CN115403070A - Method for hydro-thermal synthesis of bismuthyl trisulfide-reduced graphene oxide composite thermoelectric material - Google Patents
Method for hydro-thermal synthesis of bismuthyl trisulfide-reduced graphene oxide composite thermoelectric material Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 29
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 18
- 238000001027 hydrothermal synthesis Methods 0.000 title claims description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 9
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G29/00—Compounds of bismuth
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
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- C01B32/184—Preparation
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/32—Thermal properties
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
Abstract
The invention discloses a method for hydrothermally synthesizing a bismuthyl trisulfide-reduced graphene oxide composite thermoelectric material. Bi prepared by the reaction 2 S 3 The composite thermoelectric material is obtained by sintering rGO powder in a tabletting tube manner. The addition of the rGO in the invention can not only improve the electric conductivity of the rGO, but also reduce the heat conductivity of the matrix material, and the heat of the rGO is improved under the synergistic action of the rGO and the matrix materialAnd (4) electrical property. Bi 2 S 3 Compared with the traditional Te-based thermoelectric material, the base thermoelectric material is nontoxic and low in price. Bi prepared by the invention 2 S 3 The thermoelectric performance of the-rGO composite thermoelectric material is further optimized, and the Bi is widened 2 S 3 The base material has application prospect in the field of thermoelectric materials in medium-temperature regions.
Description
Technical Field
The invention relates to the field of thermoelectric materials, in particular to a method for hydrothermally synthesizing a bismuthyl trisulfide-reduced graphene oxide composite thermoelectric material.
Background
In recent years, various kinds of energy and environmental problems have been gradually developed along with the consumption of fossil energy by human beings. To alleviate the pressure of the above problems, researchers have focused research on thermoelectric materials. Thermoelectric devices made of thermoelectric materials can realize interconversion of heat energy and electric energy without generating any pollution, and are considered as important functional materials of future energy development strategies. Bi 2 S 3 Compared with the traditional commercial thermoelectric material Bi 2 Te 3 Compared with the low price and the non-toxicity, the medium-temperature thermoelectric material with higher Seebeck coefficient and lower thermal conductivity is considered to have the most development potential. Hydrothermal method for preparing Bi with simple synthesis steps 2 S 3 -rGO composite thermoelectric material, which on one hand will form certain conductive channels, optimizing the electrical conductivity of the matrix material. On the other hand, rGO is uniformly distributed in Bi 2 S 3 A number of interfaces are formed in the substrate. The presence of these interfaces effectively enhances phonon scattering, further reducing the thermal conductivity of the matrix material. Optimizes Bi under the synergistic action of the two 2 S 3 The thermoelectric properties of (1).
Compared with a melting method, a ball milling method, a powder metallurgy method and a rapid hot pressing method, the hydrothermal method has the characteristics of simple process and low energy consumption. Bi is prepared by combining the method with a tube furnace sintering technology 2 S 3 rGO further reduces the production cost of the material. Therefore, the present invention aims to find a Bi with low cost and feasible method 2 S 3 The preparation technology of the base composite thermoelectric material shows no toxicity,Low cost of 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-rGO 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 -rGO composite thermoelectric material.
In order to realize the purpose, the invention adopts the following technical scheme:
a method for hydrothermally synthesizing a bismuthyl trisulfide-reduced graphene oxide composite thermoelectric material comprises the following specific steps:
(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) Mixing rGO 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 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 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 (5) tabletting the dried powder obtained in the step (8), and sintering in a tube furnace.
In step (1), bi (NO) 3 ) 3 ·5H 2 O was added in an amount of 4.85g, and deionized37.5ml of 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 concentration of the rGO in the step (4) is 4mg/ml, the addition amount of the rGO is divided into 5ml,10ml,15ml and 20ml, 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 (8) the rotating speed of the centrifugal machine is 9000r/min, and the time is 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:
although most of the oxygen-containing functional groups (-OH, -COOH) in rGO are reduced, a small amount of oxygen-containing functional groups are still present. Thus, rGO is homogeneously dispersible in water. Can be uniformly dispersed in Bi in the hydrothermal reaction process 2 S 3 In a matrix. The rGO in the Bi2S3 matrix not only can be used as a second phase to enhance phonon scattering, but also can prevent the migration of a liquid matrix to limit the growth of grains. This results in a large reduction in the thermal conductivity of the composite. In addition, the two-dimensional nano material rGO has certain conductive capability, a certain conductive channel can be formed in the Bi2S3 to improve the conductivity, and the Bi is enabled to be conductive in the two aspects 2 S 3 The thermoelectric property of the base composite material is improved. The method is simple to operate and low in cost, and the thermoelectric composite material Bi2S3-rGO with good thermoelectric performance is prepared. The prepared composite thermoelectric material is nontoxic and low in price and is Bi 2 S 3 Development of base thermoelectric material in intermediate temperature zone thermoelectric material field providesThe new direction.
Drawings
FIG. 1 shows Bi2S3 and Bi in the process of the present invention 2 S 3 -crystal structure diagram of rGO.
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.
FIGS. 3a, b, c, d are Bi in example 3 of the present invention 2 S 3 -EDS of rGO (10 ml); e, f, g, h are Bi in example 5 of the present invention 2 S 3 EDS of rGO (20 ml).
FIG. 4a is a graph of the conductivity of samples from examples 1, 2, 3, 4, 5 of the present invention; b is the seebeck coefficient of the samples in the embodiment 1, the embodiment 2, the embodiment 3, the embodiment 4 and the embodiment 5 of the invention; c is the power factor of the samples in the embodiments 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 hydrothermally synthesizing a bismuthyl trisulfide 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) 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；
(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 Slowly dripping the S solution into the Bi (N) in the step (3)O 3 ) 3 Uniformly stirring the solution;
(5) 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 600K -1 ·m -1 . The thermoelectric figure of merit ZT can reach 0.15 at 578K at most.
Example 2
A method for hydrothermally synthesizing a bismuthyl trisulfide-reduced graphene oxide (5 ml) 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 5ml rGO 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 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 property test result shows that Bi 2 S 3 -thermal conductivity of rGO (5 ml) can be as low as 0.19 wk between 300K and 600K -1 ·m -1 ，Bi 2 S 3 -a thermoelectric figure of merit ZT of rGO (5 ml) of up to 0.17.
Example 3
A method for hydrothermally synthesizing a bismuthyl trisulfide-reduced graphene oxide (10 ml) 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 10ml rGO into the solution, carrying out 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 solution S into the mixed solution 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 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 -thermal conductivity of rGO (10 ml) can be as low as 0.22 WK between 300K and 600K -1 ·m -1 The conductivity sigma is higher than that of pure phase Bi prepared in example 1 in the temperature interval below 450K 2 S 3 At the whole temperature interval Bi 2 S 3 -thermoelectric figure of merit ZT of GO (10 ml) is up to 0.22.
Example 4
A method for hydrothermally synthesizing a bismuthyl trisulfide-reduced graphene oxide (15 ml) 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 15ml rGO into the solution, carrying out 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 solution S into the mixed solution 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 -thermal conductivity of rGO (15 ml) can be as low as 0.17 WK between 300K and 600K -1 ·m -1 ，Bi 2 S 3 -a thermoelectric figure of merit ZT of GO (15 ml) of up to 0.14.
Example 5
A method for hydrothermally synthesizing a bismuthyl trisulfide-reduced graphene oxide (20 ml) 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 20ml rGO into the solution, carrying out 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 solution S into the mixed solution 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 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 property test result shows that Bi 2 S 3 The thermal conductivity of-GO (1 wt%) can be as low as 0.12 W.K between 300K and 600K -1 ·m -1 ，Bi 2 S 3 Thermoelectric figure of merit ZT of-GO (1 wt%) can reach up to 0.09.
In conclusion, the Bi provided by the invention 2 S 3 Preparation method of-rGO composite thermoelectric material, and rGO is compounded in Bi 2 S 3 The heat conductivity of the base material is reduced and Bi is improved 2 S 3 Thermoelectric properties of the base material. The presence of rGO can hinder grain growth during sintering, forming numerous grain boundaries. Meanwhile, rGO is compact with Bi due to the existence of oxygen-containing functional group 2 S 3 Bonded together to form a number of interfaces. Under the synergistic action of the two components, bi 2 S 3 The thermal conductivity of the-rGO composite thermoelectric material is greatly reduced, the electrical conductivity is improved to a certain extent, and the thermoelectric performance is optimized. Bi prepared in example 5 is found by thermoelectric property test 2 S 3 -rGO (20 ml) thermal conductivity as low as 0.12 WK -1 ·m -1 Pure phase Bi from example 1 2 S 3 The comparison is reduced by nearly 69%. Bi 2 S 3 -rGO (10 ml) with a maximum thermoelectric figure of merit of up to 0.22, in phase pure Bi as prepared in example 1 2 S 3 Compared with the prior art, the improvement is nearly 47 percent. 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 hydro-thermally synthesizing a bismuthyl trisulfide-reduced graphene oxide composite thermoelectric material is characterized by comprising the following specific steps:
(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) Mixing rGO (4 mg/ml) into the mixed solution in the step (1), wherein the addition amount of the rGO is divided into 5ml,10ml,15ml and 20ml, and the mixing and stirring time is 10min;
(5) Reacting CH in step (2) 5 N 3 Slowly dripping the solution into the mixed solution 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 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 hydrothermally synthesizing a bismuthyl trisulfide-reduced graphene oxide composite thermoelectric material as claimed in claim 1, wherein in 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 hydrothermally synthesizing a bismuthyl trisulfide-reduced graphene oxide composite thermoelectric material according to claim 1, wherein in 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 hydrothermal synthesis of Bi according to claim 1 2 S 3 A method for reducing the graphene oxide composite thermoelectric material, wherein 0.3gCH is required to be added in the step (3) 4 N 2 O and 5ml of deionized water, and the mixing and stirring time is 5min.
5. The method for hydrothermally synthesizing the bismuthyl trisulfide-reduced graphene oxide composite thermoelectric material according to claim 1, wherein the stirring time in the step (5) is 5min.
6. The method for hydrothermally synthesizing the bismuthyl trisulfide-reduced graphene oxide composite thermoelectric material according to claim 1, wherein the stirring time in the step (6) is 5min.
7. The method for hydrothermally synthesizing the bismuthyl trisulfide-reduced 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 hydrothermally synthesizing the bismuthyl trisulfide-reduced graphene oxide composite thermoelectric material according to claim 1, wherein the centrifuge rotating speed in the step (8) is 9000r/min, the time is 5min, and the drying is carried out for 12h at the temperature of 80 ℃.
9. The method for hydrothermally synthesizing the bismuthyl trisulfide-reduced graphene oxide composite thermoelectric material according to claim 1, wherein the tablet press in the step (9) has a pressure of 20MPa for 5min, an argon atmosphere of 100%, a heating rate of 2 ℃/min and a holding time of 2h.
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| CN116130184A (en) * | 2023-02-25 | 2023-05-16 | 合肥工业大学 | High-precision thin film chip resistor for automobile |
| CN116351437A (en) * | 2022-12-07 | 2023-06-30 | 烟台大学 | Bismuth sulfide nanorod photocatalyst and preparation method and application thereof |
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| CN116351437A (en) * | 2022-12-07 | 2023-06-30 | 烟台大学 | Bismuth sulfide nanorod photocatalyst and preparation method and application thereof |
| CN116351437B (en) * | 2022-12-07 | 2024-01-26 | 烟台大学 | Bismuth sulfide nanorod photocatalyst and preparation method and application thereof |
| CN116130184A (en) * | 2023-02-25 | 2023-05-16 | 合肥工业大学 | High-precision thin film chip resistor for automobile |
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Application publication date: 20221129 |