CN115286388A - Method for simply synthesizing bismuthyl trisulfide-graphene oxide composite thermoelectric material - Google Patents
Method for simply synthesizing bismuthyl trisulfide-graphene oxide composite thermoelectric material Download PDFInfo
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- 239000004202 carbamide Substances 0.000 abstract 1
- BRWIZMBXBAOCCF-UHFFFAOYSA-N hydrazinecarbothioamide Chemical compound NNC(N)=S BRWIZMBXBAOCCF-UHFFFAOYSA-N 0.000 abstract 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 abstract 1
- 239000002086 nanomaterial Substances 0.000 abstract 1
- 231100000956 nontoxicity Toxicity 0.000 abstract 1
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- 229910052786 argon Inorganic materials 0.000 description 5
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- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a method for simply synthesizing a bismuthyl trisulfide-graphene oxide composite thermoelectric material, which comprises the steps of adding a proper amount of Graphene Oxide (GO) into a bismuth nitrate solution, uniformly stirring, then respectively adding a thiosemicarbazide solution and a urea solution for hydrothermal reaction, and finally sintering by using a tubular furnace to obtain Bi 2 S 3 -GO composite thermoelectric material. GO is present in Bi as a second phase 2 S 3 The Bi in the matrix can be obviously reduced 2 S 3 The thermal conductivity of the base material improves the thermoelectric figure of merit. The invention combines simple hydrothermal synthesis technology and tubular sintering technology to prepare the composite thermoelectric material with lower thermal conductivity. Bi 2 S 3 The base thermoelectric material has the characteristics of no toxicity, low price and the like, and Bi is doped 2 S 3 the-GO composite nano material shows excellent thermoelectric performance and shows wide application prospect in the field of thermoelectric materials in intermediate temperature regions.
Description
Technical Field
The invention relates to the field of thermoelectric materials, in particular to a method for simply synthesizing a bismuthyl trisulfide-graphene oxide composite thermoelectric material.
Background
The exacerbation of fossil energy consumption has further raised concerns over energy issues since the twenty-first century. Since the thermoelectric material is a functional material capable of realizing mutual conversion between heat energy and electric energy, the thermoelectric material is widely applied to the fields of thermoelectric refrigeration and waste heat power generation to relieve energy pressure. Bi 2 Te 3 Is a class of commercial thermoelectric materials with wide application, but the further application of Te is limited due to the high toxicity and scarcity of Te. Bi formed by substituting Te with S which is low in price and toxicity 2 S 3 The medium-temperature thermoelectric material with the highest development potential is considered to have higher seebeck coefficient and lower thermal conductivity. Bi preparation by hydrothermal method with simple synthesis steps 2 S 3 -GO composite thermoelectric material, GO being homogeneously distributed in Bi 2 S 3 A plurality of interfaces are formed in the substrate. The existence of the interfaces can effectively enhance phonon scattering and further reduce the thermal conductivity of the matrix material, thereby optimizing Bi 2 S 3 The thermoelectric property of (2).
Methods for preparing thermoelectric materials reported so far are a melting method, a ball milling method, a powder metallurgy method, and a rapid thermal pressing method. Compared with the preparation method, the hydrothermal method has the advantages of simple process and lower energy consumption, and the production cost of the material is further reduced by combining the tube furnace sintering technology. Therefore, the present invention aims to find a Bi with low cost and feasible method 2 S 3 Preparation technology of base composite thermoelectric materialAnd shows non-toxic and low-cost Bi 2 S 3 The application prospect of the base composite thermoelectric material is wide.
Disclosure of Invention
The invention aims to provide a non-toxic, low-cost and good-thermoelectric-property Bi 2 S 3 Base thermoelectric material: bi 2 S 3 The preparation method of the-GO composite thermoelectric material aims at the problems of high production cost of the existing thermoelectric material, high toxicity and high price of the indoor medium-temperature Te-based thermoelectric material and the like, and realizes the low-cost preparation of the nontoxic, low-price and good thermoelectric property medium-temperature Bi 2 S 3 -GO composite thermoelectric material.
In order to achieve the purpose, the invention adopts the following technical scheme:
simple synthesis of Bi 2 S 3 -a method for graphene oxidation, comprising the specific steps of:
(1) Dissolving Bi (NO) in water bath under the condition of magnetic stirring 3 ) 3 ·5H 2 O；
(2) Dissolving CH in water bath under magnetic stirring 5 N 3 S；
(3) Dissolving CH under magnetic stirring 4 N 2 O；
(4) Adding GO into the mixed solution in the step (1), and uniformly stirring;
(5) Reacting CH in step (2) 5 N 3 Slowly dripping the solution into the mixed solution obtained in the step (3), and uniformly stirring;
(6) The CH obtained in the step (3) 4 N 2 Dripping the O solution into the mixed solution obtained in the step (5), and uniformly stirring;
(7) Adding the mixed solution obtained in the step (6) into a reaction kettle for reaction;
(8) Centrifuging, cleaning and drying the reaction solution obtained in the step (7);
(9) And (4) tabletting the dried powder obtained in the step (8), and sintering in a tube furnace.
In step (1), bi (NO) 3 ) 3 ·5H 2 The amount of O added was 4.85g,37.5ml of deionized water, 60 ℃ of water bath temperature and 5min of mixing and stirring time.
CH in step (2) 5 N 3 The addition amount of S is 1.52g, the deionized water is 37.5ml, the water bath temperature is 60 ℃, and the mixing and stirring time is 5min.
In the step (3), 0.3gCH needs to be added 4 N 2 O and 5ml of deionized water, and the mixing and stirring time is 5min.
The GO in the step (4) is 350 meshes, the addition amount of the GO is divided into 0.25wt%,0.5wt%,0.75wt% and 1wt%, and the mixing and stirring time is 10min.
The stirring time in the step (5) is 5min.
The stirring time in the step (6) is 5min.
The hydrothermal reaction in the step (7) needs to be carried out for 12 hours at the temperature of 100 ℃.
And (5) the rotating speed of the centrifuge in the step (8) is 9000r/min for 5min. Drying at 80 deg.C for 12h.
And (9) pressing the tablet machine to 20Mpa for 5min. The argon atmosphere is 100 percent, the heating rate is 2 ℃/min, and the heat preservation time is 2h.
The invention has the beneficial effects that:
the invention firstly reacts with Bi due to the oxygen-containing functional groups (-OH, -COOH) existing in GO 3+ In combination, GO in the composite material prepared by the hydrothermal reaction can be uniformly distributed in Bi 2 S 3 In the matrix. Thanks to the presence of the second phase GO, GO can further hinder mass transfer during sintering and inhibit grain growth. The thermoelectric performance test result shows that Bi 2 S 3 The thermal conductivity of the GO composite is reduced, optimizing its thermoelectric properties. The reason is that the crystal face of fine crystal grains and the existence of the second phase GO can greatly enhance the scattering effect of phonons, so that Bi is enabled to be in a high-purity state 2 S 3 The thermoelectric property of the base composite material is improved. The method adopts simple and low-cost hydrothermal synthesis technology to prepare the non-toxic, low-price and good-thermoelectric-property Bi 2 S 3 A base composite thermoelectric material. Broadens the application range of thermoelectric materials in the intermediate temperature region and optimizes Bi 2 S 3 The thermoelectric property of the material providesA new idea is provided. Optimized Bi 2 S 3 The base thermoelectric material has a wide development prospect in the two fields of thermoelectric refrigeration and waste heat power generation.
Drawings
FIG. 1 shows Bi of the present invention 2 S 3 Schematic of the crystal structure of (a).
FIGS. 2a, b are XRDs of powder samples from examples 1, 2, 3, 4, 5 of the present invention; c and d are XRD of the bulk samples in examples 1, 2, 3, 4 and 5 of the present invention.
FIG. 3a shows Bi in example 1 of the present invention 2 S 3 SEM picture of (g); b is Bi in example 3 of the present invention 2 S 3 SEM image of GO (0.5 wt%); c, d, e, f are Bi in example 3 of the present invention 2 S 3 EDS of GO (0.5 wt%).
FIG. 4a is a graph showing the thermal conductivity of samples of examples 1, 2, 3, 4 and 5 of the present invention; b is the total thermal conductivity of the samples in example 1, example 2, example 3, example 4, example 5 of the present invention; c is the electron thermal conductivity of the samples in the examples 1, 2, 3, 4 and 5 of the invention; d is the lattice thermal conductivity of the samples in examples 1, 2, 3, 4 and 5 of the present invention.
Fig. 5 shows thermoelectric figure of merit ZT of samples in examples 1, 2, 3, 4, and 5 of the present invention.
Detailed Description
The present invention is further illustrated by the following examples, wherein the details are not set forth in any detail as part of the common general knowledge or the technical skill in the art.
Example 1
A method for simply synthesizing a bismuthyl trisulfide composite thermoelectric material comprises the following specific steps:
(1) Dissolving 4.85g Bi (NO) in 37.5ml deionized water under the conditions of 60 ℃ water bath and magnetic stirring 3 ) 3 ·5H 2 O；
(2) Water bath at 60 deg.C under magnetic stirring at 37 deg.C5ml of deionized water to dissolve 1.52g of CH 5 N 3 S；
(3) 0.3g of CH was dissolved in 5ml of deionized water with stirring 4 N 2 O；
(4) Reacting CH in step (2) 5 N 3 The S solution is slowly dripped into Bi (NO) in the step (3) 3 ) 3 Uniformly stirring the solution;
(5) The CH obtained in the step (3) 4 N 2 Dripping the O solution into the mixed solution in the step (4), and uniformly stirring;
(6) Adding the mixed solution obtained in the step (5) into a 200ml reaction kettle, and reacting for 12h at the temperature of 100 ℃;
(7) Centrifuging the reaction solution obtained in the step (6) at a rotating speed of 9000r/min, and then cleaning and drying (drying at 80 ℃ for 12 h);
(8) Tabletting (20 Mpa, 5 min) the dried powder obtained in step (7), and introducing argon gas into a tube furnace (20 cm) 3 Min) is heated to 350 ℃ at a speed of 2 ℃/min and is kept for 2h.
The thermoelectric performance test result shows that the pure phase Bi 2 S 3 The thermal conductivity of the material can be as low as 0.36 W.K between 300K and 650K -1 ·m -1 . The thermoelectric figure of merit ZT was highest at 628K to 0.22, which was highest in all samples prepared in examples. But below 578K, bi from example 3 2 S 3 Thermoelectric figure of merit ZT of-GO (0.5 wt%) is higher than that of pure phase Bi 2 S 3 。
Example 2
A method for simply synthesizing a bismuthyl trisulfide-graphene oxide (0.25 wt%) composite thermoelectric material comprises the following specific steps:
(1) Dissolving 4.85g Bi (NO) in 37.5ml deionized water under the conditions of 60 ℃ water bath and magnetic stirring 3 ) 3 ·5H 2 O；
(2) Bi (NO) in step (1) 3 ) 3 Adding 0.01305gGO into the solution, performing ultrasonic treatment for 10min, and stirring for 10min;
(3) Dissolving 1.52g of C in 37.5ml of deionized water in a water bath at 60 ℃ under the condition of magnetic stirringH 5 N 3 S；
(4) 0.3g of CH was dissolved in 5ml of deionized water with stirring 4 N 2 O；
(5) Converting CH in step (3) 5 N 3 Slowly dripping the solution S into the mixed solution obtained in the step (2), and uniformly stirring;
(6) The CH obtained in the step (4) 4 N 2 Dripping the O solution into the mixed solution in the step (5), and uniformly stirring;
(7) Adding the mixed solution obtained in the step (5) into a 200ml reaction kettle, and reacting for 12h at the temperature of 100 ℃;
(8) Centrifuging the reaction solution obtained in the step (6) at a rotating speed of 9000r/min, and then cleaning and drying (drying at 80 ℃ for 12 h);
(9) Tabletting (20 Mpa, 5 min) the dried powder obtained in step (7), and introducing argon gas into a tube furnace (20 cm) 3 Min) is heated to 350 ℃ at a speed of 2 ℃/min and is kept for 2h.
The thermoelectric performance test result shows that Bi 2 S 3 The thermal conductivity of-GO (0.25 wt%) can be as low as 0.39 W.K between 300K and 650K -1 ·m -1 ，Bi 2 S 3 Thermoelectric figure of merit ZT of-GO (0.25 wt%) can be up to 0.11.
Example 3
A method for simply synthesizing a bismuthyl trisulfide-graphene oxide (0.5 wt%) composite thermoelectric material comprises the following specific steps:
(1) Dissolving 4.85g Bi (NO) in 37.5ml deionized water under the conditions of 60 ℃ water bath and magnetic stirring 3 ) 3 ·5H 2 O；
(2) Bi (NO) in step (1) 3 ) 3 Adding 0.0261gGO into the solution, performing ultrasonic treatment for 10min, and stirring for 10min;
(3) Dissolving 1.52g of CH in 37.5ml of deionized water in a water bath at 60 ℃ under the condition of magnetic stirring 5 N 3 S；
(4) 0.3g of CH was dissolved in 5ml of deionized water with stirring 4 N 2 O；
(5) The step (A) is3) In (CH) 5 N 3 Slowly dripping the solution S into the mixed solution obtained in the step (2), and uniformly stirring;
(6) CH obtained in the step (4) 4 N 2 Dripping the O solution into the mixed solution obtained in the step (5), and uniformly stirring;
(7) Adding the mixed solution obtained in the step (5) into a 200ml reaction kettle, and reacting for 12h at the temperature of 100 ℃;
(8) Centrifuging the reaction solution obtained in the step (6) at a rotating speed of 9000r/min, and then cleaning and drying (drying at 80 ℃ for 12 h);
(9) Tabletting (20 Mpa, 5 min) the dried powder obtained in step (7), and introducing argon gas into a tube furnace (20 cm) 3 Min) at 2 ℃/min to 350 ℃ for 2h.
The thermoelectric performance test result shows that Bi 2 S 3 Thermal conductivity of-GO (0.5 wt%) can be as low as 0.32 W.K between 300K and 650K -1 ·m -1 ，Bi 2 S 3 Thermoelectric figure of merit ZT of-GO (0.5 wt%) can be up to 0.17. Thermoelectric figure of merit ZT in the temperature range below 573K is higher than that of pure phase Bi prepared in example 1 2 S 3 。
Example 4
A method for simply synthesizing a bismuthyl trisulfide-graphene oxide (0.75 wt%) composite thermoelectric material comprises the following specific steps:
(1) Dissolving 4.85g Bi (NO) in 37.5ml deionized water under the conditions of 60 ℃ water bath and magnetic stirring 3 ) 3 ·5H 2 O；
(2) Bi (NO) in step (1) 3 ) 3 Adding 0.03915gGO into the solution, performing ultrasonic treatment for 10min, and stirring for 10min;
(3) Dissolve 1.52g CH in 37.5ml deionized water under magnetic stirring in a water bath at 60 deg.C 5 N 3 S；
(4) 0.3g of CH was dissolved in 5ml of deionized water with stirring 4 N 2 O；
(5) Converting CH in step (3) 5 N 3 Slowly dripping the S solution into the mixed solution in the step (2)Stirring uniformly in the solution;
(6) CH obtained in the step (4) 4 N 2 Dripping the O solution into the mixed solution in the step (5), and uniformly stirring;
(7) Adding the mixed solution obtained in the step (5) into a 200ml reaction kettle, and reacting for 12h at the temperature of 100 ℃;
(8) Centrifuging the reaction solution obtained in the step (6) at a rotating speed of 9000r/min, and then cleaning and drying (drying at 80 ℃ for 12 h);
(9) Tabletting (20 Mpa, 5 min) the dried powder obtained in step (7), and introducing argon gas into a tube furnace (20 cm) 3 Min) is heated to 350 ℃ at a speed of 2 ℃/min and is kept for 2h.
The thermoelectric property test result shows that Bi 2 S 3 The thermal conductivity of-GO (0.75 wt%) can be as low as 0.38 W.K between 300K and 650K -1 ·m -1 ，Bi 2 S 3 Thermoelectric figure of merit ZT of-GO (0.75 wt%) is up to 0.14.
Example 5
A method for simply synthesizing a bismuthyl trisulfide-graphene oxide (1 wt%) composite thermoelectric material comprises the following specific steps:
(1) 4.85g of Bi (NO) was dissolved in 37.5ml of deionized water in a water bath at 60 ℃ under magnetic stirring 3 ) 3 ·5H 2 O；
(2) Bi (NO) in step (1) 3 ) 3 Adding 0.0522gGO into the solution, performing ultrasonic treatment for 10min, and stirring for 10min;
(3) Dissolving 1.52g of CH in 37.5ml of deionized water in a water bath at 60 ℃ under the condition of magnetic stirring 5 N 3 S；
(4) 0.3g of CH was dissolved in 5ml of deionized water with stirring 4 N 2 O；
(5) Converting CH in step (3) 5 N 3 Slowly dripping the solution S into the mixed solution in the step (2), and uniformly stirring;
(6) CH obtained in the step (4) 4 N 2 Dripping the O solution into the mixed solution obtained in the step (5), and uniformly stirring;
(7) Adding the mixed solution obtained in the step (5) into a 200ml reaction kettle, and reacting for 12h at the temperature of 100 ℃;
(8) Centrifuging the reaction solution obtained in the step (6) at a rotating speed of 9000r/min, and then cleaning and drying (drying at 80 ℃ for 12 h);
(9) Tabletting (20 Mpa, 5 min) the dried powder obtained in step (7), and introducing argon gas into a tube furnace (20 cm) 3 Min) is heated to 350 ℃ at a speed of 2 ℃/min and is kept for 2h.
The thermoelectric property test result shows that Bi 2 S 3 The thermal conductivity of-GO (1 wt%) can be as low as 0.37 W.K between 300K and 650K -1 ·m -1 ，Bi 2 S 3 Thermoelectric figure of merit ZT of GO (1 wt%) is up to 0.168.
In conclusion, the Bi provided by the invention 2 S 3 Preparation method of-GO composite thermoelectric material by compounding GO in Bi 2 S 3 The heat conductivity of the base material is reduced and the Bi content is improved 2 S 3 Thermoelectric properties of the base material. The presence of GO can hinder grain growth during sintering, forming many grain boundaries. Meanwhile, GO is compact with Bi due to the existence of oxygen-containing functional groups 2 S 3 Bonded together to form a plurality of interfaces. Under the synergistic effect of the two, bi 2 S 3 The thermal conductivity of the GO composite thermoelectric material is greatly reduced, and the thermoelectric performance is optimized. The Bi prepared in example 3 is found to be tested by thermoelectric performance 2 S 3 The thermal conductivity of-GO (0.5 wt%) can be as low as 0.32 W.K -1 ·m -1 The maximum thermoelectric figure of merit can reach 0.17, and the thermoelectric figure of merit below 573K is higher than that of pure phase Bi 2 S 3 . In addition, the invention also combines a simple hydrothermal synthesis technology and tubular sintering, thereby further reducing the production cost. The invention widens Bi 2 S 3 Application in the field of thermoelectric materials in intermediate temperature region for optimizing Bi 2 S 3 Thermoelectric performance provides a new concept.
Claims (9)
1. A method for simply synthesizing a bismuthyl trisulfide-graphene oxide composite thermoelectric material is characterized by comprising the following specific steps:
(1) Dissolving Bi (NO) under the conditions of water bath and magnetic stirring 3 ) 3 ·5H 2 O；
(2) Dissolving CH in water bath under magnetic stirring 5 N 3 S；
(3) Dissolving CH under magnetic stirring 4 N 2 O；
(4) GO (325 meshes) is doped into the mixed solution in the step (1), the addition amounts are 0.25wt%,0.5wt%,0.75wt% and 1wt%, and the mixture is mixed and stirred for 10min;
(5) Reacting CH in step (2) 5 N 3 Slowly dripping the solution into the mixed solution obtained in the step (3), and uniformly stirring;
(6) CH obtained in the step (3) 4 N 2 Dripping the O solution into the mixed solution obtained in the step (5), and uniformly stirring;
(7) Adding the mixed solution obtained in the step (6) into a reaction kettle for reaction;
(8) Centrifuging, cleaning and drying the reaction solution obtained in the step (7);
(9) And (4) tabletting the dried powder obtained in the step (8), and sintering in a tube furnace.
2. The method for simply synthesizing the bismuthyl trisulfide-graphene oxide composite thermoelectric material as claimed in claim 1, wherein in the step (1), bi (NO) is added 3 ) 3 ·5H 2 The addition amount of O is 4.85g, the deionized water is 37.5ml, the water bath temperature is 60 ℃, and the mixing and stirring time is 5min.
3. The method for simply synthesizing the bismuthyl trisulfide-graphene oxide composite thermoelectric material as claimed in claim 1, wherein in the step (2), CH 5 N 3 The addition amount of S is 1.52g, the deionized water is 37.5ml, the water bath temperature is 60 ℃, and the mixing and stirring time is 5min.
4. The method for simply synthesizing the bismuthyl trisulfide-graphene oxide composite thermoelectric material as claimed in claim 1, wherein in the step (3), 0.3gCH needs to be added 4 N 2 O and 5ml of deionized water, and the mixing and stirring time is 5min.
5. The method for simply synthesizing the bismuthyl trisulfide-graphene oxide composite thermoelectric material according to claim 1, wherein the stirring time in the step (5) is 5min.
6. The method for simply synthesizing the bismuthyl trisulfide-graphene oxide composite thermoelectric material according to claim 1, wherein the stirring time in the step (6) is 5min.
7. The method for simply synthesizing the bismuthyl trisulfide-graphene oxide composite thermoelectric material according to claim 1, wherein the hydrothermal reaction in the step (7) requires reaction at 100 ℃ for 12 hours.
8. The method for simply synthesizing the bismuthyl trisulfide-graphene oxide composite thermoelectric material according to claim 1, wherein the centrifuge rotating speed in the step (8) is 9000r/min, and the time is 5min; drying at 80 deg.C for 12h.
9. The simple synthesis method of the bismuthyl trisulfide-graphene oxide composite thermoelectric material according to claim 1, wherein the tablet press of step (9) has a pressure of 20Mpa for 5min; the argon atmosphere is 100 percent, the heating rate is 2 ℃/min, and the heat preservation time is 2h.
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| CN102910617A (en) * | 2012-09-24 | 2013-02-06 | 同济大学 | Chemical preparation method of graphene-bismuth sulfide nanocomposite material |
| US20150318544A1 (en) * | 2012-11-20 | 2015-11-05 | Yau Wai Denis Yu | Method for forming a reduced graphene oxide/metal sulfide composite and its use as an anode for batteries |
| CN107026263A (en) * | 2017-06-02 | 2017-08-08 | 扬州大学 | Sea urchin shape bismuth sulfide/macropore graphene composite material, preparation method and applications |
| CN112209437A (en) * | 2020-10-16 | 2021-01-12 | 南开大学 | Preparation method of bismuth sulfide nano particle and graphene composite material |
| CN113087016A (en) * | 2021-04-06 | 2021-07-09 | 浙江加州国际纳米技术研究院台州分院 | Preparation method of rod-shaped bismuth sulfide/reduced graphene oxide composite material |
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| CN102910617A (en) * | 2012-09-24 | 2013-02-06 | 同济大学 | Chemical preparation method of graphene-bismuth sulfide nanocomposite material |
| US20150318544A1 (en) * | 2012-11-20 | 2015-11-05 | Yau Wai Denis Yu | Method for forming a reduced graphene oxide/metal sulfide composite and its use as an anode for batteries |
| CN107026263A (en) * | 2017-06-02 | 2017-08-08 | 扬州大学 | Sea urchin shape bismuth sulfide/macropore graphene composite material, preparation method and applications |
| CN112209437A (en) * | 2020-10-16 | 2021-01-12 | 南开大学 | Preparation method of bismuth sulfide nano particle and graphene composite material |
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