CN106410023A - Method for preparing graphene composite thermoelectric material - Google Patents

Method for preparing graphene composite thermoelectric material Download PDF

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Publication number
CN106410023A
CN106410023A CN201611172750.2A CN201611172750A CN106410023A CN 106410023 A CN106410023 A CN 106410023A CN 201611172750 A CN201611172750 A CN 201611172750A CN 106410023 A CN106410023 A CN 106410023A
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thermoelectric
ball
powder
snseal
graphene composite
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不公告发明人
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Suzhou Sichuang Yuanbo Electronic Technology Co Ltd
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Suzhou Sichuang Yuanbo Electronic Technology Co Ltd
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Priority to CN201611172750.2A priority Critical patent/CN106410023A/en
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    • 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
    • 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
    • H10N10/01—Manufacture or treatment
    • 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

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The invention discloses a method for preparing a graphene composite thermoelectric material. For the graphene composite SnSe-based thermoelectric material obtained by the preparation method, thermoelectric performance of SnSe-based block material is substantially improved, the method directly utilizes SPS sintering to perform in-situ reaction, and the prepared material has high density, uniform components and excellent performance.

Description

A kind of preparation method of Graphene composite thermoelectric material
Technical field
The present invention relates to thermoelectricity composite functional material field is and in particular to a kind of preparation side of Graphene composite thermoelectric material Method.
Background technology
Thermoelectric material (Thermoelectric Materials) is also referred to as thermoelectric material.Thermoelectric material is mainly used in Prepare thermoelectric cooling device and Thermoelectric Generator.Temperature gradient field heat to electricity conversion principle abbreviation thermoelectric principle (Thermoe1ectric), its discovery can trace back to for 19th century, 1822, and ThomasSeebeck finds thermoelectromotive force effect Answer (thermoelectric material electricity generating principle, i.e. Seebeck principle)；1834, Jean Peltier found two difference in current loop Effects of reduced temperature (thermoelectric material refrigeration principle, i.e. Peltier principle) at material conductor junction interface.The 1950's finds Some semi-conducting materials are good thermoelectric materials.The operating efficiency of thermoelectric device depends on a dimensionless ginseng of material Number：ZT.TE requirement on devices ZT is the bigger the better, and ZT is bigger, and efficiency is higher.Generally the material of ZT ＞ 0.5 is called thermoelectric material.
It is published within 2014《nature》Correlative study on magazine is pointed out, SnSe has ultralow thermal conductivity, monocrystalline SnSe has record-breaking high electric heating value.This makes SnSe as a new thermoelectric material system, starts to cause research people The extensive attention of member, its excellent performance shows that SnSe is the very promising thermoelectric material of one kind.Thus, the synthesis to SnSe and Its performance study has very important significance.
Content of the invention
The present invention provides a kind of preparation method of Graphene composite thermoelectric material, and the Graphene that this preparation method obtains is combined SnSe base thermoelectricity material, is greatly improved the thermoelectricity capability of SnSe base block materials, and the method is directly carried out former using SPS sintering Position reaction, the material density of preparation is high, composition is uniform, excellent performance.
To achieve these goals, the invention provides a kind of preparation method of Graphene composite thermoelectric material, the method Comprise the steps：
（1）Prepare doping vario-property thermoelectric composite material powder
According to chemical formula SnSeAl in argon atmospher glove boxxEach element content proportioning, wherein 0.02≤x≤0.03, by powder End mixes, and is sealed in ball grinder under protective atmosphere, is placed on high energy ball mill and carries out ball milling, and Ball-milling Time is 15- 18h, ratio of grinding media to material is 10:1, drum's speed of rotation is 500-800r/min, obtains SnSeAlxMatrix powder；
By the SnSeAl of preparation in argon atmospher glove boxxPowder according to Graphene mass ratio y is respectively：50：1≤y≤ 100：1 proportioning mixes, and carries out ball milling, Ball-milling Time 2-4h on high speed ball mill, and ratio of grinding media to material is 10：1, ball mill turns Speed is 500-800r/min, the doping vario-property thermoelectric composite material powder being uniformly mixed；
（2）Doping vario-property thermoelectric composite material powder is loaded in graphite grinding tool and is compacted, exist together with grinding tool<The vacuum of 10Pa Under the conditions of be sintered, programming rate be 25 DEG C/min-50 DEG C/min, sintering temperature be 600-900 DEG C, pressure be 75- 95MPa, sintering time be 10-20h minute, raw material sintering during carry out reaction in-situ generate target substance, simultaneously plus Pressure can make it densified again, finally gives the block Graphene composite thermoelectric material of densification.
Specific embodiment
Embodiment one
According to chemical formula SnSeAl in argon atmospher glove boxxEach element content proportioning, wherein x=0.02, by powder mixing all Even, it is sealed under protective atmosphere in ball grinder, is placed on high energy ball mill and carries out ball milling, Ball-milling Time is 15h, ratio of grinding media to material is 10:1, drum's speed of rotation is 500r/min, obtains SnSeAlxMatrix powder.
By the SnSeAl of preparation in argon atmospher glove boxxPowder respectively according to Graphene mass ratio y be 50：1 join Ratio mixes, and carries out ball milling, Ball-milling Time 2h on high speed ball mill, and ratio of grinding media to material is 10：1, drum's speed of rotation is 500r/ Min, the doping vario-property thermoelectric composite material powder being uniformly mixed.
Doping vario-property thermoelectric composite material powder is loaded in graphite grinding tool and is compacted, exist together with grinding tool<10Pa's is true It is sintered under empty condition, programming rate is 25 DEG C/min, sintering temperature is 600 DEG C, pressure is 75MPa, sintering time is 10 Minute, raw material carries out reaction in-situ during sintering and generates target substance, and pressurization simultaneously can make it densified again, final To fine and close Graphene composite thermoelectric material.
Embodiment two
According to chemical formula SnSeAl in argon atmospher glove boxxEach element content proportioning, wherein x=0.03, by powder mixing all Even, it is sealed under protective atmosphere in ball grinder, is placed on high energy ball mill and carries out ball milling, Ball-milling Time is 18h, ratio of grinding media to material is 10:1, drum's speed of rotation is 800r/min, obtains SnSeAlxMatrix powder.
By the SnSeAl of preparation in argon atmospher glove boxxPowder respectively according to Graphene mass ratio y be 100：1 join Ratio mixes, and carries out ball milling, Ball-milling Time 4h on high speed ball mill, and ratio of grinding media to material is 10：1, drum's speed of rotation is 800r/ Min, the doping vario-property thermoelectric composite material powder being uniformly mixed.
Doping vario-property thermoelectric composite material powder is loaded in graphite grinding tool and is compacted, exist together with grinding tool<10Pa's is true It is sintered under empty condition, programming rate is 50 DEG C/min, sintering temperature is 900 DEG C, pressure is 95MPa, sintering time is 20 Minute, raw material carries out reaction in-situ during sintering and generates target substance, and pressurization simultaneously can make it densified again, final To fine and close Graphene composite thermoelectric material.

Claims (1)

1. a kind of preparation method of Graphene composite thermoelectric material, the method comprises the steps：
（1）Prepare doping vario-property thermoelectric composite material powder
According to chemical formula SnSeAl in argon atmospher glove boxxEach element content proportioning, wherein 0.02≤x≤0.03, by powder Mix, be sealed under protective atmosphere in ball grinder, be placed on high energy ball mill and carry out ball milling, Ball-milling Time is 15- 18h, ratio of grinding media to material is 10:1, drum's speed of rotation is 500-800r/min, obtains SnSeAlxMatrix powder；
By the SnSeAl of preparation in argon atmospher glove boxxPowder according to Graphene mass ratio y is respectively：50：1≤y≤100： 1 proportioning mixes, and carries out ball milling, Ball-milling Time 2-4h on high speed ball mill, and ratio of grinding media to material is 10：1, drum's speed of rotation is 500-800r/min, the doping vario-property thermoelectric composite material powder being uniformly mixed；
（2）Doping vario-property thermoelectric composite material powder is loaded in graphite grinding tool and is compacted, exist together with grinding tool<The vacuum of 10Pa Under the conditions of be sintered, programming rate be 25 DEG C/min-50 DEG C/min, sintering temperature be 600-900 DEG C, pressure be 75- 95MPa, sintering time be 10-20h minute, raw material sintering during carry out reaction in-situ generate target substance, simultaneously plus Pressure can make it densified again, finally gives the block Graphene composite thermoelectric material of densification.
CN201611172750.2A 2016-12-18 2016-12-18 Method for preparing graphene composite thermoelectric material Pending CN106410023A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106910817A (en) * 2017-04-09 2017-06-30 苏州思创源博电子科技有限公司 A kind of quick method for preparing copper selenide composite thermoelectric material
CN107017331A (en) * 2017-04-09 2017-08-04 苏州思创源博电子科技有限公司 A kind of quick method for preparing cobalt antimony composite thermoelectric material
CN110707206A (en) * 2019-11-01 2020-01-17 重庆大学 SnSe/rGO thermoelectric composite material and preparation method thereof
CN112899550A (en) * 2021-01-18 2021-06-04 四川大学 Zirconium-nickel-tin-based half-heusler-graphene composite thermoelectric material and preparation method thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101905972A (en) * 2009-06-04 2010-12-08 清华大学 Aluminum-doped zinc oxide-based thermoelectric material and preparation method thereof
CN103180982A (en) * 2010-10-19 2013-06-26 加利福尼亚理工学院 Self-tuning of carrier concentration for high thermoelectric performance
CN103706792A (en) * 2013-12-30 2014-04-09 北京科技大学 Al-doped ZnO texture thermoelectric material manufacturing method
CN104046876A (en) * 2014-06-16 2014-09-17 济南大学 Graphene/Cu2AX3 type thermoelectric composite material and preparation method thereof
CN105122485A (en) * 2013-02-14 2015-12-02 曼彻斯特大学 Thermoelectric materials and devices comprising graphene
CN105895795A (en) * 2016-04-23 2016-08-24 北京工业大学 Method for preparing composite tin selenide based thermoelectric material
CN105977372A (en) * 2016-05-13 2016-09-28 南方科技大学 K hole doped polycrystalline SnSe and preparation method therefor

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101905972A (en) * 2009-06-04 2010-12-08 清华大学 Aluminum-doped zinc oxide-based thermoelectric material and preparation method thereof
CN103180982A (en) * 2010-10-19 2013-06-26 加利福尼亚理工学院 Self-tuning of carrier concentration for high thermoelectric performance
CN105122485A (en) * 2013-02-14 2015-12-02 曼彻斯特大学 Thermoelectric materials and devices comprising graphene
CN103706792A (en) * 2013-12-30 2014-04-09 北京科技大学 Al-doped ZnO texture thermoelectric material manufacturing method
CN104046876A (en) * 2014-06-16 2014-09-17 济南大学 Graphene/Cu2AX3 type thermoelectric composite material and preparation method thereof
CN105895795A (en) * 2016-04-23 2016-08-24 北京工业大学 Method for preparing composite tin selenide based thermoelectric material
CN105977372A (en) * 2016-05-13 2016-09-28 南方科技大学 K hole doped polycrystalline SnSe and preparation method therefor

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106910817A (en) * 2017-04-09 2017-06-30 苏州思创源博电子科技有限公司 A kind of quick method for preparing copper selenide composite thermoelectric material
CN107017331A (en) * 2017-04-09 2017-08-04 苏州思创源博电子科技有限公司 A kind of quick method for preparing cobalt antimony composite thermoelectric material
CN110707206A (en) * 2019-11-01 2020-01-17 重庆大学 SnSe/rGO thermoelectric composite material and preparation method thereof
CN112899550A (en) * 2021-01-18 2021-06-04 四川大学 Zirconium-nickel-tin-based half-heusler-graphene composite thermoelectric material and preparation method thereof

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