CN117915745A - Prussian blue modified electrode-based thermoelectric conversion device and preparation method thereof - Google Patents
Prussian blue modified electrode-based thermoelectric conversion device and preparation method thereof Download PDFInfo
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- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 title claims abstract description 50
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- VAPQAGMSICPBKJ-UHFFFAOYSA-N 2-nitroacridine Chemical compound C1=CC=CC2=CC3=CC([N+](=O)[O-])=CC=C3N=C21 VAPQAGMSICPBKJ-UHFFFAOYSA-N 0.000 claims description 4
- KPGXRSRHYNQIFN-UHFFFAOYSA-N 2-oxoglutaric acid Chemical compound OC(=O)CCC(=O)C(O)=O KPGXRSRHYNQIFN-UHFFFAOYSA-N 0.000 claims description 4
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- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
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- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 2
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- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
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- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 claims description 2
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- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical group CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 3
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Abstract
The invention discloses a thermoelectric conversion device based on a Prussian blue modified electrode and a preparation method thereof, wherein the preparation of the Prussian blue electrode comprises the following preparation steps: s1: mixing CuSO 4 solution and K 3Fe(CN)6 solution for reaction, and collecting precipitate; s2: washing and centrifuging the precipitate, and drying to obtain Prussian blue electrode raw material; s3: mixing Prussian blue electrode raw material, a conductive agent and a binder, grinding, and adding an organic solvent to obtain mixed slurry; s4: and coating the slurry on carbon cloth, and drying to obtain the Prussian blue electrode. The thermoelectric conversion device comprises a Prussian blue modified electrode, a counter electrode and an ionic hydrogel, wherein the two electrodes are respectively arranged on two surfaces of the ionic hydrogel. The thermoelectric conversion device provided by the invention can utilize Prussian blue and the counter electrode as secondary batteries to store electric energy converted from heat energy, realizes the integration of thermoelectric conversion and electric energy storage functions, and can provide stable power supply for wearing equipment and an Internet of things system.
Description
Technical Field
The invention relates to the field of ion thermochemical batteries, in particular to a thermoelectric conversion device based on Prussian blue modified electrodes and a preparation method thereof.
Background
With the increasing demand and rapid development of wearable electronic devices and internet of things systems in the field of Artificial Intelligence (AI), medical devices and environmental monitoring, it becomes important how to study the power supply system providing drive for them. Although the battery/supercapacitor developed and applied at present meets the requirements in the size, the battery/supercapacitor has a problem that the capacity is limited and frequent charging is required. The characteristic that the thermoelectric material can collect low-grade waste heat and convert the low-grade waste heat into electric energy charges batteries and capacitors of flexible electronic equipment and systems, so that the frequency of charging is reduced, and a new way is provided for the operation of flexible wearable equipment and micro internet of things equipment.
Thermoelectric materials currently include electronic thermoelectric materials and ionic thermoelectric materials. The traditional electronic thermoelectric material consists of a semiconductor or a semi-metal, has a relatively small Seebeck coefficient, is usually in the order of 10-100 mu V/K, and has the problems of low working temperature range, mechanical brittleness, complex processing technology, environmental protection and the like. The ion thermoelectric material has a completely different thermoelectric conversion mechanism, ions do not enter the electrode but rearrange at the electrode surface, and a voltage difference is generated between cold and hot electrodes. The ion thermoelectric material has the advantages of high Seebeck coefficient, low cost, easy processing, small environmental pollution, self-healing capacity and the like. Among them, ionic hydrogels are outstanding as ion thermoelectric materials, which are polymer materials with high water content and three-dimensional cross-linked network, and abundant water in hydrogels can provide good conductivity and efficient ion migration.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a thermoelectric conversion device based on Prussian blue modified electrodes, develop an ion thermochemical battery formed by combining ion hydrogel and modified electrodes in a synergistic effect manner, and provide stable power supply for various wearable devices.
In order to achieve the above purpose, the invention adopts the following technical scheme:
The first aspect of the invention provides a preparation method of a Prussian blue modified electrode, which is characterized by comprising the following preparation steps:
S1: mixing CuSO 4 solution and K 3Fe(CN)6 solution for reaction, and collecting precipitate after the reaction is finished;
S2: washing and centrifuging the precipitate, and drying to obtain Prussian blue electrode raw material;
S3: mixing Prussian blue electrode raw material, a conductive agent and a binder, grinding, adding an organic solvent, and mixing to obtain mixed slurry;
S4: and coating the mixed slurry on carbon cloth, and drying to obtain the Prussian blue electrode.
In some embodiments, in step S1, the concentration of the CuSO 4 solution is 0.2-1mol/L, the concentration of the K 3Fe(CN)6 solution is 0.1-1mol/L, and the molar ratio of the CuSO 4 solution to the K 3Fe(CN)6 solution is 1:0.8-1.2, and the reaction time is 6-10h.
In some embodiments, in step S2, the detergent is deionized water, the drying temperature is 60-100 ℃, and the drying time is 10-15 hours.
In some embodiments, in step S3, the binder is at least one selected from polyvinylidene fluoride, nafion and carboxymethyl cellulose, the conductive agent is at least one selected from conductive carbon powder, ketjen black and acetylene black, and the mass ratio of the raw materials of the prussian blue electrode to the conductive agent and the binder is 7:2:1.
The second aspect of the invention is to provide a Prussian blue modified electrode.
The Prussian blue material electrode provided by the invention has an open frame structure, hydrogen ions can be quickly embedded into the Prussian blue material electrode to form a rich hydrogen bond lattice water network, and meanwhile, the hydrogen ions are used as working ions, so that a quick charge transmission mechanism which cannot be provided by a traditional metal ion battery can be provided.
The third aspect of the invention provides a prussian blue modified electrode-based thermoelectric conversion device, which comprises a prussian blue modified electrode, a counter electrode and an ionic hydrogel, wherein the counter electrode and the prussian blue modified electrode are respectively arranged on two surfaces of the ionic hydrogel. The thermoelectric conversion device provided by the invention can provide stable power supply for wearable equipment and an Internet of things system.
In some embodiments, the method of preparing a counter electrode comprises the steps of: mixing active carbon, a conductive agent and a binder, grinding, adding an organic solvent, and mixing to obtain mixed slurry; and (3) coating the mixed slurry on carbon cloth, and drying to obtain the counter electrode.
In some embodiments, the conductive agent is selected from at least one of conductive carbon powder, ketjen black, and acetylene black; the binder is at least one selected from polyvinylidene fluoride, nafion and carboxymethyl cellulose; the mass ratio of the active carbon to the conductive agent to the binder is 7:2:1.
In some embodiments, the method of preparing an ionic hydrogel comprises the steps of: preparing an unsaturated monomer aqueous solution, wherein the unsaturated monomer is at least one selected from acrylamide, acrylic acid, potassium acrylate, methacrylic acid, sodium methacrylate and isopropyl acrylamide, adding a cross-linking agent and a photoinitiator into the unsaturated monomer aqueous solution, stirring, mixing, performing polymerization reaction under an ultraviolet lamp, and performing ion exchange in acid liquor after the polymerization reaction is finished to obtain the ionic hydrogel.
In some embodiments, the cross-linking agent is selected from at least one of N, N' -methylene bisacrylamide, pentaerythritol triacrylate, pentaerythritol triethyl ester and polyethylene glycol diacrylate, the photoinitiator is 2-hydroxy-2-methyl propiophenone or 2-ketoglutaric acid, the molar amount of the cross-linking agent is 0.05-0.40% of the molar amount of the unsaturated monomer, and the molar ratio of the unsaturated monomer to the photoinitiator is 100:1-5; the irradiation time of the ultraviolet lamp is 5-20 min, the acid liquor is dilute sulfuric acid solution, and the concentration of the acid liquor is 0.5-1 mol/L.
According to the invention, hydrogen ions are added into an ionic hydrogel system, so that hydrogen ions not only form hydrogen bonds in a hydrogel network, but also migrate from a hot end to a cold end as transport ions to realize hydrogen ion concentration difference and obtain high thermoelectric potential and open-circuit voltage; the thermoelectric effect triggers a redox reaction between the ionic hydrogel and the electrode, and electron transfer occurs between the electrode and the redox ions at the electrode/electrolyte interface, so that the redox ions move in the electrolyte under a temperature gradient to generate a continuous current.
The beneficial effects of the invention include:
(1) The invention provides a method for preparing Prussian blue electrodes and assembling the Prussian blue electrodes with ionic hydrogel, which not only can improve the power density of a thermoelectric device under a lower temperature difference near room temperature, but also can utilize Prussian blue and a counter electrode as secondary batteries to store electric energy converted from heat energy.
(2) The Prussian blue material electrode provided by the invention has an open frame structure, hydrogen ions can be quickly embedded into the Prussian blue material electrode to form a rich hydrogen bond lattice water network, and meanwhile, the hydrogen ions are used as working ions, so that a quick charge transmission mechanism which cannot be provided by a traditional metal ion battery can be provided.
(3) The invention provides a thermoelectric conversion device based on Prussian blue modified electrodes, which can realize the integration of thermoelectric conversion and electric energy storage functions and can provide stable power for wearable equipment and an Internet of things system.
(4) The invention adds hydrogen ions into the ionic hydrogel system, not only forms hydrogen bonds in the hydrogel network, but also realizes that the concentration difference of the hydrogen ions obtains high thermoelectric potential, and continuous current is generated under a certain temperature gradient.
Drawings
FIG. 1 is a graph of open circuit voltage for a comparative example at different temperature differentials;
FIG. 2 is a graph showing open circuit voltage at different temperature differences according to an embodiment;
FIG. 3 is a graph of current density versus voltage versus power for an embodiment;
FIG. 4 is a graph of power density at different external resistances for an embodiment;
FIG. 5 is a graph of energy density at different external resistances for an embodiment;
FIG. 6 is a cyclic voltammogram of an example at different scan speeds.
Detailed Description
The invention is described in further detail below with reference to the accompanying drawings, by way of which the embodiments are described for the purpose of illustrating the invention and are not to be construed as limiting the invention.
Examples
S1: preparation of ionic hydrogels
Weighing 3.75g of acrylamide and 6.25g of potassium acrylate in a beaker, adding 18mL of deionized water into the beaker, and stirring and mixing uniformly to obtain an unsaturated monomer aqueous solution; adding 0.5mL of N, N' -methylenebisacrylamide aqueous solution with the concentration of 0.01g/mL and 100 mu L of 2-hydroxy-2-methyl propiophenone into the unsaturated monomer aqueous solution, stirring uniformly, performing ultrasonic treatment for 5 minutes to remove bubbles, pouring the mixed solution into a cylindrical silica gel mold (with the diameter and the height of 15 mm), performing polymerization reaction under an ultraviolet lamp for 7 minutes, performing ion exchange in 0.5mol/L dilute sulfuric acid solution after the polymerization reaction is finished, replacing the dilute sulfuric acid solution every 24 hours, and performing ion exchange for 3 days to obtain ionic hydrogel;
S2: preparation of Prussian blue electrode
Dropwise adding 40mL of CuSO 4 solution with the concentration of 0.2mol/L into 40mL of K 3Fe(CN)6 solution with the concentration of 0.1mol/L under magnetic stirring, reacting for 6 hours, collecting olive green precipitate, washing the precipitate with deionized water and centrifuging for multiple times, and then drying in an oven at 60 ℃ for 12 hours to obtain Prussian blue electrode raw materials;
taking 0.14g of Prussian blue electrode raw material, adding 0.04g of conductive carbon powder and 0.02g of polyvinylidene fluoride, mixing and grinding, then adding 3mL of N-methylpyrrolidone, uniformly stirring, coating on carbon cloth, and naturally drying to obtain the Prussian blue electrode;
S3: preparation of activated carbon counter electrode
Adding 0.04g of conductive carbon powder into 0.14g of active carbon, grinding, sieving with a 200-mesh sieve, adding 0.02g of polyvinylidene fluoride, adding 3mL of N-methylpyrrolidone, stirring, coating on carbon cloth, and naturally drying to obtain the active carbon counter electrode.
S4: and assembling the ion hydrogel, the Prussian blue electrode and the active carbon counter electrode, wherein the counter electrode and the Prussian blue modified electrode are respectively arranged on two surfaces of the ion hydrogel, so that a Prussian blue electrode-ion hydrogel-active carbon counter electrode structure is assembled, and a thermoelectric conversion device is obtained.
Comparative example
S1: preparation of ionic hydrogels
Weighing 3.75g of acrylamide and 1.25g of potassium acrylate in a beaker, adding 18mL of deionized water into the beaker, and stirring and mixing uniformly to obtain an unsaturated monomer aqueous solution; adding 0.5mL of N, N' -methylenebisacrylamide aqueous solution with the concentration of 0.01g/mL and 100 mu L of 2-hydroxy-2-methyl propiophenone into the unsaturated monomer aqueous solution, stirring uniformly, performing ultrasonic treatment for 5 minutes to remove bubbles, pouring the mixed solution into a cylindrical silica gel mold (with the diameter and the height of 15 mm), performing polymerization reaction under an ultraviolet lamp for 7 minutes, performing ion exchange in 0.5mol/L dilute sulfuric acid solution after the polymerization reaction is finished, replacing the dilute sulfuric acid solution every 24 hours, and performing ion exchange for 3 days to obtain ionic hydrogel;
S2: two pieces of carbon cloth are respectively arranged on two surfaces of the ion hydrogel, and the ion hydrogel thermoelectric conversion device is assembled.
Comparative test
The thermoelectric conversion devices of the examples and the comparative examples are tested for thermal voltages under different temperature differences by an electrochemical workstation and a temperature controller, and the results show that the thermoelectric conversion devices have strong dependence on temperature, the open-circuit voltage is in an ascending trend along with the increase of the temperature difference, and the thermoelectric conversion devices provided by the examples obtain 452mV open-circuit voltage when the temperature difference is 20K, which is about 250mV higher than the thermoelectric conversion devices provided by the comparative examples, so that the performance of the thermoelectric conversion devices is greatly improved.
As shown in fig. 3, the current density-voltage-power curve of the thermoelectric conversion device provided by the embodiment shows that the instant power density is increased from 50mw·m -2 when the temperature difference is 5K to 500mw·m -2 when the temperature difference is 20K, which indicates that the instant power density is greater when the temperature difference of the thermoelectric conversion device provided by the invention is greater.
The continuous output power density and the energy density are important parameters for measuring the performance of the ion thermoelectric cell, and the energy density of one hour is determined by integrating an output power curve obtained through an external load, so that the external working capacity of the thermoelectric conversion device provided by the embodiment is analyzed, and the results are shown in fig. 4 and 5. As can be seen from fig. 4 and 5, in the external resistance studied, the energy density showed a tendency to rise and then fall, and when the external load was 3.8kΩ, the highest energy density was 130j·m -2 and the highest average power was 4mw·m -2.
In fig. 6, the cyclic voltammogram of the thermoelectric conversion device assembled by the prussian blue modified electrode has obvious oxidation-reduction peak current, which indicates that the prussian blue modified electrode can reversibly store and release hydrogen ions, and electrons are obtained/released in the process, so that the conversion between ions and electrons at the interface between the hydrogel and the prussian blue modified electrode is completed, and the device has better thermoelectric conversion performance and can store electric energy obtained in the thermoelectric conversion process as proved by combining fig. 3 and fig. 4.
What has been described above is merely some embodiments of the present invention. It will be apparent to those skilled in the art that various modifications and improvements can be made without departing from the spirit of the invention.
Claims (10)
1. The preparation method of the Prussian blue modified electrode is characterized by comprising the following preparation steps of:
S1: mixing CuSO 4 solution and K 3Fe(CN)6 solution for reaction, and collecting precipitate after the reaction is finished;
S2: washing and centrifuging the precipitate, and drying to obtain Prussian blue electrode raw material;
S3: mixing Prussian blue electrode raw material, a conductive agent and a binder, grinding, adding an organic solvent, and mixing to obtain mixed slurry;
s4: and coating the mixed slurry on carbon cloth, and drying to obtain the Prussian blue electrode.
2. The method for preparing a Prussian blue modified electrode according to claim 1, wherein in the step S1, the concentration of the CuSO 4 solution is 0.2-1mol/L, the concentration of the K 3Fe(CN)6 solution is 0.1-1mol/L, the molar ratio of the CuSO 4 to the K 3Fe(CN)6 is 1:0.8-1.2, and the reaction time is 6-10h.
3. The method for preparing a Prussian blue modified electrode according to claim 1, wherein in the step S2, the detergent is deionized water, the drying temperature is 60-100 ℃, and the drying time is 10-15h.
4. The method for preparing the Prussian blue modified electrode according to claim 1, wherein in the step S3, the binder is at least one selected from polyvinylidene fluoride, nafion and carboxymethyl cellulose, the conductive agent is at least one selected from conductive carbon powder, ketjen black and acetylene black, and the mass ratio of the raw materials of the Prussian blue electrode to the conductive agent and the binder is 7:2:1.
5. The Prussian blue modified electrode according to any one of claims 1 to 4.
6. A prussian blue modified electrode-based thermoelectric conversion device comprising the prussian blue modified electrode of claim 5, a counter electrode and an ionic hydrogel, said counter electrode and said prussian blue modified electrode being respectively disposed on both surfaces of said ionic hydrogel.
7. The thermoelectric conversion device according to claim 6, characterized in that the method for producing the counter electrode comprises the following production steps: mixing active carbon, a conductive agent and a binder, grinding, adding an organic solvent, and mixing to obtain mixed slurry; and coating the mixed slurry on carbon cloth, and drying to obtain the counter electrode.
8. The thermoelectric conversion device according to claim 7, wherein the conductive agent is selected from at least one of conductive carbon powder, ketjen black, and acetylene black; the binder is at least one selected from polyvinylidene fluoride, nafion and carboxymethyl cellulose; the mass ratio of the active carbon to the conductive agent to the binder is 7:2:1.
9. The thermoelectric conversion device according to claim 6, characterized in that the method for producing the ionic hydrogel comprises the following production steps: preparing an unsaturated monomer aqueous solution, adding a cross-linking agent and a photoinitiator into the unsaturated monomer aqueous solution, mixing, performing polymerization reaction under an ultraviolet lamp, and performing ion exchange in acid liquor after the polymerization reaction is finished to obtain the ionic hydrogel; the unsaturated monomer is at least one selected from acrylamide, acrylic acid, potassium acrylate, methacrylic acid, sodium methacrylate and isopropyl acrylamide.
10. The device according to claim 9, wherein the cross-linking agent is at least one selected from the group consisting of N, N' -methylenebisacrylamide, pentaerythritol triacrylate, pentaerythritol triethyl, and polyethylene glycol diacrylate, the photoinitiator is 2-hydroxy-2-methylpropaneketone or 2-ketoglutaric acid, the molar amount of the cross-linking agent is 0.05-0.40% of the molar amount of the unsaturated monomer, the molar ratio of the unsaturated monomer to the photoinitiator is 100:1-5, the irradiation time of the ultraviolet lamp is 5-20 min, the acid solution is a dilute sulfuric acid solution, and the acid solution concentration is 0.5-1 mol/L.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202311764687.1A CN117915745A (en) | 2023-12-20 | 2023-12-20 | Prussian blue modified electrode-based thermoelectric conversion device and preparation method thereof |
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| CN202311764687.1A CN117915745A (en) | 2023-12-20 | 2023-12-20 | Prussian blue modified electrode-based thermoelectric conversion device and preparation method thereof |
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