℃ of temperature, and pressure 40 Pa, temperature retention time is 5 min.Obtain at last the Cu that trace copper mixes 0.01Bi 1.99S 3Thermoelectric material, its power factor is 175 μ Wm during through test, calculating 573 K -1K -2, thermal conductivity is 0.65 Wm -1K -1
Example 5
Press Cu:Bi: S mol ratio 0.05:1.99:3 is high-purity (99.99%) Cu powder, Bi powder and the S powder of weighing respectively, mixes, and puts into ball grinder, is filled with Ar gas after vacuumizing, and circulates three times, makes Ar gas be full of ball grinder, and ball grinder is airtight.Then ball grinder is put into ball mill, 600 rpm ball millings, 20 h take out ball grinder after complete, inject the 100ml absolute ethyl alcohol in ball grinder, in this process, keep the Ar air-flow logical, so as not to the destruction inert protective atmosphere, 350 rpm wet-millings, 5 h.Powder is taken out, put into the drying box drying, temperature is 80 ℃, and the time is 2 h.The powder of drying is become block with discharge plasma sintering, and mould diameter is 30 mm, and programming rate is 100 ℃/min, 600 ℃ of temperature, and pressure 60 Pa, temperature retention time is 5 min.Obtain at last the Cu that trace copper mixes 0.05Bi 1.95S 3Thermoelectric material, its power factor is 198 μ Wm during through test, calculating 573 K -1K -2, thermal conductivity is 0.66 Wm -1K -1
Example 6
Press Cu:Bi: S mol ratio 0.025:1.975:3 is high-purity (99.99%) Cu powder, Bi powder and the S powder of weighing respectively, mixes, and puts into ball grinder, is filled with Ar gas after vacuumizing, and circulates three times, makes Ar gas be full of ball grinder, and ball grinder is airtight.Then ball grinder is put into ball mill, 425 rpm ball millings, 20 h take out ball grinder after complete, inject the 50ml absolute ethyl alcohol in ball grinder, in this process, keep the Ar air-flow logical, so as not to the destruction inert protective atmosphere, 350 rpm wet-millings, 5 h.Powder is taken out, put into the drying box drying, temperature is 80 ℃, and the time is 2 h.The powder of drying is become block with discharge plasma sintering, and mould diameter is 20 mm, and programming rate is 100 ℃/min, 600 ℃ of temperature, and pressure 60 Pa, temperature retention time is 5 min.Obtain at last the Cu that trace copper mixes 0.05Bi 1.95S 3Thermoelectric material, its power factor is 220 μ Wm during through test, calculating 573 K -1K -2, thermal conductivity is 0.69 Wm -1K -1
Example 7
Press Cu:Bi: S mol ratio 0.045:1.955:3 is high-purity (99.99%) Cu powder, Bi powder and the S powder of weighing respectively, mixes, and puts into ball grinder, is filled with Ar gas after vacuumizing, and circulates three times, makes Ar gas be full of ball grinder, and ball grinder is airtight.Then ball grinder is put into ball mill, 450 rpm ball millings, 20 h take out ball grinder after complete, inject the 80ml absolute ethyl alcohol in ball grinder, in this process, keep the Ar air-flow logical, so as not to the destruction inert protective atmosphere, 350 rpm wet-millings, 5 h.Powder is taken out, put into the drying box drying, temperature is 80 ℃, and the time is 2 h.The powder of drying is become block with discharge plasma sintering, and mould diameter is 20 mm, and programming rate is 100 ℃/min, 600 ℃ of temperature, and pressure 60 Pa, temperature retention time is 5 min.Obtain at last the Cu that trace copper mixes 0.05Bi 1.95S 3Thermoelectric material, its power factor is 201 μ Wm during through test, calculating 573 K -1K -2, thermal conductivity is 0.68 Wm -1K -1

Claims (8)

1. micro Cu doping Bi 2S 3Base thermoelectricity material is characterized in that: the composition of this material take purity as 99.99% metal simple-substance Bi, Cu powder and simple substance S powder be as raw material, chemical general formula is Cu x Bi 2- x S 3, wherein xBe the molar fraction of Cu component, xSpan is 0.001≤ x≤ 0.05.
2. According to claim 1A kind of micro Cu doping Bi 2S 3Base thermoelectricity material is characterized in that: work as X=0.001, chemical formula is Cu 0.001Bi 1.999S 3Thermoelectric material, its power factor is 200 μ Wm during through test, calculating 573 K -1K -2, thermal conductivity is 0.6 Wm -1K -1
3. According to claim 1A kind of micro Cu doping Bi 2S 3Base thermoelectricity material is characterized in that: work as X=0.002, chemical formula is Cu 0.002Bi 1.998S 3Thermoelectric material, its power factor is 240 μ Wm during through test, calculating 573 K -1K -2, thermal conductivity is 0.54 Wm -1K -1
4. According to claim 1A kind of micro Cu doping Bi 2S 3Base thermoelectricity material is characterized in that: work as X=0.007, chemical formula is Cu 0.007Bi 1.993S 3Thermoelectric material, its power factor is 303 μ Wm during through test, calculating 573 K -1K -2, thermal conductivity is 0.3 Wm -1K -1
5. According to claim 1A kind of micro Cu doping Bi 2S 3Base thermoelectricity material is characterized in that: work as X=0.01, chemical formula is Cu 0.01Bi 1.99S 3Thermoelectric material, its power factor is 175 μ Wm during through test, calculating 573 K -1K -2, thermal conductivity is 0.65 Wm -1K -1
6. According to claim 1A kind of micro Cu doping Bi 2S 3Base thermoelectricity material is characterized in that: work as X=0.05, chemical formula is Cu 0.05Bi 1.95S 3Thermoelectric material, its power factor is 198 μ Wm during through test, calculating 573 K -1K -2, thermal conductivity is 0.66 Wm -1K -1
7. According to claim 1A kind of micro Cu doping Bi 2S 3Base thermoelectricity material is characterized in that: work as X=0.025, chemical formula is Cu 0.01Bi 1.975S 3Thermoelectric material, its power factor is 220 μ Wm during through test, calculating 573 K -1K -2, thermal conductivity is 0.69 Wm -1K -1
8. According to claim 1A kind of micro Cu doping Bi 2S 3Base thermoelectricity material is characterized in that: work as X=0.045, chemical formula is Cu 0.045Bi 1.955S 3Thermoelectric material, its power factor is 201 μ Wm during through test, calculating 573 K -1K -2, thermal conductivity is 0.68 Wm -1K -1
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CN104591103A (en) * 2014-12-30 2015-05-06 华中科技大学 Bi2Te3-xSx thermoelectric material and preparation method thereof
CN104692448B (en) * 2015-03-18 2017-01-25 武汉理工大学 Synthesis method of dynamic load of Ag2S (Silver Sulfide)-based compound and reactive assistant thereof
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CN106587135B (en) * 2016-12-28 2017-12-29 中国科学院上海高等研究院 Cu S base thermoelectricity materials of I doping and preparation method thereof
CN109659425B (en) * 2018-12-29 2020-07-10 昆明理工大学 Bismuth-based thermoelectric material with doping effect improved by using barrier layer and preparation method thereof
CN111304492B (en) * 2020-03-12 2021-07-06 中南大学 Low-temperature n-type thermoelectric material and preparation method thereof
CN112299482B (en) * 2020-09-22 2022-09-27 南京理工大学 Method for reducing thermal conductivity of bismuth sulfide thermoelectric material
CN113511897B (en) * 2021-04-25 2022-09-13 郑州大学 Bi 2 S 3 Block thermoelectric material and high-voltage preparation method thereof

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