CN115849378A - Preparation method of molybdenum-based MXene thermoelectric material - Google Patents
Preparation method of molybdenum-based MXene thermoelectric material Download PDFInfo
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- CN115849378A CN115849378A CN202211391508.XA CN202211391508A CN115849378A CN 115849378 A CN115849378 A CN 115849378A CN 202211391508 A CN202211391508 A CN 202211391508A CN 115849378 A CN115849378 A CN 115849378A
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- molybdenum
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- 239000000463 material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 21
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 239000011733 molybdenum Substances 0.000 title claims abstract description 19
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000006228 supernatant Substances 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 238000007731 hot pressing Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000003825 pressing Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 10
- 229910010041 TiAlC Inorganic materials 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- 230000007547 defect Effects 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000013590 bulk material Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000005678 Seebeck effect Effects 0.000 description 1
- 229910010067 TiC2 Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Chemical group 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000005619 thermoelectricity Effects 0.000 description 1
- -1 transition metal carbides Chemical class 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Abstract
The invention relates to a preparation method of a molybdenum-based MXene thermoelectric material, which comprises the following steps: heating MAX and hydrofluoric acid according to a certain proportion and stirring to obtain reacted liquid; centrifuging the reacted liquid for a period of time under the centrifugal condition, and pouring out supernatant; adding water into the centrifuged solid, shaking up, and repeatedly centrifuging and washing until the pH of the supernatant is =7; pouring out the supernatant, and drying the residual solid into powder; and (3) applying pressure of 20-25Mpa to the powder at a certain temperature, and hot-pressing the powder into a sheet to obtain the molybdenum-based MXene thermoelectric material. The preparation method improves the Seebeck coefficient of MXene, overcomes the defect of low yield of MXene in the preparation process, greatly shortens the preparation time and simplifies the preparation process.
Description
Technical Field
The invention relates to the technical field of thermoelectric materials, in particular to a preparation method of a molybdenum-based MXene thermoelectric material.
Background
Thermoelectric materials refer to a class of functional materials capable of realizing the interconversion of thermal energy and electric energy, and mainly utilize the relationship between the temperature gradient and voltage inside the materials, namely, the voltage is generated when the temperature difference is applied (seebeck effect) or the temperature difference is generated when the voltage is applied (peltier)Effects) to achieve direct conversion of electrical energy to thermal energy. The thermoelectric material has the main advantages of no noise, no pollution, low maintenance cost and wide application prospect in thermoelectric power generation and semiconductor refrigeration. The thermoelectric figure of merit (zT) and the Power Factor (PF) are common parameters for measuring the performance of thermoelectric materials, and are represented by the formula ZT = σ S 2 T/κ、PF＝σS 2 Where S is the Seebeck coefficient of the material, σ is the electrical conductivity of the material, T is the temperature, and κ is the thermal conductivity of the material.
MXene is a generic term for a class of two-dimensional transition metal carbides, nitrides and carbonitrides having the general chemical formula Mn +1XnTx, where M is a transition metal, X is carbon or nitrogen, and T represents a surface group thereof, such as oxygen, hydroxide, etc. The unique two-dimensional layered structure MXene has good physicochemical characteristics, and the property adjustability brought by abundant and adjustable surface groups of the MXene can be applied in different scenes. Among the MXenes, the molybdenum-based MXene has better thermoelectric performance and better application potential in the field of thermoelectric.
The unique two-dimensional structure of MXene has great application potential in the thermoelectric field, and simultaneously causes the problems of easy oxidation, complex preparation process and low yield, and restricts the practical application of MXene.
Disclosure of Invention
Based on the problems in the background art, the invention provides a preparation method of a molybdenum-based MXene thermoelectric material, which comprises the following steps:
step 1, heating and stirring MAX and hydrofluoric acid according to a certain proportion at the temperature of 20-70 ℃ to obtain reacted liquid;
step 2, centrifuging the reacted liquid for a period of time under a centrifugal condition, and pouring out supernatant;
step 3, adding water into the centrifuged solid, shaking up, and repeatedly centrifuging and washing until the pH of the supernatant is =7;
step 4, pouring out the supernatant, and drying the residual solid into powder;
and 5, applying pressure of 20-25Mpa to the powder at a certain temperature, and hot-pressing the powder into a sheet to obtain the molybdenum-based MXene thermoelectric material.
Preferably, the mass fraction of the hydrofluoric acid in the step 1 is 20-60%, and the heating and stirring time in the step 1 is 40-160 hours.
Preferably, MAX in step 1 is Mo 2 TiAlC 2 、Mo 2 Ga 2 C、Mo 2 Ti 2 AlC 3 One kind of (1).
Preferably, the ratio of MAX to hydrofluoric acid in step 1 is 1gMAX to 10-30mL hydrofluoric acid.
Preferably, the rotation speed during centrifugation in the step 2 is 3500-5500r, and the centrifugation time is 5-50min.
Preferably, the drying temperature in the step 4 is 20-50 ℃.
Preferably, the temperature of hot pressing in the step 5 is 100-300 ℃, and the hot pressing is carried out for 1-3h to form the sheet.
Compared with the prior art, carboxyl on the surface of MXene is easy to react with oxygen and water molecules, and is oxidized and degraded to generate metal oxide. This process tends to occur from the edges and defects of the MXene flakes, breaking down the MXene flakes into small fragments that become more susceptible to oxidation as the electrical properties deteriorate. In addition, to obtain a single layer of MXene, multiple layers of MXene need to be intercalated and stripped, and the step also causes waste of multiple layers of MXene which are not stripped, so that the yield is reduced.
Aiming at the problem of application of MXene in the field of thermoelectricity, the invention discloses an improved preparation method based on MXene thermoelectric materials, which improves the Seebeck coefficient of MXene, overcomes the defect of low yield of MXene in the preparation process, greatly shortens the preparation time and simplifies the preparation process.
Drawings
FIG. 1 shows Mo prepared by the improved preparation method of the invention 2 TiC 2 X-ray diffraction pattern of bulk thermoelectric material.
FIG. 2 shows Mo 2 TiC 2 The relationship graph of thermoelectric force of thermoelectric material prepared by the traditional preparation method of the bulk thermoelectric material and the improved preparation method of the invention along with the change of temperature difference.
FIG. 3 is a Seebeck coefficient chart of thermoelectric materials prepared by a conventional preparation method and an improved preparation method of the present invention.
FIG. 4 is a graph showing a comparison of the yield of the conventional production method and the improved production method of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Application example 1:
the invention provides a preparation method of a molybdenum-based MXene thermoelectric material, which comprises the following steps:
step 1, taking Mo 2 TiAlC 2 1g of Mo mixed with 30-60% hydrofluoric acid 2 TiAlC 2 Heating and stirring for 40-60 hours at 40-60 ℃ corresponding to the proportion of 10-30mL of hydrofluoric acid;
step 2, centrifuging the reacted liquid for 5-50min at the rotating speed of 3500-5500r, and pouring out the supernatant;
and 3, adding water into the centrifuged solid, shaking up, and repeatedly centrifuging and washing until the pH of the supernatant is =7.
Step 4, taking the residual solid after the supernatant liquid is poured for the last time, and drying the residual solid into powder at the temperature of 20-50 ℃;
and 5, hot-pressing the powder at 250-300 ℃ under 20-25Mpa for 1-3h to form a sheet, thus obtaining the thermoelectric material with thermoelectric performance.
The X-ray diffraction pattern shown in FIG. 1 is consistent with that in the literature (Shevchuk, K., et al. MRS Bulletin 47,545-554 (2022)), indicating that the bulk thermoelectric material prepared by the improved preparation method of the present invention is Mo 2 TiC 2 。
FIG. 2 shows Mo prepared by the conventional preparation method and the improved preparation method of the present invention in the range of 300K-335K 2 TiC 2 The thermoelectric force of the bulk thermoelectric material is changed along with the temperature difference. FIG. 3 shows a conventional system in the range of 300K-335KPreparation method and Mo prepared by improved preparation method of the invention 2 And the Seebeck coefficient of the TiC2 bulk thermoelectric material. The test was carried out by maintaining one end of the bulk material at a temperature of 300K and heating the other end to test the voltage difference across the ends. The data in the figure show Mo 2 TiC 2 The bulk thermoelectric material is an n-type thermoelectric material, and Mo is prepared by a traditional preparation method in a test range 2 TiC 2 The Seebeck coefficient of the crystal is 32-38 mu V.K -1 The invention improves the Mo prepared by the preparation method 2 TiC 2 The Seebeck coefficient of the block thermoelectric material is 40-45 mu V.K -1 Improved preparation method for preparing Mo 2 TiC 2 The thermoelectric property of the bulk material at room temperature is improved to a certain extent.
In FIG. 4, it can be seen that the yield of the conventional preparation method is 5 to 15%, whereas the yield of the improved preparation method of the present invention reaches 80 to 90% which is close to the theoretical maximum yield of 90.7%.
Application example 2:
the invention provides a preparation method of a molybdenum-based MXene thermoelectric material, which comprises the following steps:
step 1, taking Mo 2 Ga 2 1g of Mo is mixed with 49% hydrofluoric acid by mass percent 2 Ga 2 C is heated and stirred for 100 hours at the temperature of 55 ℃ corresponding to the proportion of 20mL of hydrofluoric acid;
step 2, centrifuging the reacted liquid for 5min at the rotation speed of 3500r, and pouring out the supernatant;
and 3, adding water into the centrifuged solid, shaking up, and repeatedly centrifuging and washing until the pH of the supernatant is =7.
Step 4, taking the residual solid after the supernatant liquid is poured for the last time, and drying the residual solid into powder at the temperature of 30 ℃;
and 5, hot-pressing the powder at 300 ℃ and 23MPa for 1h to form the sheet, thus obtaining the thermoelectric material with thermoelectric performance.
Application example 3:
the invention provides a preparation method of a molybdenum-based MXene thermoelectric material, which comprises the following steps:
step 1, taking Mo 2 Ti 2 AlC 3 1g of hydrofluoric acid with the mass fraction of 49 percent Mo 2 Ti 2 AlC 3 Heating and stirring the mixture for 50 hours at the temperature of 55 ℃ corresponding to the proportion of 20mL of hydrofluoric acid;
step 2, centrifuging the reacted liquid for 5min at the rotation speed of 3500r, and pouring out the supernatant;
and 3, adding water into the centrifuged solid, shaking up, and repeatedly centrifuging and washing until the pH of the supernatant is =7.
Step 4, taking the residual solid after the supernatant liquid is poured for the last time, and drying the residual solid into powder at the temperature of 30 ℃;
and 5, hot-pressing the powder at 300 ℃ and 23MPa for 1h to form the sheet, thus obtaining the thermoelectric material with thermoelectric performance.
The above are only preferred embodiments of the present invention, and it should be noted that the above preferred embodiments should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.
Claims (7)
1. The preparation method of the molybdenum-based MXene thermoelectric material is characterized by comprising the following steps of:
step 1, heating and stirring MAX and hydrofluoric acid according to a certain proportion at the temperature of 20-70 ℃ to obtain reacted liquid;
step 2, centrifuging the reacted liquid for a period of time under a centrifugal condition, and pouring out supernatant;
step 3, adding water into the centrifuged solid, shaking up, and repeatedly centrifuging and washing until the pH of the supernatant is =7;
step 4, pouring out the supernatant, and drying the residual solid into powder;
and step 5, applying pressure of 20-25Mpa to the powder at a certain temperature, and performing hot pressing to form the sheet, thereby obtaining the molybdenum-based MXene thermoelectric material.
2. The method for preparing the molybdenum-based MXene thermoelectric material according to claim 1, wherein: the mass fraction of the hydrofluoric acid in the step 1 is 20-60%, and the heating and stirring time in the step 1 is 40-160 hours.
3. The method of claim 1 for preparing a molybdenum-based MXene thermoelectric material, wherein the method comprises the following steps: in the step 1, MAX is Mo 2 TiAlC 2 、Mo 2 Ga 2 C、Mo 2 Ti 2 AlC 3 One kind of (1).
4. The method for preparing the molybdenum-based MXene thermoelectric material according to claim 1, wherein: in the step 1, the ratio of MAX to hydrofluoric acid is 1gMAX, which corresponds to 10-30mL of hydrofluoric acid.
5. The method for preparing the molybdenum-based MXene thermoelectric material according to claim 1, wherein: the rotation speed in the centrifugation in the step 2 is 3500-5500r, and the centrifugation time is 5-50min.
6. The method for preparing the molybdenum-based MXene thermoelectric material according to claim 1, wherein: the drying temperature in the step 4 is 20-50 ℃.
7. The method of claim 1 for preparing a molybdenum-based MXene thermoelectric material, wherein the method comprises the following steps: the temperature of hot pressing in the step 5 is 100-300 ℃, and the hot pressing is carried out for 1-3h to form the sheet.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180064031A (en) * | 2016-12-05 | 2018-06-14 | 성균관대학교산학협력단 | Method of preparing MXene for electrode material and CMOS devices including the MXene electrode |
| US20190189884A1 (en) * | 2017-12-18 | 2019-06-20 | Korea Institute Of Science And Technology | Thermoelectric composite material comprising mxene and method for manufacturing the same |
| US20210139379A1 (en) * | 2019-11-12 | 2021-05-13 | Government Of The United States, As Represented By The Secretary Of The Air Force | Preparation of Layered MXene via Elemental Halogen Etching of MAX Phase |
| CN114650717A (en) * | 2020-12-21 | 2022-06-21 | 苏州北科纳米科技有限公司 | Preparation method of large-area high-conductivity anti-oxidation MXene film |
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2022
- 2022-11-08 CN CN202211391508.XA patent/CN115849378A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180064031A (en) * | 2016-12-05 | 2018-06-14 | 성균관대학교산학협력단 | Method of preparing MXene for electrode material and CMOS devices including the MXene electrode |
| US20190189884A1 (en) * | 2017-12-18 | 2019-06-20 | Korea Institute Of Science And Technology | Thermoelectric composite material comprising mxene and method for manufacturing the same |
| US20210139379A1 (en) * | 2019-11-12 | 2021-05-13 | Government Of The United States, As Represented By The Secretary Of The Air Force | Preparation of Layered MXene via Elemental Halogen Etching of MAX Phase |
| CN114650717A (en) * | 2020-12-21 | 2022-06-21 | 苏州北科纳米科技有限公司 | Preparation method of large-area high-conductivity anti-oxidation MXene film |
Non-Patent Citations (1)
| Title |
|---|
| 周阳: "钛基及钼基MXene在催化中的应用", 工程科技Ⅰ辑, no. 01, pages 22 * |
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