CN113984235A - Flexible stretchable thermocouple based on ionic thermoelectric hydrogel and preparation method thereof - Google Patents
Flexible stretchable thermocouple based on ionic thermoelectric hydrogel and preparation method thereof Download PDFInfo
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Images
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
- G01K7/00—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements
- G01K7/02—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements using thermoelectric elements, e.g. thermocouples
Abstract
The invention provides a flexible and stretchable thermocouple based on ionic thermoelectric hydrogel and a preparation method thereof, which have excellent thermoelectric conversion characteristics and shape variability and can accurately measure temperature when deformation occurs. The flexible stretchable thermocouple includes: the n-type ionic thermoelectric hydrogel film is an elastic hydrogel which has stretchability and contains a redox couple electrolyte with a negative seebeck coefficient; the p-type ion thermoelectric hydrogel film is arranged in parallel with the n-type ion thermoelectric hydrogel film, is stretchable and comprises an elastic hydrogel with a redox couple electrolyte with a positive seebeck coefficient; the flexible temperature measuring electrode is connected with one end of the n-type ion thermoelectric hydrogel film and one end of the p-type ion thermoelectric hydrogel film to form a temperature measuring end; and the flexible reference electrode is used for connecting the other end of the n-type ion thermoelectric hydrogel film and the other end of the p-type ion thermoelectric hydrogel film with the cathode and the anode of an external measuring element respectively to form a reference end.
Description
Technical Field
The invention belongs to the technical field of thermocouple temperature measurement, and particularly relates to a flexible stretchable thermocouple based on ionic thermoelectric hydrogel and a preparation method thereof.
Background
With the coming of the internet of things, information of any article and life can be input into a network through an intelligent sensor, and the interconnection of everything is realized. Temperature, as an important measure of vital signs and the state of the article, needs to be monitored and collected in real time. The traditional thermocouple is used as a contact temperature measuring device, and the principle of the traditional thermocouple is that a thermoelectric effect of a conductor or a semiconductor is utilized to convert a temperature difference signal into an electric signal, so that the monitoring and the recording of temperature information are realized. However, most conventional thermocouples are made of metal, generally have no flexibility and stretchability, and are limited in temperature measurement by their shapes and structures. Although the conductive polymer materials such as polypyrrole and polyaniline have good flexibility and stretchability and can be designed into a resistance-type temperature sensor, the deformation can change the resistance of the material, thereby affecting the accuracy of temperature measurement.
Therefore, a temperature measuring device with excellent temperature measuring characteristics and good deformation capability does not exist at present, and the development of the flexible and stretchable thermocouple technology has great practical application significance.
Disclosure of Invention
The present invention has been made to solve the above problems, and an object of the present invention is to provide a flexible and stretchable thermocouple based on an ionic thermoelectric hydrogel, which has not only excellent thermoelectric conversion characteristics but also flexibility and stretchability, and can accurately measure temperature even if it is deformed, and a method for manufacturing the same.
In order to achieve the purpose, the invention adopts the following scheme:
< thermocouple >
The present invention provides a flexible and stretchable thermocouple based on an ionic thermoelectric hydrogel, characterized in that it comprises: the n-type ionic thermoelectric hydrogel film is an elastic hydrogel which has stretchability and contains a redox couple electrolyte with a negative seebeck coefficient; the p-type ion thermoelectric hydrogel film is arranged in parallel with the n-type ion thermoelectric hydrogel film, is stretchable and comprises an elastic hydrogel with a redox couple electrolyte with a positive seebeck coefficient; the flexible temperature measuring electrode is connected with one end of the n-type ion thermoelectric hydrogel film and one end of the p-type ion thermoelectric hydrogel film to form a temperature measuring end; and the flexible reference electrode is used for connecting the other end of the n-type ion thermoelectric hydrogel film and the other end of the p-type ion thermoelectric hydrogel film with the cathode and the anode of an external measuring element respectively to form a reference end.
Preferably, the method for preparing the flexible and stretchable thermocouple based on the ionic thermoelectric hydrogel provided by the invention further comprises the following steps: the surface of the flexible packaging substrate is fixedly adhered with an n-type ion thermoelectric hydrogel film, a p-type ion thermoelectric hydrogel film, a flexible temperature measuring electrode and a flexible reference electrode, and the bottom surface of the flexible packaging substrate can be adhered with the surface of an object to be measured.
Preferably, the method for preparing the flexible and stretchable thermocouple based on the ionic thermoelectric hydrogel provided by the invention further comprises the following steps: and the flexible protective layer is tightly attached to the flexible packaging substrate to form a sandwich structure, and is used for packaging and protecting the n-type ion thermoelectric hydrogel film, the p-type ion thermoelectric hydrogel film, the flexible temperature measuring electrode and the flexible reference electrode.
Preferably, the method for preparing the flexible and stretchable thermocouple based on the ionic thermoelectric hydrogel provided by the invention can also have the following characteristics: the elastic hydrogel is polyacrylamide hydrogel, polyacrylamide/chitosan double-network hydrogel, polyvinyl alcohol hydrogel and other hydrogels with excellent stretchability.
Preferably, the method for preparing the flexible and stretchable thermocouple based on the ionic thermoelectric hydrogel provided by the invention can also have the following characteristics: wherein, the p-type ion thermoelectric hydrogel film and the n-type ion thermoelectric hydrogel film are both strip-shaped.
Preferably, the method for preparing the flexible and stretchable thermocouple based on the ionic thermoelectric hydrogel provided by the invention can also have the following characteristics: the n-type ion thermoelectric hydrogel film and the p-type ion thermoelectric hydrogel film are obtained by soaking the elastic hydrogel in corresponding electrolyte aqueous solution containing n-type redox couple ions and p-type redox couple ions. For example, a redox couple with a negative seebeck coefficient may be K4Fe(CN)6/K3Fe(CN)6The redox couple having a positive seebeck coefficient may be FeCl3/FeCl2Or KI/KI3。
Preferably, the method for preparing the flexible and stretchable thermocouple based on the ionic thermoelectric hydrogel provided by the invention can also have the following characteristics: the redox couple electrolyte comprises an oxidation state component, a reduction state component and high-solubility inorganic salt, and the internal resistance of the hydrogel is reduced by increasing the ion concentration in the hydrogel through the high-solubility inorganic salt.
Preferably, the method for preparing the flexible and stretchable thermocouple based on the ionic thermoelectric hydrogel provided by the invention can also have the following characteristics: the high-solubility inorganic salt may be sodium chloride, lithium chloride, potassium chloride, or the like.
Preferably, the method for preparing the flexible and stretchable thermocouple based on the ionic thermoelectric hydrogel provided by the invention can also have the following characteristics: the molar concentration of the oxidized component and the reduced component in the redox couple electrolyte are the same.
Preferably, the method for preparing the flexible and stretchable thermocouple based on the ionic thermoelectric hydrogel provided by the invention can also have the following characteristics: the concentration of the oxidized component and the reduced component is 0.2 mol/L.
Preferably, the method for preparing the flexible and stretchable thermocouple based on the ionic thermoelectric hydrogel provided by the invention can also have the following characteristics: the flexible electrode is a graphite, carbon tube flexible composite material electrode or flexible conductive polymer and the like.
Preferably, the method for preparing the flexible and stretchable thermocouple based on the ionic thermoelectric hydrogel provided by the invention can also have the following characteristics: the flexible packaging substrate and the flexible protective layer are elastomers with excellent tensile properties, such as Ecoflex, polydimethylsiloxane, polyurethane, natural rubber and the like.
< preparation method >
Further, the present invention also provides a method for preparing the < thermocouple >.
Specifically, the preparation method of the flexible and stretchable thermocouple based on the ionic thermoelectric hydrogel provided by the invention comprises the following steps: in-situ synthesizing two strip-shaped elastic hydrogels which are parallel to each other in the length direction on the Ecoflex film; respectively soaking or dripping the two elastic hydrogels into an electrolyte aqueous solution containing n-type redox couple ions and p-type redox couple ions to obtain an n-type ion thermoelectric hydrogel film and a p-type ion thermoelectric hydrogel film; connecting one end of the n-type ion thermoelectric hydrogel film and one end of the p-type ion thermoelectric hydrogel film by using a flexible temperature measuring electrode to form a temperature measuring end; and connecting the other end of the n-type ion thermoelectric hydrogel film and the other end of the p-type ion thermoelectric hydrogel film with the cathode and the anode of an external measuring element respectively by adopting a flexible reference electrode to form a reference end.
Action and Effect of the invention
(1) The invention provides a stretchable thermocouple design based on the ionic thermoelectric hydrogel for the first time, the thermocouple has good flexibility and stretchability, stronger deformation capacity, no influence on the accuracy of temperature measurement due to deformation, and very high temperature measurement precision;
(2) compared with the traditional thermocouple, the thermocouple has higher flexibility, can adapt to different working environments to a certain extent, and meets the deformation requirement of equipment, the thermocouple disclosed by the invention converts a thermal signal into an electric signal, the generated voltage is only related to temperature but not to resistance (the thermal signal is converted into the electric signal by utilizing the temperature dependence of an oxidation-reduction reaction), the Seebeck coefficient of the thermocouple reaches mV/K level and is three orders of magnitude higher than that of the traditional thermoelectric material;
(3) the invention has strong universality, is film-shaped, can be attached to the surfaces of most objects, can be attached to and contacted with various surfaces with different shapes or with the shapes which can change, and is used for accurately measuring the temperature;
(4) the temperature measuring device is simple in structure, can be designed into any shape and size according to actual requirements, is convenient to integrate, can measure the temperature of a single point, can be integrated into an array to measure the temperature of one area, and can obtain a temperature cloud picture by matching with an external circuit;
(5) the invention has the advantages of low manufacturing cost, wide raw material source and low price, and has the potential of being applied to large-scale industrial production.
Drawings
FIG. 1 is a schematic diagram of the temperature measurement of a flexible and stretchable thermocouple based on an ionic thermoelectric hydrogel according to the present invention;
FIG. 2 is a schematic structural view of an ionic thermoelectric hydrogel based flexible and stretchable thermocouple according to an embodiment of the present invention;
FIG. 3 is a graph showing Seebeck coefficient test results for P-type and N-type ionothermal hydrogels for flexible and stretchable thermocouples based on ionothermal hydrogels according to embodiments of the present invention;
FIG. 4 is a graph showing the results of tensile property tests of flexible and stretchable thermocouples based on ionic thermoelectric hydrogels according to embodiments of the present invention;
FIG. 5 is a graph showing the temperature measurement effect of a flexible and stretchable thermocouple based on an ionic thermoelectric hydrogel according to an embodiment of the present invention under periodic stretching with an appropriate strength.
Detailed Description
The following detailed description of specific embodiments of the invention refers to the accompanying drawings.
< example >
As shown in fig. 2, the flexible stretchable thermocouple 10 based on the ionic thermoelectric hydrogel provided in the present embodiment includes a galvanic couple unit 20 and an encapsulation unit 30.
The galvanic couple unit 20 comprises an n-type ion thermoelectric hydrogel film 21, a p-type ion thermoelectric hydrogel film 22, a flexible temperature measuring electrode 23 and a flexible reference electrode 24.
The n-type ion thermoelectric hydrogel film 21 is a stretchable elastic hydrogel containing a redox pair electrolyte having a negative seebeck coefficient, and in the present embodiment, the n-type ion thermoelectric hydrogel film 21 is a strip shape, having a length of 7cm, a width of 2mm, and a thickness of 80 μm.
The p-type ion thermoelectric hydrogel film 22 and the n-type ion thermoelectric hydrogel film 21 are arranged in parallel, are stretchable, and comprise elastic hydrogel with redox pair electrolyte having a positive seebeck coefficient, in the embodiment, the p-type ion thermoelectric hydrogel film 22 and the n-type ion thermoelectric hydrogel film 21 have the same shape and size, and the distance between the p-type ion thermoelectric hydrogel film and the n-type ion thermoelectric hydrogel film is 2 mm.
And, in the present embodiment,the n-type ion thermoelectric hydrogel and the p-type ion thermoelectric hydrogel respectively contain Fe (CN)6 4-/Fe(CN)6 3-And Fe3+/Fe2+A redox pair ion.
The flexible temperature measuring electrode 23 is connected with one end of the n-type ion thermoelectric hydrogel film 21 and one end of the p-type ion thermoelectric hydrogel film 22 to form a node which is used as a temperature measuring end. In this embodiment, the flexible temperature measuring electrode 23 is made of a graphite conductive paste.
The flexible reference electrode 24 is used for connecting the other end of the n-type ion thermoelectric hydrogel film 21 and the other end of the p-type ion thermoelectric hydrogel film 22 with the cathode and the anode of an external temperature measurement ammeter respectively to form a reference end. In this embodiment, the flexible reference electrode 24 is also made of a graphite conductive paste.
The encapsulation unit 30 includes a flexible encapsulation substrate 31 and a flexible protection layer 32. The flexible package substrate 31 has the galvanic unit 20 fixedly attached to the surface thereof. The flexible protective layer 32 and the flexible packaging substrate 31 are tightly attached to form a sandwich structure, so that the galvanic couple unit 20 is positioned in the sandwich layer to package and protect the galvanic couple unit 20. In this embodiment, an Ecoflex elastic film is used as the flexible package substrate 31 and the flexible protection layer 32.
The flexible and stretchable thermocouple 10 provided in this embodiment is specifically prepared as follows:
1) taking an Ecoflex elastic film with the thickness of 0.5mm, respectively washing the Ecoflex elastic film with methanol and deionized water, and naturally drying the Ecoflex elastic film to be used as a flexible packaging substrate 31;
2) weighing 2g of benzophenone and 18g of ethanol to prepare a 10% benzophenone solution by mass fraction, putting the Ecoflex film cleaned in the step 1) into the prepared benzophenone solution, fully soaking the Ecoflex film for 2 minutes, taking out the Ecoflex film, washing the Ecoflex film with methanol for three times, and naturally drying the Ecoflex film for later use;
3) 1.4216g of monomer acrylamide and 250mg of chitosan are dissolved in 10ml of deionized water, heated at 80 ℃, stirred and mixed uniformly;
4) pouring 128 mu l of 20mg/ml N, N '-methylene bisacrylamide solution and 56.06mg of 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone into the mixed solution obtained in the step 3), uniformly mixing, putting into a vacuum kettle, and vacuumizing for 30 minutes to obtain an elastic hydrogel stock solution;
5) placing two strip-shaped molds on the surface of the Ecoflex film obtained in the step 2) in parallel, pouring the hydrogel stock solution in the step 4) into the two molds, and irradiating the two molds with ultraviolet light for 4 hours in a nitrogen environment to gradually form the hydrogel and adhere the hydrogel to the flexible packaging substrate 31 to form two strip-shaped hydrogel films;
6) 0.7367g of potassium ferrocyanide and 0.6585g of potassium ferricyanide were weighed into 10ml of 4mol/L sodium chloride solution to prepare 0.2mol/L Fe (CN)6 4-/Fe(CN)6 3-And (3) solution. 0.3244g of ferric chloride and 0.2535g of ferrous chloride are weighed and added into 10ml of 4mol/L sodium chloride solution to prepare 0.2mol/L Fe2+/Fe3+A solution;
7) respectively using Fe (CN) prepared in step 6)6 4-/Fe(CN)6 3-Solution and Fe2+/Fe3+Dripping the solution on two hydrogel films adhered to the Ecoflex elastomer, placing the hydrogel films in a closed culture dish for 6 hours to ensure that ions are completely diffused into hydrogel, and obtaining an n-type ion thermoelectric hydrogel film 21 and a p-type ion thermoelectric hydrogel film 22; as shown in FIG. 3, the Seebeck coefficients of the P-type and N-type ionic thermoelectric hydrogels are 2.01mV/K in total;
8) on the basis of the step 7), graphite conductive paste is smeared on the surface of the Ecoflex elastomer, so that one ends of two hydrogels are connected to form a node, and the other end of the two hydrogels are smeared with the conductive paste to facilitate external connection of a lead to prepare a flexible thermocouple layer (a thermocouple unit 20);
9) and (3) taking another piece of Ecoflex elastomer film as a flexible protective layer 32 to cover the thermocouple layer in the step 8), completing encapsulation, and preparing the flexible stretchable thermocouple 10.
And (3) performance testing:
as shown in fig. 4, the tensile properties of the flexible and stretchable thermocouple 10 were tested using a universal tensile tester test, and the maximum stretchable thermocouple 10 was stretched to 4 times its length.
As shown in figure 5, under the condition that the temperature of the thermocouple reference end is 25 ℃, the thermocouple is continuously and periodically stretched while the temperature of the temperature measuring end is kept unchanged at 32 ℃, the change of the measured voltage is extremely small and is within 1mV (corresponding to the temperature change is less than 0.5 ℃), and the temperature measuring effect is basically ignored due to the stretching.
The above embodiments are merely illustrative of the technical solutions of the present invention. The flexible and stretchable thermocouple based on the ionic thermoelectric hydrogel and the method for manufacturing the same according to the present invention are not limited to the description of the above embodiments, but are subject to the scope defined in the claims. Any modification or supplement or equivalent replacement made by a person skilled in the art on the basis of this embodiment is within the scope of the invention as claimed in the claims.
Claims (10)
1. A flexible, stretchable thermocouple based on an ionic thermoelectric hydrogel, comprising:
the n-type ionic thermoelectric hydrogel film is an elastic hydrogel which has stretchability and contains a redox couple electrolyte with a negative seebeck coefficient;
the p-type ionic thermoelectric hydrogel film is arranged in parallel with the n-type ionic thermoelectric hydrogel film, is stretchable and comprises an elastic hydrogel with a redox couple electrolyte with a positive seebeck coefficient;
the flexible temperature measuring electrode is connected with one end of the n-type ion thermoelectric hydrogel film and one end of the p-type ion thermoelectric hydrogel film to form a temperature measuring end; and
and the flexible reference electrode is used for connecting the other end of the n-type ion thermoelectric hydrogel film and the other end of the p-type ion thermoelectric hydrogel film with the cathode and the anode of an external measuring element respectively to form a reference end.
2. The ionic thermoelectric hydrogel-based flexible stretchable thermocouple of claim 1, further comprising:
the surface of the flexible packaging substrate is fixedly adhered with the n-type ion thermoelectric hydrogel film, the p-type ion thermoelectric hydrogel film, the flexible temperature measuring electrode and the flexible reference electrode, and the bottom surface of the flexible packaging substrate can be adhered with the surface of a measured object.
3. The ionic thermoelectric hydrogel-based flexible stretchable thermocouple of claim 2, further comprising:
and the flexible protective layer is tightly attached to the flexible packaging substrate to form a sandwich structure, and is used for packaging and protecting the n-type ionic thermoelectric hydrogel film, the p-type ionic thermoelectric hydrogel film, the flexible temperature measuring electrode and the flexible reference electrode.
4. The ionic thermoelectric hydrogel-based flexible stretchable thermocouple of claim 1, characterized in that:
wherein the elastic hydrogel is any one of polyacrylamide hydrogel, polyacrylamide/chitosan double-network hydrogel and polyvinyl alcohol hydrogel.
5. The ionic thermoelectric hydrogel-based flexible stretchable thermocouple of claim 1, characterized in that:
wherein the n-type ion thermoelectric hydrogel film and the p-type ion thermoelectric hydrogel film are obtained by immersing an elastic hydrogel in a corresponding aqueous electrolyte solution containing n-type redox couple ions and p-type redox couple ions.
6. The ionic thermoelectric hydrogel-based flexible stretchable thermocouple of claim 1, characterized in that:
the redox pair electrolyte comprises an oxidation state component, a reduction state component and a high-solubility inorganic salt, and the internal resistance of the hydrogel is reduced by increasing the ion concentration in the hydrogel through the high-solubility inorganic salt.
7. The ionic thermoelectric hydrogel-based flexible stretchable thermocouple of claim 1, characterized in that:
wherein the high-solubility inorganic salt is sodium chloride, lithium chloride or potassium chloride.
8. The ionic thermoelectric hydrogel-based flexible stretchable thermocouple of claim 1, characterized in that:
wherein the molar concentration of the oxidized component and the reduced component in the redox couple electrolyte are the same.
9. The ionic thermoelectric hydrogel-based flexible stretchable thermocouple of claim 8, characterized in that:
wherein the concentration of the oxidation state component and the reduction state component are both 0.2 mol/L.
10. A method of making a flexible and stretchable thermocouple according to any one of claims 1 to 9.
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|---|---|---|---|---|
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