CN112713233B - Quasi-solid ionic thermoelectric conversion material, thermoelectric conversion device and application thereof - Google Patents
Quasi-solid ionic thermoelectric conversion material, thermoelectric conversion device and application thereof Download PDFInfo
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- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 claims description 12
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/857—Thermoelectric active materials comprising compositions changing continuously or discontinuously inside the material
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Abstract
The application relates to a quasi-solid ionic thermoelectric material, which comprises a gel matrix material, water-soluble metal salt, an oxidation/reduction pair and water, wherein the gel matrix material, the water-soluble metal salt and the oxidation/reduction pair are distributed in the water. The application also relates to a thermoelectric conversion device comprising the thermoelectric conversion material, a thermoelectric power generation device comprising the thermoelectric conversion device, and a wearable apparatus comprising the thermoelectric power generation device. The quasi-solid ionic thermoelectric material can obtain high thermoelectric potential from the surrounding environment through the synergistic effect of the thermal diffusion (Soret) effect and the thermo-chemical (thermo-chemical) effect, has simple and convenient manufacturing method and low cost, is very suitable for preparing flexible ionic thermoelectric conversion devices, flexible thermoelectric generation devices and flexible wearable equipment, and has great application prospects in the fields of Internet of things and flexible wearable.
Description
Technical Field
The application belongs to the technical field of novel thermoelectric materials and thermoelectric conversion devices, and particularly relates to a quasi-solid ionic thermoelectric conversion material, a preparation method and application thereof.
Background
Along with the rapid development of the technology of the Internet of things and the requirement of building a smart city based on the requirements of China, more and more sensors or electronic equipment are applied to the system of the Internet of things and play an increasingly important role. In order to effectively ensure that a large number of discrete sensors or electronics can continue to operate autonomously and independently, self-supporting energy technology, where the sensors or electronics capture energy from the surrounding environment for continuous power supply, is a critical technology and is a hot spot of research. The thermoelectric conversion material and the thermoelectric conversion device can realize direct mutual conversion between heat energy and electric energy, have the advantages of easy miniaturization and flexibility, no noise and emission, safety and reliability and the like, and are very suitable for small sensors or electronic equipment applied in an Internet of things system.
Thermoelectric conversion devices based on electron-transporting semiconductor thermoelectric conversion materials are typical representatives of converting thermal energy into electrical energy by utilizing the Seebeck effect in the presence of a temperature difference, through the directional transport of electrons. At present, the adopted and researched thermoelectric conversion material captures energy in a room temperature environment, and can achieve mW-level output power for a sensor in the Internet of things to work, but the thermoelectric potential value is difficult to break through +/-200 mu V/K due to the influence of the electroacoustic transport behavior of a semiconductor. This means that if a voltage between 1 and 3V is to be obtained for the sensor to operate properly, thousands of pairs of n/p thermoelectric pairs need to be connected in series [1] Greatly increases the complexity and integration of the device, or requires the voltage to be increased by an external boost chip [2] As a result, power consumption is increased and cost is increased.
Thermoelectric conversion materials based on ion migration have unique advantages in achieving conversion of low-grade waste heat energy into electrical energy. Such an ion type thermoelectric conversion material [3] The oxidation/reduction couple in the electrolyte is utilized to continuously convert environmental heat energy into electric energy under the temperature gradient formed by the temperature difference, and toxic and harmful gas is not released, and the generated thermoelectric potential is in the mV/K order. Therefore, compared with the high raw materials of the electron transfer type semiconductor thermoelectric conversion device and the thermoelectric potential of mu V/K magnitude, the ionic thermoelectric conversion material has more advantages, is expected to replace the traditional solid semiconductor thermoelectric device in the temperature range below 100 ℃ and has wider application space.
The liquid ionic thermoelectric material studied at present uses oxidation/reduction couple and adopts thermo-electrochemical (thermo-chemical) effect to obtain thermoelectric potential with only a few mV/K, and meanwhile, a series of problems such as (1) liquid leakage problem exist, which seriously affect practical application; (2) Convection phenomenon resistance existing in solutionPreventing the internal heat transfer of the device and being unfavorable for the establishment of temperature difference [4-7] . Recently, X.Crispin [8] Group utilization of Soret effect on Na-containing + The ionic polyethylene oxide electrolyte obtains p-type thermoelectric potential of +11mV/K, L.Hu group [9] Using Soret effect on Na-containing + A p-type thermoelectric potential of +24mV/K was obtained in the polyethylene oxide electrolyte-impregnated cellulose membrane. But there is still a lack of n-type ionic thermoelectric materials that can be matched to their thermoelectric potential.
Disclosure of Invention
In order to overcome the above problems of the liquid ionic thermoelectric material, the present application aims to provide a quasi-solid ionic thermoelectric conversion material, which can obtain high thermoelectric potential through the synergistic effect of the double effects of thermal diffusion (Soret) effect and thermo-chemical (thermogalvanic) effect, and provides possibility for the application of thermoelectric conversion devices using the material in the fields of flexible wearable and internet of things.
Accordingly, in one aspect, the present application provides a quasi-solid ionic thermoelectric material comprising a gelling matrix material, a water-soluble metal salt, an oxidation/reduction pair, and water, wherein the gelling matrix material, the water-soluble metal salt, and the oxidation/reduction pair are distributed in water.
The gel matrix material in the quasi-solid ionic thermoelectric material can be any polymer material which is gelled after being dissolved in water. The gel matrix material is a matrix of quasi-solid ionic thermoelectric material for carrying alkali or alkaline earth metal salt additives and oxidation/reduction pairs. In particular embodiments of the present application, the gelling matrix material may be, for example, gelatin, polyvinyl alcohol, chitosan, polyacrylic acid or acrylamide or the like.
The water-soluble metal salt in the quasi-solid ionic thermoelectric material is dissociated into metal cations and counter anions in the quasi-solid ionic thermoelectric material, and the function of Soret effect is exerted in the quasi-solid ionic thermoelectric material. In a specific embodiment of the application, the water-soluble metal salt is an alkali metal or alkaline earth metal salt. In a preferred embodiment of the application, the alkali metal or baseThe earth metal salt is an alkali metal or alkaline earth metal halide, or an alkali metal or alkaline earth metal nitrate, or an alkali metal or alkaline earth metal sulfate. In a more preferred embodiment of the application, the alkali or alkaline earth metal halide is KCl, KBr, KI, naCl, mgCl 2 、CaCl 2 、SrCl 2 、BaCl 2 The nitrate of alkali metal or alkaline earth metal is KNO 3 、NaNO 3 、LiNO 3 、Mg(NO 3 ) 2 、Cu(NO 3 ) 2 、Co(NO 3 ) 2 Or Mn (NO) 3 ) 2 The sulfate of alkali metal or alkaline earth metal is K 2 SO 4 、Na 2 SO 4 、CoSO 4 Or MnSO 4 。
The oxidation/reduction couple in the quasi-solid ionic thermoelectric material acts as a thermoelectric effect in the quasi-solid ionic thermoelectric material. In a specific embodiment of the application, the oxidation/reduction pair is potassium ferricyanide/potassium ferrocyanide.
In a specific embodiment of the present application, the water in the quasi-solid ionic thermoelectric material is deionized water or distilled water.
In a specific embodiment of the present application, the gel matrix material is present in an amount ranging from 0.01 to 1g/ml, such as 0.01, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, or 1g/ml, by volume of the quasi-solid ionic thermoelectric material; the alkali metal or alkaline earth metal salt additive is present in an amount in the range of 0.001 to 5mol/L, for example 0.005, 0.01, 0.05, 0.1, 0.5, 1, 2, 3, 4 or 5mol/L; the content of the oxidation/reduction couple is in the range of 0.001/0.001-0.8/0.8mol/L and the ratio of the oxidation/reduction couple may be equal or unequal, preferably unequal, e.g. the ratio of the oxidation/reduction couple is 0.001/0.001, 0.03/0.05, 0.06/0.1, 0.2/0.2, 0.18/0.3, 0.25/0.42, 0.5/0.5, 0.36/0.6, 0.7/0.7 or 0.8/0.8mol/L. In a preferred embodiment of the present application, the gel matrix material is present in an amount ranging from 0.1 to 0.5g/ml, the alkali or alkaline earth metal salt additive is present in an amount ranging from 0.1 to 3mol/L, and the oxidation/reduction couple is present in an amount ranging from 0.1/0.1 to 0.5/0.5mol/L, based on the volume of the quasi-solid ionic thermoelectric material.
The quasi-solid ionic thermoelectric material can be prepared by the following method:
(1) Adding an appropriate amount of the gelling matrix material, the alkali metal or alkaline earth metal salt additive and the oxidation/reduction pair to an appropriate amount of water (e.g., deionized water) such that the content of the gelling matrix material, the alkali metal or alkaline earth metal salt additive and the oxidation/reduction pair in the resulting mixture is within the specified content range, respectively;
(2) And stirring the obtained mixture at a temperature of between room temperature and 95 ℃ at a stirring speed of 400-500rpm for 0.5-24 hours to form gel, and cooling to obtain the quasi-solid ionic thermoelectric material.
The thermoelectric potential of the quasi-solid ionic thermoelectric material of the present application may be measured to be 0 to-20 mV/K.
In a second aspect, the present application provides an ionic thermoelectric conversion device comprising electrode materials and a quasi-solid ionic thermoelectric material of the first aspect of the present application, wherein the quasi-solid ionic thermoelectric material is located between and in contact with the electrode materials. In a specific embodiment of the application, the electrode material is a copper foil, aluminum foil or carbon foil electrode sheet. In a specific embodiment of the present application, the ion-type thermoelectric conversion device may be encapsulated with a polyethylene film, a polypropylene film, or an aluminum plastic film. In particular embodiments of the present application, the ionic thermoelectric conversion device may be in the form of a thermoelectric chemical unit.
The ionic thermoelectric conversion device can be prepared by the following method: and coating the prepared quasi-solid ionic thermoelectric material on one electrode plate in air atmosphere, covering the coating with the other electrode plate to form a sandwich structure, and finally packaging to assemble the ionic thermoelectric conversion device.
In a third aspect, the present application provides a thermoelectric generation device comprising the ionic thermoelectric conversion device of the second aspect of the present application. The thermoelectric generation device may include one or more of the ion type thermoelectric conversion devices of the second aspect of the present application, for example, 1 to 100 ion type thermoelectric conversion devices in series, as required.
According to measurement, the thermoelectric power generation device can obtain 0-3V voltage by utilizing human body temperature difference to recycle electric energy.
In a fourth aspect, the present application provides a wearable apparatus comprising the thermoelectric generation device of the third aspect of the present application and a wearable substrate in parallel therewith. The donning substrate may be, for example, a glove, hat, coat, undergarment, pants, shoe, sock, bracelet, earring, necklace, or the like.
The application has the beneficial effects that:
1. the quasi-solid ionic thermoelectric material can obtain high thermoelectric potential from the surrounding environment through the synergistic effect of the double effects of thermal diffusion (Soret) effect and thermo-chemical (thermo-chemical) effect, is 2 orders of magnitude higher than that of the traditional semiconductor thermoelectric material, has strong operability, no noise and no emission, and is environment-friendly.
2. The raw materials used for the quasi-solid ionic thermoelectric material are gelled matrix materials, alkali metal or alkaline earth metal salt additives and oxidation/reduction pairs, are easy to obtain, have low cost, can be prepared by adjusting the types and the concentration of the matrix materials and the additives and the concentration of the oxidation/reduction pairs by a stirring and mixing method, and are simple and convenient.
3. The quasi-solid ionic thermoelectric material is a quasi-solid cementing material, so that the problem of liquid leakage is avoided, the internal solution convection phenomenon is greatly reduced, and the establishment of temperature difference is facilitated.
4. The quasi-solid ionic thermoelectric material can be conveniently coated on electrode plates such as copper foil, aluminum foil, carbon foil and the like to form a sandwich structure, and then the sandwich structure is packaged and assembled into the ionic thermoelectric conversion device.
5. The quasi-solid ionic thermoelectric material is a flexible gel material, and is very suitable for preparing flexible ionic thermoelectric conversion devices, flexible thermoelectric generation devices and flexible wearable equipment.
6. The ionic thermoelectric conversion device can be used for manufacturing thermoelectric power generation devices, can be applied to wearable equipment, and has a huge application prospect in the fields of Internet of things and flexible wearable by utilizing high voltage recovered by human body temperature difference.
Drawings
FIG. 1 is a schematic diagram of the theory of the quasi-solid ionic thermoelectric material of the present application that obtains high thermoelectric potential by the synergy of thermal diffusion (Soret) effect and thermo-chemical (thermo-chemical) effect;
FIG. 2 is a representative flexible physical diagram of an ionic thermoelectric conversion device of the present application comprising a quasi-solid state ionic thermoelectric material of the present application and electrode pads;
FIG. 3 is a schematic diagram of an open circuit voltage of an ion-type thermoelectric conversion device using temperature difference to generate electricity according to an embodiment of the present application;
fig. 4 is a schematic diagram of open circuit voltage generated by human body temperature difference through a wearable device according to an application example of the present application, wherein the wearable device is formed by arranging a plurality of thermoelectric devices according to the present application, which are integrated together, on a glove.
Detailed Description
The application will be described in further detail by means of the following detailed description in conjunction with the accompanying drawings.
As shown in fig. 1, the quasi-solid ionic thermoelectric material of the present application obtains a high thermoelectric potential from the surrounding environment by the synergistic effect of the double effect of thermal diffusion (Soret) effect and thermoelectric chemical (thermochemical) effect. Specifically, a quasi-solid ionic thermoelectric material comprising a gel matrix material, anions and cations (formed by soluble metal salts) and oxidation/reduction pairs (such as potassium ferricyanide/potassium ferrocyanide) is sandwiched between electrode plates to form an ionic thermoelectric conversion device, so that one electrode plate of the ionic thermoelectric conversion device is positioned at a hot end with a higher temperature, and the other electrode plate is positioned at a cold end with a lower temperature. As shown in the left panel of fig. 1, in the quasi-solid ionic thermoelectric material of the present application, cations are mainly bound by the gel matrix material with anions, and anions migrate to the cold-end electrode plates in the presence of a temperature field and aggregate to form an electric double layer structure, so that a thermoelectric potential is formed between the two electrode plates, which is the Soret effect. As in the middle of figure 1As shown in the figure, oxidation reaction Fe (CN) occurs at the hot end due to the existence of oxidation/reduction couple in the quasi-solid ionic thermoelectric material 6 4- -e→Fe(CN) 6 3- The released electrons are gathered on the hot end electrode plate, and are connected through an external circuit, the electrons return to the cold end, and a reduction reaction Fe (CN) occurs near the cold end electrode plate 6 3- +e→Fe(CN) 6 4- The oxidation products and the reduction products return to the counter electrode under convective diffusion. Thereby a thermoelectric potential is formed between the two electrode plates, which is a thermo-chemical (thermo-chemical) effect. As shown in the right panel of fig. 1, the quasi-solid ionic thermoelectric material of the present application can generate a high thermoelectric potential between two electrode sheets by the synergistic effect of the Soret effect and the thermo-chemical (thermo-chemical) effect.
The quasi-solid ionic thermoelectric material can be used for manufacturing ionic thermoelectric conversion devices. Because the quasi-solid ionic thermoelectric material takes the flexible cementing matrix material as a matrix, a very soft ionic thermoelectric conversion device can be manufactured by using the flexible electrode plate and the quasi-solid ionic thermoelectric material. Fig. 2 shows a representative flexible physical diagram of an ionic thermoelectric conversion device comprising a quasi-solid state ionic thermoelectric material and a flexible electrode sheet of the present application. The exemplary ionic thermoelectric conversion device shown in fig. 2 is fabricated to a length of about 4cm and is very flexible and can be crimped over a finger. The potential application prospect of the quasi-solid ionic thermoelectric material and the ionic thermoelectric conversion device in the wearable field and the Internet of things field is shown. The ion type thermoelectric conversion device can be used for further manufacturing a flexible thermoelectric generation device and flexible wearable equipment, and product development and application in the wearable field and the Internet of things field are realized.
The application is further illustrated by the following non-limiting examples.
Example 1
1g of polyvinyl alcohol (final concentration 0.1 g/ml), 0.3728g of potassium chloride (final concentration 0.5 mol/L), 0.1975g of potassium ferricyanide (final concentration 0.06 mol/L) and 0.4224g of potassium ferrocyanide (final concentration 0.1 mol/L) were weighed into approximately 5ml of deionized water. The mixture was magnetically stirred at a temperature of 60℃for 5 hours at a stirring speed of 500rpm, and the mixture was thoroughly mixed. And then adding deionized water to a volume of 10ml, continuously and uniformly stirring until gelation, and cooling to obtain the quasi-solid ionic thermoelectric material.
The prepared gel state ionic thermoelectric material is coated on a piece of copper foil electrode slice with the square of 1.5cm multiplied by 1.5cm, and the thickness of the coating is about 2mm. And then another same copper foil electrode plate is covered on the coating to form a sandwich structure of the electrode plate, the quasi-solid ionic thermoelectric material and the electrode plate. And finally, packaging by using a polyethylene film, and assembling the ion type thermoelectric conversion device.
As shown in FIG. 3, the open-circuit voltage and the temperature difference of the ionic thermoelectric conversion device in this embodiment have a corresponding relationship, and the slope after linear fitting corresponds to the thermoelectric value, and the obtained thermoelectric value is-1.6 mV/K.
Example 2
4g of chitosan (final concentration 0.4 g/ml), 0.07455g of potassium chloride (final concentration 0.1 mol/L), 0.3292g of potassium ferricyanide (final concentration 0.1 mol/L) and 0.8448g of potassium ferrocyanide (final concentration 0.2 mol/L) were weighed into approximately 5ml of deionized water. The mixture was magnetically stirred at a temperature of 60℃for 5 hours at a stirring speed of 500rpm, and the mixture was thoroughly mixed. And then adding deionized water to a volume of 10ml, continuously and uniformly stirring until gelation, and cooling to obtain the quasi-solid ionic thermoelectric material.
The prepared gel state ionic thermoelectric material is coated on a piece of copper foil electrode slice with the square of 1.5cm multiplied by 1.5cm, and the thickness of the coating is about 2mm. And then another same copper foil electrode plate is covered on the coating to form a sandwich structure of the electrode plate, the quasi-solid ionic thermoelectric material and the electrode plate. And finally, packaging by using a polyethylene film, and assembling the ion type thermoelectric conversion device.
As shown in FIG. 3, the open-circuit voltage and the temperature difference of the ionic thermoelectric conversion device in this embodiment have a corresponding relationship, and the slope after linear fitting corresponds to the thermoelectric value, and the obtained thermoelectric value is-3.0 mV/K.
Example 3
2g of polyacrylic acid (final concentration 0.2 g/ml), 0.1491g of potassium chloride (final concentration 0.2 mol/L), 0.6585g of potassium ferricyanide (final concentration 0.2 mol/L) and 1.2673g of potassium ferrocyanide (final concentration 0.3 mol/L) were weighed into approximately 5ml of deionized water. The mixture was magnetically stirred at a temperature of 60℃for 5 hours at a stirring speed of 500rpm, and the mixture was thoroughly mixed. And then adding deionized water to a volume of 10ml, continuously and uniformly stirring until gelation, and cooling to obtain the quasi-solid ionic thermoelectric material.
The prepared gel state ionic thermoelectric material is coated on a piece of copper foil electrode slice with the square of 1.5cm multiplied by 1.5cm, and the thickness of the coating is about 2mm. And then another same copper foil electrode plate is covered on the coating to form a sandwich structure of the electrode plate, the quasi-solid ionic thermoelectric material and the electrode plate. And finally, packaging by using a polyethylene film, and assembling the ion type thermoelectric conversion device.
As shown in FIG. 3, the open-circuit voltage and the temperature difference of the ionic thermoelectric conversion device in this embodiment have a corresponding relationship, and the slope after linear fitting corresponds to the thermoelectric value, and the obtained thermoelectric value is-2.2 mV/K.
Example 4
1g of acrylamide (final concentration 0.1 g/ml), 0.5964g of potassium chloride (final concentration 0.8 mol/L), 0.3292g of potassium ferricyanide (final concentration 0.1 mol/L) and 0.4224g of potassium ferrocyanide (final concentration 0.1 mol/L) were weighed into approximately 5ml of deionized water. The mixture was magnetically stirred at a temperature of 60℃for 5 hours at a stirring speed of 500rpm, and the mixture was thoroughly mixed. And then adding deionized water to a volume of 10ml, continuously and uniformly stirring until gelation, and cooling to obtain the quasi-solid ionic thermoelectric material.
The prepared gel state ionic thermoelectric material is coated on a piece of aluminum foil electrode plate with the square of 1.5cm multiplied by 1.5cm, and the thickness of the coating is about 2mm. And then another same aluminum foil electrode plate is covered on the coating to form a sandwich structure of the electrode plate, the quasi-solid ionic thermoelectric material and the electrode plate. And finally, packaging by using a polypropylene film, and assembling the ion type thermoelectric conversion device.
As shown in FIG. 3, the open-circuit voltage and the temperature difference of the ionic thermoelectric conversion device in this embodiment have a corresponding relationship, and the slope after linear fitting corresponds to the thermoelectric value, and the obtained thermoelectric value is-4.0 mV/K.
Example 5
0.1g gelatin (final concentration 0.01 g/ml), 0.0007g potassium chloride (final concentration 0.001 mol/L), 0.0033g potassium ferricyanide (final concentration 0.001 mol/L) and 0.0084g potassium ferrocyanide (final concentration 0.002 mol/L) were weighed into approximately 5ml deionized water. The mixture was magnetically stirred at a temperature of 60℃for 5 hours at a stirring speed of 500rpm, and the mixture was thoroughly mixed. And then adding deionized water to a volume of 10ml, continuously and uniformly stirring until gelation, and cooling to obtain the quasi-solid ionic thermoelectric material.
The prepared gel state ionic thermoelectric material is coated on a piece of aluminum foil electrode plate with the square of 1.5cm multiplied by 1.5cm, and the thickness of the coating is about 2mm. And then another same aluminum foil electrode plate is covered on the coating to form a sandwich structure of the electrode plate, the quasi-solid ionic thermoelectric material and the electrode plate. And finally, packaging by using a polypropylene film, and assembling the ion type thermoelectric conversion device.
As shown in FIG. 3, the open-circuit voltage and the temperature difference of the ionic thermoelectric conversion device in this embodiment have a corresponding relationship, and the slope after linear fitting corresponds to the thermoelectric value, and the obtained thermoelectric value is-5.4 mV/K.
Example 6
0.5g gelatin (final concentration 0.05 g/ml), 0.0074g potassium chloride (final concentration 0.01 mol/L), 0.0329g potassium ferricyanide (final concentration 0.01 mol/L) and 0.0845g potassium ferrocyanide (final concentration 0.02 mol/L) were weighed into approximately 5ml deionized water. The mixture was magnetically stirred at a temperature of 60℃for 5 hours at a stirring speed of 500rpm, and the mixture was thoroughly mixed. And then adding deionized water to a volume of 10ml, continuously and uniformly stirring until gelation, and cooling to obtain the quasi-solid ionic thermoelectric material.
The prepared gel state ionic thermoelectric material is coated on a piece of aluminum foil electrode plate with the square of 1.5cm multiplied by 1.5cm, and the thickness of the coating is about 2mm. And then another same aluminum foil electrode plate is covered on the coating to form a sandwich structure of the electrode plate, the quasi-solid ionic thermoelectric material and the electrode plate. And finally, packaging by using a polypropylene film, and assembling the ion type thermoelectric conversion device.
As shown in FIG. 3, the open-circuit voltage and the temperature difference of the ionic thermoelectric conversion device in this embodiment have a corresponding relationship, and the slope after linear fitting corresponds to the thermoelectric value, and the obtained thermoelectric value is-6.7 mV/K.
Example 7
1g of gelatin (final concentration 0.1 g/ml), 0.0746g of potassium chloride (final concentration 0.1 mol/L), 2.6339g of potassium ferricyanide (final concentration 0.8 mol/L) and 3.3794g of potassium ferrocyanide (final concentration 0.8 mol/L) were weighed into approximately 5ml of deionized water. The mixture was magnetically stirred at a temperature of 60℃for 5 hours at a stirring speed of 500rpm, and the mixture was thoroughly mixed. And then adding deionized water to a volume of 10ml, continuously and uniformly stirring until gelation, and cooling to obtain the quasi-solid ionic thermoelectric material.
The prepared gel state ionic thermoelectric material is coated on a piece of carbon foil electrode plate with the square of 1.5cm multiplied by 1.5cm, and the thickness of the coating is about 2mm. And then another same carbon foil electrode plate is covered on the coating to form a sandwich structure of the electrode plate, the quasi-solid ionic thermoelectric material and the electrode plate. And finally, packaging by using an aluminum plastic film, and assembling the ion type thermoelectric conversion device.
As shown in FIG. 3, the open-circuit voltage and the temperature difference of the ionic thermoelectric conversion device in this embodiment have a corresponding relationship, and the slope after linear fitting corresponds to the thermoelectric value, and the obtained thermoelectric value is-4.8 mV/K.
Example 8
3g of gelatin (final concentration 0.3 g/ml), 0.8946g of potassium chloride (final concentration 1.2 mol/L), 0.7902g of potassium ferricyanide (final concentration 0.25 mol/L) and 1.7742g of potassium ferrocyanide (final concentration 0.42 mol/L) were weighed into approximately 5ml of deionized water. The mixture was magnetically stirred at a temperature of 60℃for 5 hours at a stirring speed of 500rpm, and the mixture was thoroughly mixed. And then adding deionized water to a volume of 10ml, continuously and uniformly stirring until gelation, and cooling to obtain the quasi-solid ionic thermoelectric material.
The prepared gel state ionic thermoelectric material is coated on a piece of carbon foil electrode plate with the square of 1.5cm multiplied by 1.5cm, and the thickness of the coating is about 2mm. And then another same carbon foil electrode plate is covered on the coating to form a sandwich structure of the electrode plate, the quasi-solid ionic thermoelectric material and the electrode plate. And finally, packaging by using an aluminum plastic film, and assembling the ion type thermoelectric conversion device.
As shown in FIG. 3, the open-circuit voltage and the temperature difference of the ionic thermoelectric conversion device in this embodiment have a corresponding relationship, and the slope after linear fitting corresponds to the thermoelectric value, and the obtained thermoelectric value is-17.0 mV/K.
Example 9
10g of gelatin (final concentration 1 g/ml), 3.7275g of potassium chloride (final concentration 5 mol/L), 0.1975g of potassium ferricyanide (final concentration 0.06 mol/L) and 0.4224g of potassium ferrocyanide (final concentration 0.1 mol/L) were weighed into approximately 5ml of deionized water. The mixture was magnetically stirred at a temperature of 60℃for 5 hours at a stirring speed of 500rpm, and the mixture was thoroughly mixed. And then adding deionized water to a volume of 10ml, continuously and uniformly stirring until gelation, and cooling to obtain the quasi-solid ionic thermoelectric material.
The prepared gel state ionic thermoelectric material is coated on a piece of carbon foil electrode plate with the square of 1.5cm multiplied by 1.5cm, and the thickness of the coating is about 2mm. And then another same carbon foil electrode plate is covered on the coating to form a sandwich structure of the electrode plate, the quasi-solid ionic thermoelectric material and the electrode plate. And finally, packaging by using an aluminum plastic film, and assembling the ion type thermoelectric conversion device.
As shown in FIG. 3, the open-circuit voltage and the temperature difference of the ionic thermoelectric conversion device in this embodiment have a corresponding relationship, and the slope after linear fitting corresponds to the thermoelectric value, and the obtained thermoelectric value is-9.5 mV/K.
Application example
The thermoelectric values of the ionic thermoelectric conversion devices of examples 1-9 above were between-1.6 and-17.0 mV/K, whereas as described in the "background art" section above, the thermoelectric values of conventional semiconductor thermoelectric conversion materials hardly broke through + -0.2 mV/K. Therefore, the ion type thermoelectric converter of the applicationThe element can obtain high thermoelectric voltage from the surrounding environment, is 2 orders of magnitude higher than that of the traditional semiconductor thermoelectric material, and can be compared with a shoulder X.Crispin group [8] And group L.Hu [9] The obtained p-type thermoelectric potential shows good application prospect in thermoelectric generation.
The thermoelectric cell manufactured in example 8 was used to manufacture a thermoelectric device and a wearable apparatus. As shown in fig. 4, 25 thermoelectric conversion units fabricated in example 8 were sequentially connected in series with a conductive copper tape, and a thermoelectric device was fabricated. The temperature difference power generation device is tightly stuck on the corresponding part of the back of the hand by using the transparent adhesive tape, and the flexible wearable temperature difference power generation device is manufactured.
Fig. 4 also shows a schematic diagram of open circuit voltage of the manufactured wearable device generated by using human body temperature difference. As shown in the figure, after the flexible wearable thermoelectric generation device is worn on the hand, the temperature of one side of the thermoelectric generation device close to the skin of the hand (T Skin of a person ) A temperature (T) higher than a side of the thermoelectric power generation device close to the ambient air Environment (environment) ) Thereby forming a temperature difference at both sides of the thermoelectric power generation device, and generating a voltage through the Soret effect and the thermo-chemical (thermo-chemical) effect of the quasi-solid ionic thermoelectric material in the thermoelectric power generation device. The voltage gradually increased over time and at 16 minutes Δv reached 2.15V. That is, in the present application example, only 25 thermoelectric conversion units constitute the thermoelectric power generation device, and a thermal voltage of 2.15V can be realized.
This means that the thermoelectric conversion device based on the quasi-solid ionic thermoelectric material of the present application can meet the requirement of the operating voltage between the usual sensors 1 to 3V by only tens or at most tens of thermoelectric conversion devices, and the complexity and integration of the device can be reduced. In contrast, as described in the background section above, using thermoelectric conversion devices based on electron-transporting semiconductor thermoelectric conversion materials would require thousands of n/p thermoelectric pairs in series to achieve an operating voltage between 1 and 3V, greatly increasing the complexity and integration of the device. Therefore, the thermoelectric conversion device, the thermoelectric power generation device and the wearable equipment manufactured by the quasi-solid ionic thermoelectric material have wide application prospects in the technical field of Internet of things and the technical field of wearable equipment.
Reference is made to:
[1]Mu,E.et al.A novel self-powering ultrathin TEG device based on micro/nano emitter for radiative cooling.Nano Energy 55,494-500(2019).
[2]Iezzi,B.,Ankireddy,K.,Twiddy,J.,Losego,M.D.,Jur,J.S.Printed,metallic thermoelectric generators integrated with pipe insu lation for powering wireless sensors.Appl.Energy 208,758-765(2017).
[3]R.Zito,AIAA J.1,2133-2138(1963)
[4]T.J.Abraham,D.R.MacFarlane,J.M.Pringle,Energy Environ.Sci.6,2639-2645(2013).
[5]M.S.Romano et al.,Adv.Mater.25,6602-6606(2013).
[6]H.Im et al.,Nat.Commun.7,10600(2016).
[7]J.Duan et al.,Nat.Commun.9,5146(2018).
[8]D.Zhao et al.,Energy Environ.Sci.9,1450-1457(2016).
[9]T.Li et al.,Nat.Mater.18,608-613(2019).
the application has been described with particular reference to the examples which are intended to be illustrative of the application and not limiting. Several simple deductions, modifications or substitutions may also be made by a person skilled in the art according to the idea of the application. Such deductions, modifications or alternatives fall within the scope of the claims of the present application.
Claims (9)
1. A quasi-solid ionic thermoelectric material characterized by comprising a gel matrix material, a water-soluble metal salt, an oxidation/reduction pair and water, wherein the gel matrix material, the water-soluble metal salt, the oxidation/reduction pair are distributed in the water;
the gel matrix material is gelatin, polyvinyl alcohol, chitosan, polyacrylic acid or acrylamide;
the water-solubleThe sexual metal salt is alkali metal halide; the alkali metal halide is KCl, KBr, KI, naCl, mgCl 2 、CaCl 2 、SrCl 2 Or BaCl 2 ；
The oxidation/reduction pair is potassium ferricyanide/potassium ferrocyanide.
2. The quasi-solid state ionic thermoelectric material of claim 1 wherein the water is deionized or distilled water.
3. The quasi-solid state ionic thermoelectric material according to any one of claims 1 to 2, wherein the content of the gel matrix material is in the range of 0.01 to 1g/ml, the content of the water-soluble metal salt is in the range of 0.001 to 5mol/L, and the content of the oxidation/reduction pair is in the range of 0.001/0.001 to 0.8/0.8mol/L, based on the volume of the quasi-solid state ionic thermoelectric material.
4. The quasi-solid ionic thermoelectric material according to claim 3, wherein the gel matrix material is contained in an amount ranging from 0.1 to 0.5g/ml, the water-soluble metal salt is contained in an amount ranging from 0.1 to 3mol/L, and the oxidation/reduction couple is contained in an amount ranging from 0.1/0.1 to 0.5/0.5mol/L, based on the volume of the quasi-solid ionic thermoelectric material.
5. An ionic thermoelectric conversion device comprising electrode materials and a quasi-solid ionic thermoelectric material according to any one of claims 1 to 4, wherein the quasi-solid ionic thermoelectric material is located between and in contact with the electrode materials.
6. The ionic thermoelectric conversion device according to claim 5, wherein the electrode material is a copper foil, an aluminum foil or a carbon foil electrode sheet.
7. The ion type thermoelectric conversion device according to claim 6, wherein the ion type thermoelectric conversion device is packaged with a polyethylene film, a polypropylene film, or an aluminum plastic film.
8. A thermoelectric generation device characterized in that it comprises one or more ionic thermoelectric conversion devices according to claim 6 or 7.
9. A wearable apparatus, characterized in that it comprises a thermoelectric generation device according to claim 8.
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