A thermoelectric hydrogel with high strength, toughness, fatigue resistance, and high thermoelectric properties, its preparation method, and its application.

Abstract

This invention relates to the field of materials science, disclosing a thermoelectric hydrogel possessing high strength, toughness, fatigue resistance, and high thermoelectric properties, its preparation method, and applications. The preparation method includes: adding polyvinyl alcohol to an aramid nanofiber dispersion, stirring and removing bubbles, immersing in glycerol to complete dimethyl sulfoxide-glycerol solvent exchange, obtaining an ANFs / PVA gel; annealing the ANFs / PVA gel at 100–150°C, immersing in deionized water to prepare an ANFs / PVA hydrogel; immersing the ANFs / PVA hydrogel in a mixed aqueous solution containing potassium ferrocyanide, potassium ferrocyanide, and guanidine hydrochloride to obtain a thermoelectric hydrogel. The thermoelectric hydrogel prepared by this invention exhibits excellent mechanical strength and thermoelectric properties, has a simple preparation process, can be mass-produced, is safe and non-toxic, and has broad application prospects in flexible thermoelectric conversion, medical sensing and monitoring, and other fields.

Description

Technical Field

[0001] This invention relates to the field of materials science, specifically to a thermoelectric hydrogel with high strength, toughness, fatigue resistance, and high thermoelectric properties, as well as its preparation method and applications. Background Technology

[0002] With the advancement of electronic technology, the demand for environmentally friendly and sustainable flexible electronic power sources has become increasingly important. Stretchable thermoelectric materials based on the Seebeck effect have attracted widespread attention due to their high stretchability, energy conversion efficiency, and ability to harvest low-grade heat energy from the environment for power generation. However, traditional non-intrinsic thermoelectric materials, typically derived from inorganic semiconductors, are limited by low thermal power (Sg). c The limitations of flexible quasi-solid-state thermal cells include mechanical brittleness, high cost, and complex manufacturing processes. Flexible quasi-solid-state thermal cells possess excellent stretchability and high S-value. c Its resistance to leakage makes it a promising candidate for use in wearable electronics.

[0003] In practical applications, prolonged load cycling can lead to fatigue damage and crack formation in quasi-solid-state thermal batteries. However, because the network structure of flexible quasi-solid-state thermal batteries is mainly composed of weakly hydrogen-bonded or ionicly cross-linked materials, they exhibit notch sensitivity, resulting in low fracture energy and fatigue threshold, which severely impacts their performance stability and lifespan. Therefore, fabricating quasi-solid-state thermal batteries with high fatigue resistance and excellent thermoelectric performance has always been a challenging and highly sought-after goal. Improving fatigue resistance can be categorized into two main mechanisms. One approach focuses on structural engineering, involving techniques such as mechanical training, directional freezing, and ice templates. These methods aim to fabricate anisotropic micro / nanostructures to enhance the fracture energy and fatigue threshold of the thermal battery. However, these anisotropic structures only exhibit stress enhancement in specific directions, limiting their practical application. The second mechanism involves molecular engineering, introducing a stronger double-crosslinked network or hard domain phase than polymer chains, which can improve fracture energy, reduce fatigue crack propagation, and decrease notch sensitivity. Therefore, designing dense and randomly cross-linked nanonetworks or polymer crystal domains holds promise for constructing hydrogel thermal batteries with high strength and fatigue resistance.

[0004] By selecting a suitable additive to incorporate a redox couple and then introducing it into a hydrogel, a flexible thermal battery with enhanced thermoelectric performance based on ion conduction can be further designed. In currently reported studies, different types of Fe redox couples have been introduced... 2+ / Fe 3+ or Fe(CN)6 3- / Fe(CN)6 4-All of these methods resulted in low Seebeck coefficients and electrical conductivity, which are insufficient to meet practical requirements. Therefore, additives were used to further rearrange the redox couple solvation layer to develop a thermoelectric hydrogel with high fracture strength, excellent fatigue resistance, high Seebeck coefficient, and high specific power density, which is expected to show great application potential in wearable electronics, body temperature monitoring, and human body cooling. Summary of the Invention

[0005] Based on this, the present invention aims to develop a thermoelectric material with high fracture strength, excellent fatigue resistance, high Seebeck coefficient, and high specific power density, and provides a thermoelectric hydrogel with high strength, toughness, fatigue resistance and high thermoelectric performance, as well as its preparation method and application.

[0006] To achieve the above objectives, on the one hand, the present invention provides a method for preparing a thermoelectric hydrogel with high strength, toughness, fatigue resistance, and high thermoelectric properties. First, an ANFs / PVA hydrogel is prepared by solvent exchange-assisted annealing. Then, by leveraging the chaotic effect to enhance the thermoelectric effect, the hydrogel is immersed in a mixed thermoelectric solution of potassium ferricyanide (K3Fe(CN)6, abbreviated as K3FCN), potassium ferrocyanide (K4Fe(CN)6, abbreviated as K4FCN), and guanidine hydrochloride (GdmCl) to obtain the thermoelectric hydrogel.

[0007] The exchange of good solvents to poor solvents enhances the intermolecular interactions between ANFs and PVA, promoting the formation of cross-linked polymer networks. Subsequent annealing adjusts the macromolecular conformation, enabling the polymer chains to move and entangle fully, forming multi-hydrogen bonded interactions and highly crystalline macromolecular crystal domains. This improves the fracture strength of the thermal cell and results in an order-of-magnitude improvement in fatigue resistance. Introducing GdmCl into the hydrogel, which exhibits strong disorientation and excellent stability in the ANFs / PVA solution system, can maximize the rearrangement of the redox couple solvation layer, further enhancing the thermoelectric properties of the hydrogel.

[0008] Its preparation method specifically includes the following steps:

[0009] S1. Kevlar fibers and potassium hydroxide (KOH) are added to dimethyl sulfoxide (DMSO) and stirred until well mixed to obtain aramid nanofibers (ANFs) DMSO dispersion;

[0010] S2. Add polyvinyl alcohol to the ANFs / DMSO dispersion from step S1, stir and mix well to obtain an ANFs / PVA / DMSO solution.

[0011] S3. After removing bubbles from the ANFs / PVA DMSO solution obtained in step S2, immerse it in glycerol to complete the dimethyl sulfoxide-glycerol solvent exchange and obtain ANFs / PVA gel.

[0012] S4. Anneal the ANFs / PVA gel from step S3 at a high temperature of 100-150°C, and then soak it in deionized water to prepare ANFs / PVA hydrogel.

[0013] S5. The ANFs / PVA hydrogel from step S4 is immersed in a mixed aqueous solution containing potassium ferrocyanide (K3Fe(CN)6, abbreviated as K3FCN), potassium ferrocyanide (K4Fe(CN)6, abbreviated as K4FCN), and guanidine hydrochloride (GdmCl) to obtain a thermoelectric hydrogel with high strength, toughness, fatigue resistance and high thermoelectric properties.

[0014] In this invention, GdmCl can maximally promote the rearrangement of the solvation layers of K3Fe(CN)6 and K4Fe(CN)6, inducing the crystallization of redox couples. Preferably, in step S5, the ANFs / PVA hydrogel is immersed in a mixed aqueous solution of K3FCN, K4FCN, and GdmCl at high temperature for 1-4 hours, then removed and cooled at room temperature. Due to the binding of guanidine salts with K4FCN, a very thin crystalline layer forms on the surface of the hydrogel. More preferably, in the mixed aqueous solution of step S5, the concentrations of potassium ferrocyanide and potassium ferrocyanide are 0.05-0.4 mol / L. -1 The concentration of guanidine hydrochloride is 0.5-4 mol / L. -1 .

[0015] As a further preferred embodiment of the present invention, the mass percentage concentration of the ANFs DMSO dispersion in step S1 is 0.01-1%, and / or the mass ratio of polyvinyl alcohol to ANFs DMSO dispersion in step S2 is 1:1.5-1:4.

[0016] As a further preferred technical solution of the present invention, in step S1, magnetic stirring is performed at a temperature of 60-80°C for 5-15 days.

[0017] As a further preferred technical solution of the present invention, in step S3, the ANFs / PVA DMSO solution is placed in the mold and the ANFs / PVA DMSO solution is immersed in glycerol.

[0018] As a further preferred technical solution of the present invention, in step S4, the annealing temperature is 115-125°C and the annealing holding time is 1-5 hours.

[0019] According to another aspect of the present invention, the present invention also provides a thermoelectric hydrogel with high strength, toughness, fatigue resistance and high thermoelectric properties, which is prepared by the above-described method.

[0020] According to another aspect of the present invention, the invention also provides the application of a thermoelectric hydrogel possessing high strength, toughness, fatigue resistance, and high thermoelectric performance in the preparation of hydrogel thermal batteries. A hydrogel thermal battery is formed by cutting the thermoelectric hydrogel into a square shape and connecting conductive metal sheets as electrodes to the left and right ends of the thermoelectric hydrogel. The conductive metal sheets are preferably made of materials such as platinum, gold, or silver. The resulting hydrogel thermal battery meets practical applications in wearable electronic products, stretchable artificial tendons, and temperature monitoring.

[0021] Compared with the prior art, the present invention can achieve the following beneficial effects:

[0022] (1) The thermoelectric hydrogel prepared by the present invention has excellent mechanical strength (fatigue resistance) and thermoelectric properties. The preparation process is simple, can be mass-produced, and is safe and non-toxic. It has broad application prospects in the fields of flexible thermoelectric conversion and medical sensing and monitoring.

[0023] (2) The present invention is based on a hydrogel thermal battery with high strength, toughness, fatigue resistance and high thermoelectric performance. It can be used as a flexible thermoelectric device and has good application prospects in the fields of thermoelectric power generation, body temperature monitoring, stretchable artificial tendon and temperature monitoring. Attached Figure Description

[0024] The present invention will now be described in further detail with reference to the accompanying drawings and specific embodiments.

[0025] Figure 1 The mechanical properties of ANFs / PVA hydrogels prepared in Examples 1-4 and Comparative Example 1 with different ANFs DMSO dispersion concentrations are shown.

[0026] Figure 2 The storage modulus (G') and loss modulus (G”) of the ANFs / PVA hydrogel prepared in Example 1 are measured under constant shear strain (0.5%) during temperature scanning.

[0027] Figure 3 The electrical performance test results of the thermoelectric hydrogel obtained after soaking the ANFs / PVA hydrogel prepared in Example 1 in mixed aqueous solutions of different concentrations are shown.

[0028] Figure 4 The thermoelectric hydrogel obtained in Example 1 exhibits high thermoelectric properties under different temperature differences.

[0029] Figure 5 This describes the working principle of the thermoelectric hydrogel in Example 1.

[0030] Figure 6 The results show the mechanical properties and fatigue resistance of the thermoelectric hydrogel in Example 1.

[0031] Figure 7 Seebeck coefficients are the two sets of thermoelectric hydrogels prepared in Example 1 and Comparative Example 1 with DMSO dispersions containing 0.5% ANFs and without ANFs, respectively.

[0032] Figure 8 Seebeck coefficient and conductivity of the five thermoelectric hydrogels prepared in Examples 5-9 and the five thermoelectric hydrogels prepared in Examples 10-14.

[0033] The objectives, features, and advantages of this invention will be further explained in conjunction with the embodiments and with reference to the accompanying drawings. Detailed Implementation

[0034] The specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are for illustration and explanation only and are not intended to limit the present invention.

[0035] Unless otherwise defined, the technical terms used in the following embodiments have the same meanings as commonly understood by those skilled in the art to which this invention pertains. Unless otherwise specified, the experimental reagents used in the following embodiments are conventional biochemical reagents; and the experimental methods described are conventional methods.

[0036] The following materials were provided by Shanghai Maclean Biochemical Technology Co., Ltd.: polyvinyl alcohol, potassium hydroxide, potassium ferrocyanide, and guanidine hydrochloride; Kevlar fiber was purchased from DuPont China Co., Ltd. Shanghai Branch; potassium ferrocyanide and glycerin were purchased from Tianjin Xiens Opd Technology Co., Ltd.; and dimethyl sulfoxide was purchased from Shanghai Titan Technology Co., Ltd.

[0037] The testing methods involved in this embodiment are as follows: The Seebeck coefficient of the thermoelectric hydrogel was tested using a self-built testing device; the temperature difference between the left and right ends of the sample was controlled using a low-voltage power supply and a commercial Peltier heating module; the open-circuit voltage across the hydrogel was measured using a Keithley 2450 data acquisition system; simultaneously, the real-time temperature of the left and right ends of the hydrogel was collected using thermocouples, and the Seebeck coefficient was calculated. Taking a long strip structure as an example, the effective length, width, and thickness of the thermoelectric hydrogel designed in this embodiment were measured using vernier calipers. A platinum sheet was used as an electrode connected to both ends of the thermoelectric hydrogel. The resistance at both ends of the thermoelectric hydrogel was measured using a Keithley 2450. Based on the length, resistance, and cross-sectional area of ​​the thermoelectric hydrogel, its resistivity was calculated and converted to conductivity. The stress-strain test of the hydrogel was performed using a universal testing machine system; the fatigue test of the hydrogel was performed using a fatigue testing machine, and the electrical signals were recorded in real-time via a Keithley 2450 interconnect. Tensile photographs of the notched hydrogel were obtained using a high-speed camera.

[0038] Example 1

[0039] The method for preparing a thermoelectric hydrogel with high strength, toughness, fatigue resistance, and high thermoelectric performance, and the method for fabricating a device based on the thermoelectric hydrogel provided in this embodiment are as follows:

[0040] (1) Kevlar fibers and potassium hydroxide (KOH) were added to 500 ml of dimethyl sulfoxide (DMSO) and heated at 70 °C with magnetic stirring for 14 days to prepare an aramid nanofiber (ANFs) DMSO dispersion with a mass percentage concentration of 0.5% and a dark red color.

[0041] (2) Add 20g PVA-1799 to the 80g ANFs DMSO dispersion in step (1) and stir vigorously at 80℃ for 14 days to obtain ANFs / PVA DMSO solution.

[0042] (3) After removing the bubbles from the ANFs / PVADMSO solution in step (2) by vacuum, pour it into the mold and immerse it in glycerol at room temperature to complete the DMSO-glycerol solvent exchange and obtain ANFs / PVA gel.

[0043] (4) Anneal the ANFs / PVA gel from step (3) at 120°C for 3 hours, and then soak it in deionized water to exchange glycerol with water to prepare ANFs / PVA hydrogel.

[0044] (5) The hydrogel from step (4) is placed in a mixed aqueous solution of 0.2M potassium ferrocyanide-potassium ferrocyanide / 3.0M guanidine hydrochloride, soaked for 4 hours, and then taken out to obtain the thermoelectric hydrogel with high strength, toughness, fatigue resistance and high thermoelectric performance of the present invention.

[0045] (6) Cut the thermoelectric hydrogel from step (5) into strips of 4cm×1cm and connect the two ends of the thermoelectric hydrogel with platinum sheets as electrodes to obtain a hydrogel thermoelectric device (also known as a hydrogel thermal battery) with an effective electrode length of 2cm.

[0046] Comparative Example 1

[0047] As a control experiment of Example 1, the difference from Example 1 is that step (1) is omitted and the ANFs DMSO dispersion in step (2) is replaced with DMSO without ANFs. The subsequent steps are the same as in Example 1, and finally a thermoelectric hydrogel without ANFs is obtained.

[0048] Examples 2-4

[0049] Based on Example 1, three sets of examples were provided by changing the process. The difference between them and Example 1 is that the mass percentage concentration of the ANFs DMSO dispersion obtained in step (1) is different, and the concentrations are 0.1%, 0.25%, and 1% respectively. The remaining steps are the same as in Example 1.

[0050] Figure 1 The mechanical properties of ANFs / PVA hydrogels prepared in Examples 1-4 and Comparative Example 1 with different ANFs DMSO dispersion concentrations are presented. It can be seen that the tensile strength of the pure PVA hydrogel (referring to the hydrogel in Comparative Example 1 without ANFs) is 4.6 MPa. The tensile strength of the gel increases with increasing ANFs concentration from 0.1% to 1%, reaching its highest value (1130%) at an ANFs concentration of 0.5% and an elongation at break of 5.7 MPa. This test indicates that at a 0.5% ANFs concentration, the PVA chains interact best through hydrogen bonding with the ANFs network, promoting load transfer through the rigid aromatic polyamide backbone.

[0051] Figure 2 The storage modulus (G') and loss modulus (G”) of the ANFs / PVA hydrogel prepared in Example 1 are demonstrated during temperature scanning under constant shear strain (0.5%). Within the temperature range of 20–150 °C, the storage modulus consistently exceeds the loss modulus, exhibiting solid-like and elastic properties. In the initial stage of heating, the thermal motion of the ANFs / PVA gel molecular chains intensifies, weakening intermolecular forces and leading to a decrease in modulus. As the temperature continues to rise (above 110 °C), the molecular chain motion forms new entanglements or a more ordered structure, thereby increasing the storage modulus again. Based on this, we selected a temperature point above 110 °C (120 °C) to anneal the ANFs / PVA gel at 120 °C to rearrange the ANFs / PVA polymer molecular aggregates, enhance crystallinity, and improve the mechanical properties of the gel.

[0052] Figure 3 The electrical properties of the thermoelectric hydrogels obtained after immersing the ANFs / PVA hydrogel prepared in Example 1 in mixed aqueous solutions of different concentrations are demonstrated. The properties were obtained by immersing the hydrogel in guanidine hydrochloride solutions of different concentrations (potassium ferricyanide / potassium ferrocyanide concentration of 0.2 mol / L). -1 Images of the Seebeck coefficient and conductivity after immersion in guanidine hydrochloride show that the conductivity increases with increasing guanidine hydrochloride concentration, from 0.9 S / m. -1 Increased to 3.1S m -1 The Seebeck coefficient first increases and then decreases.

[0053] Figure 4 The thermoelectric hydrogel obtained in Example 1 exhibits high thermoelectric properties under different temperature differences. Figure 4 At temperature differences of 10K, 15K, 20K, 25K, and 30K, the maximum output power density is 620mW / m³. -2 .from Figure 4 As can be seen from b, the maximum output power density of the thermoelectric hydrogel gradually increases with the increase of temperature difference, and the normalized maximum output power density is approximately 714 μW / m³. -2 K -2 This is higher than that of currently reported anti-fatigue gel thermoelectric materials based on thermoelectrochemical effects.

[0054] Figure 5 To illustrate the working principle of the thermoelectric hydrogel in Example 1, guanidine hydrochloride selectively induces [Fe(CN)6]. 4- The crystallization of [Fe(CN)6] occurs when guanidine hydrochloride is added to the redox solution. 4- It is easy to use with Gdm + The reaction combines to form crystals on the cold side and then dissolves on the hot side. The accelerated redox reaction enhances charge transfer, resulting in higher thermal power.

[0055] Figure 6 The mechanical properties and fatigue resistance of the thermoelectric hydrogel in Example 1 are described. Figure 6 As can be seen, the thermoelectric hydrogel can achieve a fracture strength of 6.2 MPa and a fracture energy of approximately 153 kJ / m. -2 The fracture strain is approximately 800%. Figure 6 The inset photo in a shows an optimized thermoelectric hydrogel ring with a diameter of 6 mm, capable of lifting a 5 kg dumbbell without breaking, demonstrating remarkable strength and exceptional toughness; Figure 6 b is a scatter plot of the crack propagation rate versus energy release rate of the thermoelectric hydrogel after 5000 cycles at 600% strain, where the critical energy release rate is equal to the fatigue threshold, approximately 4.1 kJ / m². -2 . Figure 6The inset image in b shows real-time tensile images of the thermoelectric hydrogel after 5000 cycles at 0%, 100%, and 600% strain, demonstrating good toughness and fatigue resistance.

[0056] Figure 7 Seebeck coefficients of two groups of thermoelectric hydrogels prepared in Example 1 and Comparative Example 1 with DMSO dispersions containing 0.5% ANFs and without ANFs are given. As can be seen from the figure, the addition of ANFs has almost no effect on the Seebeck coefficient, which indicates that the interaction between ANFs and PVA polymers has little effect on the Seebeck coefficient and mainly affects the mechanical properties.

[0057] Examples 5-9

[0058] Five sets of examples were provided based on Example 1 by modifying the process. The difference between these examples and Example 1 is that the soaking mixed aqueous solution in step (5) was changed to a potassium ferrocyanide-potassium ferrocyanide aqueous solution (concentration in the range of 0.05-0.4 mol / L). -1 The concentrations were 0.05M, 0.1M, 0.2M, 0.3M, and 0.4M respectively, with guanidine hydrochloride omitted. The remaining steps were the same as in Example 1, and five groups of thermoelectric hydrogels were finally obtained.

[0059] Through testing and calculation Figure 8 a presents the Seebeck coefficient and conductivity of the five groups of thermoelectric hydrogels prepared in Examples 5-9 after immersion in potassium ferrocyanide / potassium ferrocyanide solutions of different concentrations. It can be seen that the Seebeck coefficient does not change significantly with increasing concentration, remaining at 1.56 mV K. -1 about.

[0060] Examples 10-14

[0061] Based on the preparation method of Example 1, and building upon Examples 5-9, 1.0 mol L of [a specific ingredient] was added to the soaking solution. -1 Guanidine hydrochloride was added, and the remaining steps were the same as in Example 1, ultimately yielding five groups of thermoelectric hydrogels.

[0062] Through testing, Figure 8 b presents five groups of thermoelectric hydrogels prepared in Examples 10-14 in different concentrations of potassium ferrocyanide / potassium ferrocyanide solutions (guanidine hydrochloride concentration 1.0 mol L). -1 The Seebeck coefficient and conductivity after immersion in 0.2 mol L were as follows: conductivity gradually decreased with increasing concentration. -1 At that time, the Seebeck coefficient reached a maximum of 5.1 mV K. -1 The conductivity is 1.24 S m. -1 .

[0063] It should be further noted that, through solvent exchange-assisted annealing and the strategy of enhancing thermoelectric effects through chaotic effects, the thermoelectric hydrogel prepared in this invention exhibits excellent mechanical strength, fatigue resistance, and high thermoelectric properties. Within a tensile strain range of 0% to 150%, the average Seebeck coefficient remains at 4.6 mV K. -1 Around 620 mW / m² at a temperature difference of 30 K. -2 Normalized maximum power density (P max / ΔT 2 Up to 714 μW m -2 K -2 This is the highest value reported so far for stretchable fatigue-resistant gel thermoelectric materials of this system.

[0064] While specific embodiments of the present invention have been described above, those skilled in the art should understand that these are merely illustrative examples, and various changes or modifications can be made to these embodiments without departing from the principles and essence of the present invention. The scope of protection of the present invention is defined only by the appended claims.

Claims

1. A method for preparing a thermoelectric hydrogel possessing high strength, toughness, fatigue resistance, and high thermoelectric properties, characterized in that, Includes the following steps: S1. Add Kevlar fiber and potassium hydroxide to dimethyl sulfoxide, stir and mix well to obtain ANFs DMSO dispersion; S2. Add polyvinyl alcohol to the ANFs DMSO dispersion from step S1, stir and mix well to obtain an ANFs / PVA DMSO solution. S3. After removing bubbles from the ANFs / PVA DMSO solution obtained in step S2, immerse it in glycerol to complete the dimethyl sulfoxide-glycerol solvent exchange and obtain ANFs / PVA gel. S4. Anneal the ANFs / PVA gel from step S3 at a high temperature of 100-150°C, and then soak it in deionized water to prepare ANFs / PVA hydrogel. S5. The ANFs / PVA hydrogel from step S4 is immersed in a mixed aqueous solution containing potassium ferrocyanide, potassium ferrocyanide, and guanidine hydrochloride to obtain a thermoelectric hydrogel with high strength, toughness, fatigue resistance, and high thermoelectric properties.

2. The method for preparing a thermoelectric hydrogel with high strength, toughness, fatigue resistance, and high thermoelectric properties according to claim 1, characterized in that, In step S1, the mass percentage concentration of the ANFs DMSO dispersion is 0.1% to 1%, and / or, in step S2, the mass ratio of polyvinyl alcohol to the ANFs DMSO dispersion is 1:1.5 to 1:

4.

3. The method for preparing a thermoelectric hydrogel with high strength, toughness, fatigue resistance, and high thermoelectric properties according to claim 1, characterized in that, In step S1, the mixture is magnetically stirred at a temperature of 60–80°C for 5–15 days.

4. The method for preparing a thermoelectric hydrogel with high strength, toughness, fatigue resistance, and high thermoelectric properties according to claim 1, characterized in that, In step S3, the ANFs / PVADMSO solution is placed in a mold, and then the ANFs / PVADMSO solution is immersed in glycerol.

5. The method for preparing a thermoelectric hydrogel with high strength, toughness, fatigue resistance, and high thermoelectric properties according to claim 1, characterized in that, In step S4, the annealing holding time is 1-5 hours.

6. The method for preparing a thermoelectric hydrogel with high strength, toughness, fatigue resistance, and high thermoelectric properties according to claim 1, characterized in that, In the mixed aqueous solution of step S5, the concentrations of potassium ferrocyanide and potassium ferrocyanide are 0.05-0.4 mol / L. -1 The concentration of guanidine hydrochloride is 0.5-4 mol / L. -1 .

7. The method for preparing a thermoelectric hydrogel with high strength, toughness, fatigue resistance, and high thermoelectric properties according to claim 1, characterized in that, In step S5, the soaking time is 1-4 hours.

8. A method for preparing a thermoelectric hydrogel possessing high strength, toughness, fatigue resistance, and high thermoelectric properties, characterized in that, It is prepared by the method described in any one of claims 1-7.

9. The application of the thermoelectric hydrogel of claim 8, which combines high strength, toughness, fatigue resistance and high thermoelectric properties, in the preparation of hydrogel thermal batteries.

10. The application according to claim 9, characterized in that, The thermoelectric hydrogel was cut into squares, and conductive metal sheets were used as electrodes to connect to the left and right ends of the thermoelectric hydrogel.

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