阅读说明：本技术 准固态离子型热电转换材料、热电转换器件及其应用 (Quasi-solid-state ionic thermoelectric conversion material, thermoelectric conversion device and application thereof ) 是由 刘玮书 韩成功 李其锴 邓彪 于 2019-10-25 设计创作，主要内容包括：本申请涉及一种准固态离子型热电材料,其包括胶凝基体材料、水溶性金属盐、氧化/还原电对和水,其中胶凝基体材料、水溶性金属盐、氧化/还原电对分布在水中。本申请还涉及包括该热电转换材料的热电转换器件、包括该热电转换器件的温差发电装置及包括该温差发电装置的可穿戴装备。本发明的准固态离子型热电材料通过热扩散(Soret)效应和热电化学(thermogalvanic)效应的双效应协同作用,可以从周围环境中获得高的热电势,制作方法简单方便、成本低廉,非常适合制备柔性离子型热电转换器件、柔性温差发电装置和柔性可穿戴装备,在物联网及柔性可穿戴领域将具有巨大的应用前景。(The application relates to a quasi-solid ionic thermoelectric material, which comprises a gelling matrix material, a water-soluble metal salt, an oxidation/reduction couple and water, wherein the gelling matrix material, the water-soluble metal salt and the oxidation/reduction couple are distributed in the water. The present application also relates to a thermoelectric conversion device including the thermoelectric conversion material, a thermoelectric generation device including the thermoelectric conversion device, and wearable equipment including the thermoelectric generation device. The quasi-solid ionic thermoelectric material can obtain high thermoelectric force from the surrounding environment through the synergistic effect of the double effects of the thermal diffusion (Soret) effect and the thermo-electrochemical (thermogalvanic) effect, has simple and convenient manufacturing method and low cost, is very suitable for preparing a flexible ionic thermoelectric conversion device, a flexible temperature difference power generation device and flexible wearable equipment, and has huge application prospect in the fields of Internet of things and flexible wearable equipment.)

1. A quasi-solid ionic thermoelectric material comprising a gelling matrix material, a water soluble metal salt, an oxidation/reduction couple, and water, wherein the gelling matrix material, the water soluble metal salt, and the oxidation/reduction couple are distributed in the water.

2. The quasi-solid ionic thermoelectric material of claim 1, wherein the gelling matrix material is gelatin, polyvinyl alcohol, chitosan, polyacrylic acid, or acrylamide, or the like.

3. The quasi-solid ionic thermoelectric material of claim 1, wherein the water-soluble metal salt is an alkali metal or alkaline earth metal salt; preferably, the alkali metal or alkaline 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; more preferably, the alkali or alkaline earth metal halide is KCl, KBr, KI, NaCl, MgCl₂、CaCl₂、SrCl₂、BaCl₂The alkali metal or alkaline earth metal nitrate is KNO₃、NaNO₃、LiNO₃、Mg(NO₃)₂、Cu(NO₃)₂、Co(NO₃)₂Or Mn (NO)₃)₂The alkali metal or alkaline earth metal sulfate is K₂SO₄、Na₂SO₄、CoSO₄Or MnSO₄。

4. The quasi-solid ionic thermoelectric material of claim 1, wherein the oxidation/reduction couple is potassium ferricyanide/potassium ferrocyanide.

5. The quasi-solid ionic thermoelectric material of claim 1, wherein the water is deionized or distilled water.

6. The quasi-solid ionic thermoelectric material according to any one of claims 1 to 5, wherein the gel matrix material is present in an amount ranging from 0.01 to 1g/ml, the alkali or alkaline earth metal salt additive is present in an amount ranging from 0.001 to 5mol/L, and the oxidation/reduction couple is present in an amount ranging from 0.001/0.001 to 0.8/0.8mol/L, based on the volume of the quasi-solid ionic thermoelectric material; preferably, the content of the gel matrix material is in the range of 0.1-0.5g/ml, the content of the alkali metal or alkaline earth metal salt additive is in the range of 0.1-3mol/L, and the content of the oxidation/reduction couple is in the range of 0.1/0.1-0.5/0.5mol/L, based on the volume of the quasi-solid ionic thermoelectric material.

7. An ionic thermoelectric conversion device comprising electrode materials and a quasi-solid ionic thermoelectric material according to any one of claims 1 to 6, wherein the quasi-solid ionic thermoelectric material is located between and in contact with the electrode materials; preferably, the electrode material is a copper foil, an aluminum foil or a carbon foil electrode sheet.

8. The ionic thermoelectric conversion device according to claim 7, wherein the ionic thermoelectric conversion device is encapsulated with a polyethylene film, a polypropylene film, or an aluminum plastic film.

9. A thermoelectric power generation device characterized by comprising one or more ionic thermoelectric conversion devices according to claim 7 or 8.

10. A wearable apparatus, characterized in that the wearable apparatus comprises the thermoelectric generation device according to claim 9.

Technical Field

The invention 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

With the rapid development of the internet of things technology and the demand for building smart cities based on the demands of China, more and more sensors or electronic devices are applied to the internet of things system and play more and more important roles. Self-supporting energy technology, in which a large number of distributed sensors or electronic devices capture energy from the surrounding environment for continuous power supply, is a key technology and a hot spot of research in order to effectively ensure that the sensors or electronic devices can continuously operate autonomously and independently. The thermoelectric conversion material and the thermoelectric conversion device can realize direct interconversion between heat energy and electric energy, have the advantages of easy miniaturization and flexibility, no noise and emission, safety, reliability and the like, and are very suitable for small sensors or electronic equipment applied in an Internet of things system.

A thermoelectric conversion device based on an electron transfer type semiconductor thermoelectric conversion material is a typical representative of the conversion of thermal energy into electrical energy, which converts thermal energy into electrical energy by the directional transfer of electrons in the presence of a temperature difference using the Seebeck (Seebeck) effect. At present, the adopted and researched thermoelectric conversion material captures energy at room temperature, and the output power of mW magnitude can be supplied for the sensor in the Internet of things to work, but the thermoelectric potential value is difficult to break through +/-200 muV/K due to the influence of the electro-acoustic transport behavior of a semiconductor. This means that if a voltage of between 1 and 3V is to be achieved for proper operation of the sensor, thousands of pairs of n/p thermoelectric pairs need to be connected in series^[1]Greatly increasing the complexity and integration of the device, or increasing the voltage by an external boost chip^[2]The result is an increase in power consumption and increased cost.

Thermoelectric conversion materials based on ion transport have unique advantages in achieving the conversion of low grade waste heat energy to electrical energy. The ionic thermoelectric converterChanging materials^[3]The oxidation/reduction couple in the electrolyte is utilized to continuously convert the environmental heat energy into the electric energy under the temperature gradient formed by the temperature difference without releasing toxic and harmful gases, and the generated thermoelectric potential is in mV/K magnitude. Therefore, compared with the expensive raw materials of the electron migration type semiconductor thermoelectric conversion device and the thermoelectric potential of the mu V/K magnitude, the ionic thermoelectric conversion material has more advantages, and is expected to replace the traditional solid semiconductor thermoelectric device in the temperature range below 100 ℃ to obtain wider application space.

The currently researched liquid ionic thermoelectric material utilizes an oxidation/reduction couple, and the thermoelectric potential obtained by adopting a thermo-electrochemical (thermochemical) effect is only a few mV/K, and meanwhile, a series of problems also exist, such as (1) a liquid leakage problem, which seriously affects the practical application; (2) the convection phenomenon existing in the solution can obstruct the internal heat transfer of the device and is not beneficial to the establishment of temperature difference, and the like^[4-7]. Recently, x.crispin^[8]Group utilized Soret effect in Na-containing⁺The p-type thermoelectric potential of +11mV/K is obtained in ionic polyethylene oxide electrolyte, L.Hu group^[9]Using Soret effect in the presence of Na⁺The p-type thermoelectric potential of +24mV/K is obtained in the cellulose membrane soaked by the polyethylene oxide electrolyte. But currently, there is still a lack of n-type ionic thermoelectric materials that can be matched with their thermoelectric potentials.

Disclosure of Invention

In order to overcome the problems of the liquid ionic thermoelectric material, the invention aims to provide a quasi-solid ionic thermoelectric conversion material, which can obtain high thermoelectric potential through the synergistic effect of double effects of a thermal diffusion (Soret) effect and a thermo-electrochemical (thermo-electrochemical) effect, and provides possibility for application of a thermoelectric conversion device adopting the material in the fields of flexible wearability and internet of things.

Accordingly, in one aspect, the present invention provides a quasi-solid ionic thermoelectric material comprising a gelling matrix material, a water-soluble metal salt, an oxidation/reduction couple, and water, wherein the gelling matrix material, the water-soluble metal salt, and the oxidation/reduction couple are distributed in the water.

The gel matrix material in the quasi-solid ionic thermoelectric material can be any high molecular material which is gelled after being dissolved in water. The gel matrix material is a matrix of a quasi-solid ionic thermoelectric material and is used for carrying an alkali metal or alkaline earth metal salt additive and an oxidation/reduction couple. In a particular embodiment of the invention, 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-state ionic thermoelectric material dissociates into metal cations and counter anions in the quasi-solid-state ionic thermoelectric material, and plays a role of Soret effect in the quasi-solid-state ionic thermoelectric material. In a particular embodiment of the invention, the water-soluble metal salt is an alkali metal or alkaline earth metal salt. In a preferred embodiment of the invention, the alkali or alkaline earth metal salt is an alkali or alkaline earth metal halide, or an alkali or alkaline earth metal nitrate, or an alkali or alkaline earth metal sulphate. In a more preferred embodiment of the invention, the alkali or alkaline earth metal halide is KCl, KBr, KI, NaCl, MgCl₂、CaCl₂、SrCl₂、BaCl₂The alkali metal or alkaline earth metal nitrate is KNO₃、NaNO₃、LiNO₃、Mg(NO₃)₂、Cu(NO₃)₂、Co(NO₃)₂Or Mn (NO)₃)₂The alkali metal or alkaline earth metal sulfate is K₂SO₄、Na₂SO₄、CoSO₄Or MnSO₄。

The oxidation/reduction couple in the quasi-solid state ionic thermoelectric material acts as a thermo-electrochemical (thermo-electrokinetic) effect in the quasi-solid state ionic thermoelectric material. In a particular embodiment of the invention, the oxidizing/reducing couple is potassium ferricyanide/potassium ferrocyanide.

In a specific embodiment of the present invention, the water in the quasi-solid state ionic thermoelectric material is deionized water or distilled water.

In a particular embodiment of the invention, the gel matrix material is present in a range of 0.01-1g/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, based on the volume of the quasi-solid ionic thermoelectric material; the content of the alkali metal or alkaline earth metal salt additive is in the range of 0.001-5mol/L, for example 0.005, 0.01, 0.05, 0.1, 0.5, 1, 2, 3, 4 or 5 mol/L; the amount of the redox couple is in the range of 0.001/0.001-0.8/0.8mol/L, and the ratio of the redox couple may be equal or unequal, preferably unequal, for example 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 0.8/0.8 mol/L. In a preferred embodiment of the present invention, the content of the gel matrix material is in the range of 0.1 to 0.5g/ml, the content of the alkali metal or alkaline earth metal salt additive is in the range of 0.1 to 3mol/L, and the content of the oxidation/reduction couple is in the range of 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 appropriate amounts of the cementitious matrix material, alkali or alkaline earth metal salt additive, and oxidation/reduction couple to appropriate amounts of water (e.g., deionized water) such that the cementitious matrix material, alkali or alkaline earth metal salt additive, and oxidation/reduction couple are each present in the resulting mixture in the indicated ranges of amounts;

(2) stirring the obtained mixture at the temperature of between room temperature and 95 ℃ for 0.5 to 24 hours at the stirring speed of 400-500rpm 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 invention can be measured to be 0 to-20 mV/K.

In a second aspect, the present invention provides an ionic thermoelectric conversion device comprising electrode materials and the quasi-solid ionic thermoelectric material of the first aspect of the invention, wherein the quasi-solid ionic thermoelectric material is located between and in contact with the electrode materials. In a specific embodiment of the invention, the electrode material is a copper foil, an aluminum foil or a carbon foil electrode sheet. In a specific embodiment of the present invention, the ionic thermoelectric conversion device may be encapsulated with a polyethylene film, a polypropylene film, or an aluminum plastic film. In a specific embodiment of the present invention, the ionic thermoelectric conversion device may be in the form of a thermoelectric chemical unit.

The ionic thermoelectric conversion device of the present invention can be produced by the following method: and coating the prepared quasi-solid ionic thermoelectric material on one electrode plate in the 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 invention provides a thermoelectric generation device comprising the ionic thermoelectric conversion device of the second aspect of the present invention. The thermoelectric generation device may include one or more ionic thermoelectric conversion devices of the second aspect of the present invention, for example, 1 to 100 ionic thermoelectric conversion devices, which are configured in series, as necessary.

Through determination, the temperature difference power generation device can obtain the voltage of 0 to 3V by utilizing the temperature difference of the human body to recover electric energy.

In a fourth aspect, the present invention provides a wearable device comprising the thermoelectric generation device of the third aspect of the present invention and a wearable substrate connected in parallel therewith. The wearing substrate may be, for example, gloves, hats, tops, undergarments, pants, shoes, socks, bracelets, earrings, necklaces, and the like.

The invention has the beneficial effects that:

1. the quasi-solid ionic thermoelectric material can obtain high thermoelectric force from the surrounding environment through the double-effect synergistic effect of the thermal diffusion (Soret) effect and the thermo-electrochemical (thermochemical) effect, is 2 orders of magnitude higher than that of the traditional semiconductor thermoelectric material, has strong operability, is free of noise and emission, and is environment-friendly.

2. The raw materials of the quasi-solid ionic thermoelectric material provided by the invention, namely the gelled matrix material, the alkali metal or alkaline earth metal salt additive and the oxidation/reduction couple, are easy to obtain, the cost is low, the quasi-solid ionic thermoelectric material can be prepared by adjusting the type and concentration of the matrix material and the additive and the concentration of the oxidation/reduction couple and using a stirring and mixing method, and the quasi-solid ionic thermoelectric material is simple and convenient.

3. The quasi-solid ionic thermoelectric material has no leakage problem due to the quasi-solid gelled material, greatly reduces the convection phenomenon of the internal solution and is beneficial to establishing temperature difference.

4. The quasi-solid ionic thermoelectric material can be conveniently coated on electrode sheets such as copper foil, aluminum foil, carbon foil and the like to form a sandwich structure, and then packaged to assemble an ionic thermoelectric conversion device.

5. The quasi-solid-state ionic thermoelectric material is a flexible gel material, and is very suitable for preparing flexible ionic thermoelectric conversion devices, flexible thermoelectric power generation devices and flexible wearable equipment.

6. The ionic thermoelectric conversion device can be used for manufacturing a thermoelectric generation device, 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 theoretical schematic diagram of the high thermoelectric potential obtained by the double effects of thermal diffusion (Soret) effect and thermo-electrochemical (thermogalvanic) effect in the quasi-solid ionic thermoelectric material of the present invention;

FIG. 2 is a diagram of a representative flexible representation of an ionic thermoelectric conversion device of the present invention comprising a quasi-solid ionic thermoelectric material of the present invention and an electrode sheet;

fig. 3 is a schematic view of an open circuit voltage of an ionic thermoelectric conversion device for generating electricity using a temperature difference according to an embodiment of the present invention;

fig. 4 is a schematic view showing an open circuit voltage of a wearable device for generating electricity by using a human body temperature difference, the wearable device being made by arranging a temperature difference generating device of the present invention, which is constituted by integrating a plurality of ionic type thermoelectric conversion devices of the present invention, on a glove.

Detailed Description

The present invention will be described in further detail below with reference to specific embodiments and accompanying drawings.

As shown in FIG. 1, the quasi-solid ionic thermoelectric material of the present invention is prepared by thermal diffusion ofSoret) effect and thermo-electrochemical (thermogalvanic) effect achieve high thermoelectric potentials from the surrounding environment. Specifically, a quasi-solid ionic thermoelectric material comprising a gelled matrix material, anions and cations (formed from soluble metal salts) and an oxidation/reduction couple (e.g., potassium ferricyanide/potassium ferrocyanide) is sandwiched between electrode sheets to make an ionic thermoelectric conversion device, one electrode sheet of which is at a hot side at a higher temperature and the other electrode sheet at a cold side at a lower temperature. As shown in the left panel of fig. 1, in the quasi-solid ionic thermoelectric material of the present invention, cations are mainly bound by a gel matrix material with anions, and the anions migrate to the cold-end electrode plate in the presence of a temperature field and are aggregated to form an electric double layer structure, so that a thermal potential is formed between the two electrode plates, which is the Soret effect. As shown in the middle panel of FIG. 1, due to the presence of the oxidation/reduction couple in the quasi-solid ionic thermoelectric material of the present invention, the oxidation reaction Fe (CN) occurs at the hot end₆ ^4--e→Fe(CN)₆ ^3-The released electrons are gathered at the hot end electrode plate and are connected with the cold end through an external circuit, and the electrons return to the cold end and undergo reduction reaction Fe (CN) near the cold end electrode plate₆ ^3-+e→Fe(CN)₆ ^4-The oxidation products and reduction products are returned to the counter electrode by convective diffusion. A thermoelectric potential is thus formed between the two electrode pads, which is a thermo-electrochemical (thermo-electrochemical) effect. As shown in the right panel of fig. 1, the quasi-solid ionic thermoelectric material of the present invention can generate a high thermoelectric potential between two electrode sheets through the synergistic effect of Soret effect and thermo-electrochemical (thermoelectrodic) effect.

The quasi-solid-state ionic thermoelectric material can be used for manufacturing ionic thermoelectric conversion devices. Because the quasi-solid-state ionic thermoelectric material takes the flexible gel matrix material as the matrix, the flexible electrode plate and the quasi-solid-state ionic thermoelectric material can be used for manufacturing a very flexible ionic thermoelectric conversion device. Fig. 2 shows a representative flexible representation of an ionic thermoelectric conversion device comprising a quasi-solid ionic thermoelectric material of the present invention and a flexible electrode sheet. The exemplary ionic thermoelectric conversion device shown in fig. 2 was made approximately 4cm in length and was very flexible and could be rolled over a finger. The potential application prospect of the quasi-solid-state ionic thermoelectric material and the ionic thermoelectric conversion device in the wearable field and the Internet of things field is shown. The ionic 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 invention is further illustrated by the following non-limiting specific examples.

Example 1

1g of polyvinyl alcohol (final concentration 0.1g/ml), 0.3728g of potassium chloride (final concentration 0.5mol/L), 0.1975g of potassium ferricyanide (final concentration 0.06mol/L) and 0.4224g of potassium ferrocyanide (final concentration 0.1mol/L) were weighed out and added to approximately 5ml of deionized water. The mixture was magnetically stirred at a temperature of 60 ℃ for 5 hours at a stirring speed of 500rpm, allowing the mixture to mix well. And then adding deionized water to a constant volume of 10ml, continuing to uniformly stir until gelation occurs, and cooling to obtain the quasi-solid ionic thermoelectric material of the embodiment.

The prepared gel-state ionic thermoelectric material is coated on a copper foil electrode sheet with the square of 1.5cm multiplied by 1.5cm, and the thickness of the coating is about 2 mm. 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 to assemble the ionic thermoelectric conversion device.

As shown in fig. 3, the open-circuit voltage of the ionic thermoelectric conversion device of the present embodiment corresponds to the temperature difference, the slope after linear fitting corresponds to the thermoelectric voltage value, and the obtained thermoelectric voltage value is-1.6 mV/K.

Example 2

4g of chitosan (final concentration 0.4g/ml), 0.07455g of potassium chloride (final concentration 0.1mol/L), 0.3292g of potassium ferricyanide (final concentration 0.1mol/L) and 0.8448g of potassium ferrocyanide (final concentration 0.2mol/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, allowing the mixture to mix well. And then adding deionized water to a constant volume of 10ml, continuing to uniformly stir until gelation occurs, and cooling to obtain the quasi-solid ionic thermoelectric material of the embodiment.

The prepared gel-state ionic thermoelectric material is coated on a copper foil electrode sheet with the square of 1.5cm multiplied by 1.5cm, and the thickness of the coating is about 2 mm. 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 to assemble the ionic thermoelectric conversion device.

As shown in fig. 3, the open-circuit voltage of the ionic thermoelectric conversion device of the present embodiment corresponds to the temperature difference, the slope after linear fitting corresponds to the thermoelectric voltage value, and the obtained thermoelectric voltage value is-3.0 mV/K.

Example 3

2g polyacrylic acid (final concentration 0.2g/ml), 0.1491g potassium chloride (final concentration 0.2mol/L), 0.6585g potassium ferricyanide (final concentration 0.2mol/L) and 1.2673g potassium ferrocyanide (final concentration 0.3mol/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, allowing the mixture to mix well. And then adding deionized water to a constant volume of 10ml, continuing to uniformly stir until gelation occurs, and cooling to obtain the quasi-solid ionic thermoelectric material of the embodiment.

The prepared gel-state ionic thermoelectric material is coated on a copper foil electrode sheet with the square of 1.5cm multiplied by 1.5cm, and the thickness of the coating is about 2 mm. 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 to assemble the ionic thermoelectric conversion device.

As shown in fig. 3, the open-circuit voltage of the ionic thermoelectric conversion device of the present embodiment corresponds to the temperature difference, the slope after linear fitting corresponds to the thermoelectric voltage value, and the obtained thermoelectric voltage value is-2.2 mV/K.

Example 4

1g of acrylamide (final concentration 0.1g/ml), 0.5964g of potassium chloride (final concentration 0.8mol/L), 0.3292g of potassium ferricyanide (final concentration 0.1mol/L) and 0.4224g of potassium ferrocyanide (final concentration 0.1mol/L) were weighed and added to approximately 5ml of deionized water. The mixture was magnetically stirred at a temperature of 60 ℃ for 5 hours at a stirring speed of 500rpm, allowing the mixture to mix well. And then adding deionized water to a constant volume of 10ml, continuing to uniformly stir until gelation occurs, and cooling to obtain the quasi-solid ionic thermoelectric material of the embodiment.

The prepared gel-state ionic thermoelectric material is coated on a 1.5cm multiplied by 1.5cm square aluminum foil electrode plate, and the coating thickness is about 2 mm. 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 to assemble the ionic thermoelectric conversion device.

As shown in fig. 3, the open-circuit voltage of the ionic thermoelectric conversion device of the present embodiment corresponds to the temperature difference, the slope after linear fitting corresponds to the thermoelectric voltage value, and the obtained thermoelectric voltage value is-4.0 mV/K.

Example 5

0.1g of gelatin (final concentration 0.01g/ml), 0.0007g of potassium chloride (final concentration 0.001mol/L), 0.0033g of potassium ferricyanide (final concentration 0.001mol/L) and 0.0084g of potassium ferrocyanide (final concentration 0.002mol/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, allowing the mixture to mix well. And then adding deionized water to a constant volume of 10ml, continuing to uniformly stir until gelation occurs, and cooling to obtain the quasi-solid ionic thermoelectric material of the embodiment.

The prepared gel-state ionic thermoelectric material is coated on a 1.5cm multiplied by 1.5cm square aluminum foil electrode plate, and the coating thickness is about 2 mm. 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 to assemble the ionic thermoelectric conversion device.

As shown in fig. 3, the open-circuit voltage of the ionic thermoelectric conversion device of the present embodiment corresponds to the temperature difference, the slope after linear fitting corresponds to the thermoelectric voltage value, and the obtained thermoelectric voltage value is-5.4 mV/K.

Example 6

0.5g of gelatin (final concentration 0.05g/ml), 0.0074g of potassium chloride (final concentration 0.01mol/L), 0.0329g of potassium ferricyanide (final concentration 0.01mol/L) and 0.0845g of potassium ferrocyanide (final concentration 0.02mol/L) were weighed and added to approximately 5ml of deionized water. The mixture was magnetically stirred at a temperature of 60 ℃ for 5 hours at a stirring speed of 500rpm, allowing the mixture to mix well. And then adding deionized water to a constant volume of 10ml, continuing to uniformly stir until gelation occurs, and cooling to obtain the quasi-solid ionic thermoelectric material of the embodiment.

The prepared gel-state ionic thermoelectric material is coated on a 1.5cm multiplied by 1.5cm square aluminum foil electrode plate, and the coating thickness is about 2 mm. 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 to assemble the ionic thermoelectric conversion device.

As shown in fig. 3, the open-circuit voltage of the ionic thermoelectric conversion device of the present embodiment corresponds to the temperature difference, the slope after linear fitting corresponds to the thermoelectric voltage value, and the obtained thermoelectric voltage value is-6.7 mV/K.

Example 7

1g of gelatin (final concentration 0.1g/ml), 0.0746g of potassium chloride (final concentration 0.1mol/L), 2.6339g of potassium ferricyanide (final concentration 0.8mol/L) and 3.3794g of potassium ferrocyanide (final concentration 0.8mol/L) were weighed and added to approximately 5ml of deionized water. The mixture was magnetically stirred at a temperature of 60 ℃ for 5 hours at a stirring speed of 500rpm, allowing the mixture to mix well. And then adding deionized water to a constant volume of 10ml, continuing to uniformly stir until gelation occurs, and cooling to obtain the quasi-solid ionic thermoelectric material of the embodiment.

The prepared gel-state ionic thermoelectric material is coated on a carbon foil electrode sheet with the square of 1.5cm multiplied by 1.5cm, and the thickness of the coating is about 2 mm. 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 to assemble the ionic thermoelectric conversion device.

As shown in fig. 3, the open-circuit voltage of the ionic thermoelectric conversion device of the present embodiment corresponds to the temperature difference, the slope after linear fitting corresponds to the thermoelectric voltage value, and the obtained thermoelectric voltage value is-4.8 mV/K.

Example 8

3g of gelatin (final concentration 0.3g/ml), 0.8946g of potassium chloride (final concentration 1.2mol/L), 0.7902g of potassium ferricyanide (final concentration 0.25mol/L) and 1.7742g of potassium ferrocyanide (final concentration 0.42mol/L) were weighed and added to approximately 5ml of deionized water. The mixture was magnetically stirred at a temperature of 60 ℃ for 5 hours at a stirring speed of 500rpm, allowing the mixture to mix well. And then adding deionized water to a constant volume of 10ml, continuing to uniformly stir until gelation occurs, and cooling to obtain the quasi-solid ionic thermoelectric material of the embodiment.

The prepared gel-state ionic thermoelectric material is coated on a carbon foil electrode sheet with the square of 1.5cm multiplied by 1.5cm, and the thickness of the coating is about 2 mm. 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 to assemble the ionic thermoelectric conversion device.

As shown in fig. 3, the open-circuit voltage of the ionic thermoelectric conversion device of the present embodiment corresponds to the temperature difference, the slope after linear fitting corresponds to the thermoelectric voltage value, and the obtained thermoelectric voltage value is-17.0 mV/K.

Example 9

10g of gelatin (final concentration 1g/ml), 3.7275g of potassium chloride (final concentration 5mol/L), 0.1975g of potassium ferricyanide (final concentration 0.06mol/L) and 0.4224g of potassium ferrocyanide (final concentration 0.1mol/L) were weighed out and added to approximately 5ml of deionized water. The mixture was magnetically stirred at a temperature of 60 ℃ for 5 hours at a stirring speed of 500rpm, allowing the mixture to mix well. And then adding deionized water to a constant volume of 10ml, continuing to uniformly stir until gelation occurs, and cooling to obtain the quasi-solid ionic thermoelectric material of the embodiment.

The prepared gel-state ionic thermoelectric material is coated on a carbon foil electrode sheet with the square of 1.5cm multiplied by 1.5cm, and the thickness of the coating is about 2 mm. 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 to assemble the ionic thermoelectric conversion device.

As shown in fig. 3, the open-circuit voltage of the ionic thermoelectric conversion device of the present embodiment corresponds to the temperature difference, the slope after linear fitting corresponds to the thermoelectric voltage value, and the obtained thermoelectric voltage value is-9.5 mV/K.

Application example

The ionic thermoelectric conversion devices of examples 1 to 9 above had thermoelectric values between-1.6 and-17.0 mV/K, whereas the thermoelectric values of conventional semiconductor thermoelectric conversion materials hardly broke through + -0.2 mV/K, as described in the "background" section above. Therefore, the ionic thermoelectric conversion device can obtain high thermoelectric potential from the surrounding environment, is 2 orders of magnitude higher than that of the traditional semiconductor thermoelectric material, and can be compared with the shoulder X.Crispin group^[8]And L.Hu group^[9]The obtained p-type thermoelectric force shows good application prospect in thermoelectric power generation.

This application example produced a thermoelectric power generation device and a wearable device using the thermoelectric chemical cell produced in example 8. As shown in fig. 4, 25 thermoelectric conversion units produced according to example 8 were connected in series in this order using a conductive copper tape to produce a thermoelectric power generation device. The thermoelectric power generation device is tightly stuck on the corresponding part of the back of the hand by using a transparent adhesive tape, so that the flexible wearable thermoelectric power generation equipment is manufactured.

Fig. 4 also shows a schematic diagram of an open circuit voltage generated by the manufactured wearable device by utilizing the human body temperature difference. As shown in the figure, after the flexible wearable thermoelectric power generation device is worn on the hand, the temperature (T) of one side, close to the skin of the hand, of the thermoelectric power generation device is heated due to the skin temperature of the hand_Skin(s)) Will be higher than the temperature (T) of the side of the thermoelectric generation device close to the ambient air_{Environment(s)}) Thereby forming a temperature difference on both sides of the thermoelectric power generating device, and generating a voltage by a Soret effect and a thermo-chemical (thermo-electrochemical) effect of the quasi-solid ionic type thermoelectric material in the thermoelectric power generating device. The voltage gradually increasing with timeThe increase, Δ V, reached 2.15V at 16 minutes. That is, in the present application example, only 25 thermoelectric conversion units constitute the thermoelectric power generation device, and the thermoelectric voltage of 2.15V can be realized.

This means that, with the thermoelectric conversion device based on the quasi-solid-state ionic thermoelectric material of the present invention, only dozens, at most dozens of such thermoelectric conversion devices are required to meet the requirement of the operating voltage between 1 and 3V of the usual sensor, and the complexity and integration of the device can be reduced. In contrast, as described in the "background" section above, with thermoelectric conversion devices based on electromigration-type semiconductor thermoelectric conversion materials, thousands of pairs of n/p thermoelectric pairs would need to be connected in series to achieve operating voltages between 1 and 3V, greatly increasing the complexity and integration of the devices. Therefore, the thermoelectric conversion device, the thermoelectric generation device and the wearable equipment manufactured by the quasi-solid-state ionic thermoelectric material have wide application prospects in the technical field of Internet of things and the technical field of wearable equipment.

Reference documents:

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[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).

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[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 present invention has been described above using specific examples, which are only for the purpose of facilitating understanding of the present invention, and are not intended to limit the present invention. Numerous simple deductions, modifications or substitutions may be made by those skilled in the art in light of the teachings of the present invention. Such deductions, modifications or alternatives also fall within the scope of the claims of the present invention.