A double network thermoelectric gel based on inorganic super-long nanofibers and preparation method and application thereof

Abstract

The application discloses a preparation method and application of a double-network thermoelectric gel based on inorganic super-long nanofibers. The double-network gel based on inorganic super-long nanofibers is synthesized through a high-speed fluid impingement method, and then a polymer / hollow nanoparticle composite porous heat-blocking diaphragm is formed in the double-network gel through in-situ nano-polymerization, so that the thermoelectric conversion efficiency of the double-network gel is improved. The double-network thermoelectric gel is doped with P-type thermoelectric ions and N-type thermoelectric ions in the gel through a layer-by-layer penetration method, and is called a P-type thermoelectric gel and an N-type thermoelectric gel. The gel converts thermal energy into electric energy through a reversible oxidation-reduction reaction. The double-network thermoelectric gel based on inorganic super-long nanofibers has high output power, high thermoelectric conversion efficiency, the ability of continuously carrying out thermoelectric conversion, high mechanical flexibility, no risk of electrolyte leakage and biocompatibility, and can be used as a flexible energy supply device to realize energy supply for flexible electronic equipment.

Description

Technical Field

[0001] This invention belongs to the field of thermoelectric conversion technology, specifically relating to a dual-network thermoelectric gel based on inorganic ultralong nanofibers, its preparation method, and its application. Background Technology

[0002] In recent years, portable wearable flexible electronic devices have attracted increasing attention from researchers in areas such as electronic skin, human physiological activity detection, human health monitoring, stretchable touchscreens, human-machine interfaces, and soft robotics. Therefore, it is necessary to seek advanced flexible and stretchable power supply devices to power these flexible electronic devices.

[0003] Traditional energy technologies such as supercapacitors, rechargeable batteries, and solar cells require periodic charging to continuously power wearable flexible electronic devices. In contrast, thermoelectric materials, such as semiconductor thermoelectric generators and thermoelectric batteries, can provide sustainable power to flexible electronic devices by continuously collecting low-grade heat energy. Therefore, thermoelectric materials are a very promising class of energy supply devices.

[0004] The application of inorganic semiconductor thermoelectric generators in wearable flexible electronic device systems is hampered by their potential toxicity, mechanical brittleness, and low energy conversion efficiency, hindering their development and application in flexible and stretchable energy supply devices. Traditional liquid electrolyte thermoelectric batteries pose a risk of electrolyte leakage, leading to complex encapsulation and integration issues in the fabrication process. In contrast, gel thermoelectric batteries, with their advantages of high output power, high thermoelectric conversion efficiency, continuous thermoelectric conversion capability, high mechanical flexibility, no electrolyte leakage risk, and biocompatibility, can directly utilize body heat to power wearable flexible electronic devices. Gel thermoelectric batteries consist of two electrodes and a gel matrix containing redox ion pairs. Once a temperature gradient is established between the two electrodes, it disrupts the equilibrium of reversible redox reactions near the electrodes, creating a potential difference between them and converting thermal energy into electrical energy. For wearable applications, gel thermoelectric batteries avoid the complex encapsulation and integration problems associated with traditional liquid electrolytes, achieving a flexible and safe thermoelectric battery by solidifying the liquid electrolyte into a quasi-solid-state gel electrolyte. In addition, gel thermal batteries absorb a large amount of solvent to expand into a solid structure and form a gel structure with a three-dimensional network structure. They have good ion conductivity and mechanical flexibility, making them an ideal flexible and stretchable energy supply device. Summary of the Invention

[0005] One of the objectives of this invention is to provide a method for preparing a dual-network thermoelectric gel based on inorganic ultralong nanofibers.

[0006] The second objective of this invention is to provide a dual-network thermoelectric gel based on inorganic ultralong nanofibers prepared by the above-mentioned method.

[0007] A third objective of this invention is to provide applications of the aforementioned dual-network thermoelectric gel.

[0008] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0009] In a first aspect, the present invention provides a method for preparing a dual-network thermoelectric gel based on inorganic ultralong nanofibers, comprising the following steps:

[0010] (1) Synthesis of a dual-network gel based on inorganic ultralong nanofibers by high-speed fluid counter-current method:

[0011] An aqueous solution of inorganic ultralong nanofibers (number 1) was prepared and stored in a syringe pump (number 1). An aqueous solution of inorganic ultralong nanofibers (number 2) was prepared and stored in a syringe pump (number 2). An aqueous solution of metal clusters was prepared and stored in a syringe pump (number 3). All solutions required magnetic stirring and ultrasonic degassing. The syringe pumps (number 1 and number 3) were placed on the left side of the mold, and the syringe pump (number 2) was placed on the right side of the mold. The three syringe pumps simultaneously injected solutions into the mold, forming a high-speed fluid collision environment to synthesize a double-network gel. The injection speed of the three syringe pumps was the same, ranging from 1 to 10 mL / s.

[0012] (2) Synthesis of polymer / hollow nanoparticle composite porous thermal barrier membrane within a gel via in-situ nanopolymerization:

[0013] Prepare a hollow nanoparticle / propylene amino acid monomer complex solution and store it in syringe No. 1. Store the catalyst solution in syringe No. 2. Simultaneously inject the two syringes into the middle of the double network gel obtained in step (1) at high speed. The hollow nanoparticle / propylene amino acid monomer complex and the catalyst form a polymer / hollow nanoparticle composite porous heat-resistant membrane inside the gel through in-situ nanopolymerization. The injection speed of the two syringes is the same, which is 0.5 to 5 ml / s.

[0014] (3) Doping the gel with P-type and N-type thermoelectric ions through a layer-by-layer permeation method:

[0015] Prepare a homogeneous P-type thermoelectric ion solution and store it in syringe No. 1. Starting from the bottom layer of the gel obtained in step (2), slowly inject the P-type thermoelectric ion solution into the gel layer by layer to make the ions dispersed uniformly in the gel to the greatest extent, and obtain a P-type thermoelectric gel.

[0016] Prepare a homogeneous N-type thermoelectric ion solution and store it in a second syringe. Starting from the bottom layer of the gel obtained in step (2), slowly inject the N-type thermoelectric ion solution into the gel layer by layer to make the ions dispersed uniformly in the gel to the greatest extent possible, and obtain an N-type thermoelectric gel.

[0017] The injection speed of both syringes is the same, ranging from 0.1 to 3 ml / s.

[0018] (4) P-type thermogel and N-type thermogel are connected in series through flexible electrodes to form a PN combined thermogel.

[0019] Preferably, the first inorganic ultra-long nanofiber and the second inorganic ultra-long nanofiber mentioned in step (1) are selected from any two combinations of lanthanum nanofiber (La), cerium nanofiber (Ce), praseodymium nanofiber (Pr), bismuth disulfide nanofiber (BiS2), europium trisulfide nanofiber (Eu2S3), terbium triselenide nanofiber (Tb2Se3), and dysprosium triselenide nanofiber (Dy2Se3).

[0020] The metal clusters are selected from any one of europium nanoclusters (Eu), terbium nanoclusters (Tb), dysprosium nanoclusters (Dy), samarium nanoclusters (Sm), and iridium nanoclusters (Ir).

[0021] The mass ratio of the inorganic ultralong nanofibers to the metal clusters is (1-5):(0.01-1).

[0022] The solution is stirred for 1 to 5 hours. The solution is ultrasonically degassed for 5 to 30 minutes.

[0023] Preferably, the hollow nanoparticles in step (2) are selected from any one of titanium carbide (TiC), zirconium carbide (ZrC), vanadium carbide (VC), manganese sulfide (MnS), and dichromium trisulfide (Cr2S3); the propylene amino acid monomer is selected from any one of propylene lysine, propylene arginine, propylene histidine, propylene serine, and propylene tyrosine; the mass ratio of the hollow nanoparticles to the propylene amino acid monomer is (0.1-2):(1-20).

[0024] The catalyst is selected from any one of naphthalimide, phenanthreneimide, and anthraquinoneimide.

[0025] Preferably, the P-type thermoelectric ions in step (3) are selected from one of Na2SO4 / Na2SO3, Na2PO4 / Na2PO3, and NaClO4 / NaClO3. The mass of the P-type thermoelectric ions is 0.1% to 3% of the mass of the dual-network gel.

[0026] The N-type thermoelectric ions are selected from one of Mn2(SO4)3 / MnSO4, Mn(NO3)3 / Mn(NO3)2, and MnCl3 / MnCl2. The mass of the N-type thermoelectric ions is 0.1% to 3.0% of the mass of the dual-network gel.

[0027] The height of the injection layer is 0.01 to 0.1 cm per layer.

[0028] Preferably, the flexible electrode in step (4) is selected from one of platinum wire, titanium wire, graphite paper, and conductive grease.

[0029] Secondly, the present invention provides a dual-network thermoelectric gel based on inorganic ultralong nanofibers prepared by the above preparation method.

[0030] This invention discloses a dual-network thermoelectric gel based on inorganic ultra-long nanofibers. The internal cross-linking network consists of two layers: the first cross-linking network is formed by the electrostatic interaction between negatively charged first-order inorganic ultra-long nanofibers and positively charged metal clusters; the second cross-linking network is formed by the electrostatic interaction between negatively charged second-order inorganic ultra-long nanofibers and positively charged metal clusters. The first and second-order inorganic ultra-long nanofibers, possessing opposite magnetic properties, interact magnetically, causing them to become entangled and forming a dual-cross-linking network structure. An in-situ nanopolymerization process forms a polymer / hollow nanoparticle composite porous thermally insulating membrane within the dual-network thermoelectric gel, effectively reducing internal heat conduction and improving the thermoelectric conversion efficiency. The thermoelectric gel is doped with P-type and N-type thermoelectric ions through a layer-by-layer permeation method, resulting in P-type and N-type thermoelectric gels. The gels convert thermal energy into electrical energy through a reversible redox reaction. The P-type and N-type thermoelectric gels are connected in series via flexible electrodes to form a PN-combined thermoelectric gel.

[0031] Thirdly, the present invention provides the application of the above-mentioned dual-network thermoelectric gel in the preparation of flexible energy supply devices.

[0032] Multiple PN-combined thermoelectric gels are connected in series via flexible electrodes and encapsulated in a flexible substrate to form a flexible energy supply device. This device powers portable, wearable flexible electronic devices by continuously collecting low-grade heat.

[0033] The flexible electrode is selected from one of platinum wire, titanium wire, graphite paper, and conductive grease; the flexible substrate is selected from one of polyimide, polyurethane, polydimethylsiloxane, and Ecoflex elastomer.

[0034] Compared with the prior art, the present invention has the following beneficial effects:

[0035] 1) The dual-network thermoelectric gel of the present invention utilizes the heat generated by the human body to continuously power portable wearable flexible electronic devices, with high power supply efficiency and stable operation.

[0036] 2) The dual-network thermoelectric gel of the present invention achieves the mutual entanglement between fibers to form a double cross-linked network structure through the electrostatic interaction between inorganic ultra-long nanofibers and metal clusters and the magnetic interaction between inorganic ultra-long nanofibers, and provides a three-dimensional interwoven structure through the strong interaction between inorganic ultra-long nanofibers and solvent, which effectively improves the mechanical properties of gel thermal batteries, has good ion conduction ability and mechanical flexibility, and has no risk of electrolyte leakage.

[0037] 3) The dual-network thermoelectric gel of the present invention forms a polymer / hollow nanoparticle composite porous heat-insulating membrane through in-situ nanopolymerization, which effectively reduces the heat conduction inside the gel and improves the thermoelectric conversion efficiency of the dual-network thermoelectric gel.

[0038] 4) The dual-network thermoelectric gel of the present invention has advantages such as high output power, high thermoelectric conversion efficiency, continuous thermoelectric conversion capability, high mechanical flexibility, no risk of electrolyte leakage and biocompatibility, and has broad application prospects in the field of energy supply for portable wearable flexible electronic devices. Attached Figure Description

[0039] Figure 1 The cross-linked network structure inside a dual-network thermogel based on inorganic ultra-long nanofibers was depicted.

[0040] Figure 2 A three-dimensional model of a dual-network thermoelectric gel based on inorganic ultra-long nanofibers is depicted. The dual-network thermoelectric gel includes inorganic ultra-long nanofibers, metal clusters, solvent, high-valence thermoelectric ions, low-valence thermoelectric ions, and a polymer / hollow nanoparticle composite porous heat-insulating membrane.

[0041] Figure 3 The thermoelectric conversion mechanism of PN combined thermoelectric gels was described.

[0042] Figure 4 A diagram of a flexible energy supply device consisting of 12 PN-type thermoelectric gels connected in series is depicted. Using flexible electrodes as a bridge, P-type and N-type thermoelectric gels are connected in series and finally encapsulated in a flexible substrate to achieve enhanced power output.

[0043] Figure 5 The preparation process of dual-network gels using a high-speed fluid counter-current method is described.

[0044] Figure 6The preparation process of polymer / hollow nanoparticle composite porous thermal barrier membranes synthesized inside a double-network gel using in-situ nanopolymerization is described.

[0045] Figure 7 The process of doping thermoelectric ions into the interior of a double-network gel using a layer-by-layer permeation method is described.

[0046] Figure 8 The thermal power of the P-type thermogel, N-type thermogel and PN combined thermogel prepared in Example 1 is described.

[0047] Figure 9 The mechanical properties of the P-type thermogel prepared in Example 1 are described.

[0048] Figure 10 The output power of a PN-combined thermoelectric gel under a temperature gradient of 10 K is depicted. Detailed Implementation

[0049] The present invention will now be described in further detail with reference to the accompanying drawings and specific embodiments.

[0050] The internal cross-linking network of the dual-network thermoelectric gel based on inorganic ultralong nanofibers described in this invention is composed of inorganic ultralong nanofibers and metal clusters. The first cross-linking network is formed by the electrostatic interaction between a negatively charged first inorganic ultralong nanofiber and a positively charged metal cluster. The second cross-linking network is formed by the electrostatic interaction between a negatively charged second inorganic ultralong nanofiber and a positively charged metal cluster. The first and second inorganic ultralong nanofibers, possessing opposite magnetic properties, interact magnetically, causing the inorganic ultralong nanofibers to become entangled, forming a dual-cross-linking network structure (e.g., ...). Figure 1 (As shown). The dual-network thermoelectric gel incorporates an in-situ nanopolymerized polymer / hollow nanoparticle composite porous thermally insulating membrane, effectively reducing internal heat conduction and improving its thermoelectric conversion efficiency. The thermoelectric gel is further doped with P-type and N-type thermoelectric ions through a layer-by-layer permeation method, resulting in P-type and N-type thermoelectric gels, respectively. Their three-dimensional models are shown below. Figure 2 As shown, the gel converts thermal energy into electrical energy through a reversible redox reaction. P-type thermoelectric gels and N-type thermoelectric gels are connected in series via flexible electrodes to form a PN-combined thermoelectric gel.

[0051] The thermoelectric conversion mechanism of PN combined thermoelectric gels, such as Figure 3 As shown: Due to the temperature gradient between the two electrodes, the equilibrium of the reversible redox reaction near the two electrodes is disrupted. Both P-type and N-type thermoelectric ions undergo redox reactions, with ion migration occurring inside and electron migration occurring outside, thereby generating a potential difference between the two electrodes and realizing the conversion of thermal energy into electrical energy.

[0052] Example 1

[0053] (1) As Figure 5 As shown, a dual-network gel based on inorganic ultralong nanofibers was synthesized via a high-speed fluid counter-current method: ① 0.1 g of lanthanum nanofibers (La) were weighed and prepared into an aqueous solution, 0.1 g of bismuth disulfide nanofibers (BiS2) were weighed and prepared into an aqueous solution, and 0.1 g of europium nanoclusters (Eu) were weighed and prepared into an aqueous solution. All solutions were subjected to magnetic stirring for 1 hour and ultrasonic degassing for 5 minutes. ② The dual-network gel was synthesized using a high-speed fluid counter-current method in a sealed mold. The lanthanum nanofiber (La) aqueous solution was stored in injection pump No. 1, the bismuth disulfide nanofiber (BiS2) aqueous solution was stored in injection pump No. 2, and the europium nanoclusters (Eu) aqueous solution was stored in injection pump No. 3. Injection pumps No. 1 and No. 3 were located on the left side of the mold, and injection pump No. 2 was located on the right side of the mold. The three injection pumps simultaneously injected solutions into the mold at an injection rate of 1 mL / s, forming a high-speed fluid counter-current environment to synthesize the dual-network gel.

[0054] (2) Figure 6 As shown, a polymer / hollow nanoparticle composite porous thermal barrier membrane was synthesized inside a gel via in-situ nanopolymerization: Allyl lysine monomer was modified into hollow titanium carbide (TiC) nanoparticles through surface grafting modification. 0.1 g of the titanium carbide (TiC) nanoparticle / allyl lysine monomer composite was weighed and prepared into a solution, which was stored in syringe #1. 0.01 g of the catalyst naphthalimide solution was weighed and stored in syringe #2. Both syringes were simultaneously injected into the center of the gel at a high-speed injection rate of 0.5 mL / s to form the polymer / hollow titanium carbide (TiC) nanoparticle composite porous thermal barrier membrane via in-situ nanopolymerization.

[0055] (3) Figure 7 As shown, a layer-by-layer permeation method was used to dope the interior of a double-network organic gel with P-type and N-type thermoelectric ions: 0.1 g of P-type thermoelectric ion Na2SO4 / Na2SO3 was weighed and prepared into a homogeneous solution, which was stored in syringe No. 1. Starting from the bottom layer of the gel, the thermoelectric ion solution was slowly injected into the gel layer by layer at an injection layer height of 0.01 cm and an injection speed of 0.1 mL / s, so that the ions were dispersed uniformly within the gel to the greatest extent possible, thus obtaining a P-type thermoelectric gel. Similarly, 0.1 g of N-type thermoelectric ion Mn2(SO4)3 / MnSO4 was weighed and prepared into a homogeneous solution, which was stored in syringe No. 2. Starting from the bottom layer of the gel, the thermoelectric ion solution was slowly injected into the gel layer by layer at an injection layer height of 0.01 cm and an injection speed of 0.1 mL / s, so that the ions were dispersed uniformly within the gel to the greatest extent possible, thus obtaining an N-type thermoelectric gel.

[0056] (4) P-type thermogel and N-type thermogel are connected in series through flexible electrode platinum wire to form PN combined thermogel.

[0057] Twelve PN-combined thermoelectric gels are connected in series via flexible electrodes and encapsulated in a flexible polyimide substrate to form a flexible energy supply device, such as... Figure 4 As shown, a flexible electrode is used as a bridge to connect P-type thermoelectric gel and N-type thermoelectric gel in series, and finally encapsulated in a flexible substrate to achieve enhanced power output.

[0058] Voltage-time and temperature-time curves of P-type thermogel, N-type thermogel, and a PN-combined thermogel were measured in a self-made thermoelectric conversion test platform. The voltage-temperature curve was obtained by fitting the two curves, and the slope of this curve represents the thermal power (Se value). Based on the test and data analysis results, such as... Figure 8 As shown, the Se value of the P-type thermogel reaches -9.32 mV / K, the Se value of the N-type thermogel reaches 7.35 mV / K, and the Se value of a PN combined thermogel reaches 16.58 mV / K. The hot junction temperature of the thermogel is controlled by a commercial ceramic Peltier heater, and its temperature change is monitored in real time by a thermocouple. The cold junction temperature is ambient temperature, and its temperature change is monitored in real time by a thermocouple. The open-circuit voltage of the thermogel is recorded using a multimeter.

[0059] The mechanical properties of the P-type thermoelectric gel were tested using a tensile testing machine, and its stress-strain curve was obtained, as follows: Figure 9 As shown in the figure. Analysis of the data reveals that the maximum tensile strength of the P-type thermogel is 5.12 MPa, and the elongation at break reaches 2000%.

[0060] A platinum wire was used to connect a P-type thermogel and an N-type thermogel in series. The temperature at both ends of the thermogel was controlled at 10K, and the voltage-time and current-time curves were recorded using a multimeter. The current density-time curve was calculated based on the cross-sectional area of ​​the thermogel. The current density-voltage curve was obtained by fitting the current density-time curve and the voltage-time curve. The power density was calculated using the formula P=UI, and finally, the power density-voltage curve was obtained, as shown below. Figure 10 As shown in the figure. Analysis of the data reveals that the maximum power output of the P-type thermogel in this embodiment is 3255 mW / m. 2 .

[0061] Example 2

[0062] (1) As Figure 5As shown, a dual-network gel based on inorganic ultralong nanofibers was synthesized via a high-speed fluid counter-current method: ① 0.2 g of cerium nanofibers (Ce), 0.2 g of europium trisulfide nanofibers (Eu2S3), and 0.2 g of terbium nanoclusters (Tb) were weighed and prepared into an aqueous solution. All solutions were subjected to magnetic stirring for 1 hour and ultrasonic degassing for 10 minutes. ② The dual-network gel was synthesized using a high-speed fluid counter-current method in a sealed mold. The cerium nanofiber (Ce) aqueous solution was stored in injection pump No. 1, the europium trisulfide nanofiber (Eu2S3) aqueous solution was stored in injection pump No. 2, and the terbium nanoclusters (Tb) aqueous solution was stored in injection pump No. 3. Injection pumps No. 1 and No. 3 were located on the left side of the mold, and injection pump No. 2 was located on the right side of the mold. The three injection pumps simultaneously injected solutions into the mold at an injection rate of 2 mL / s, forming a high-speed fluid counter-current environment to synthesize the dual-network gel.

[0063] (2) Figure 6 As shown, a polymer / hollow nanoparticle composite porous thermal barrier membrane was synthesized inside a gel via in-situ nanopolymerization: Allyl arginine monomer was modified into hollow zirconium carbide (ZrC) nanoparticles through surface grafting modification. 0.16 g of the zirconium carbide (ZrC) nanoparticle / allyl arginine monomer composite was weighed and prepared into a solution, which was stored in syringe No. 1. 0.04 g of the catalyst naphthalimide solution was weighed and stored in syringe No. 2. Both syringes were simultaneously injected into the center of the gel at a high-speed injection rate of 1 mL / s to form the polymer / hollow zirconium carbide (ZrC) nanoparticle composite porous thermal barrier membrane via in-situ nanopolymerization.

[0064] (3) Figure 7 As shown, a layer-by-layer permeation method was used to dope the interior of a double-network organic gel with P-type and N-type thermoelectric ions: 0.3 g of P-type thermoelectric ion Na2SO4 / Na2SO3 was weighed and prepared into a homogeneous solution, which was stored in syringe No. 1. Starting from the bottom layer of the gel, the thermoelectric ion solution was slowly injected into the gel layer by layer at an injection layer height of 0.02 cm and an injection speed of 0.3 mL / s, so that the ions were dispersed uniformly within the gel to the greatest extent possible, thus obtaining a P-type thermoelectric gel. 0.3 g of N-type thermoelectric ion Mn(NO3)3 / Mn(NO3)2 was weighed and prepared into a homogeneous solution, which was stored in syringe No. 2. Starting from the bottom layer of the gel, the thermoelectric ion solution was slowly injected into the gel layer by layer at an injection layer height of 0.02 cm and an injection speed of 0.3 mL / s, so that the ions were dispersed uniformly within the gel to the greatest extent possible, thus obtaining an N-type thermoelectric gel.

[0065] (4) P-type and N-type thermogels are connected in series via flexible electrode platinum wire to form a PN combined thermogel. Twelve PN combined thermogels are connected in series via flexible electrodes and encapsulated in a flexible polyurethane substrate to form a flexible energy supply device, such as... Figure 4 As shown.

[0066] Example 3

[0067] (1) As Figure 5 As shown, a dual-network gel based on inorganic ultralong nanofibers was synthesized via a high-speed fluid counter-current method: ① 0.5 g of praseodymium nanofibers (Pr) were weighed and prepared into an aqueous solution, 0.5 g of terbium triselenide nanofibers (Tb₂Se₃) were weighed and prepared into an aqueous solution, and 0.5 g of dysprosium nanoclusters (Dy) were weighed and prepared into an aqueous solution. All solutions were subjected to magnetic stirring for 2 hours and ultrasonic degassing for 10 minutes. ② The dual-network gel was synthesized using a high-speed fluid counter-current method in a sealed mold. The praseodymium nanofiber (Pr) aqueous solution was stored in injection pump No. 1, the terbium triselenide nanofiber (Tb₂Se₃) aqueous solution was stored in injection pump No. 2, and the dysprosium nanoclusters (Dy) aqueous solution was stored in injection pump No. 3. Injection pumps No. 1 and No. 3 were located on the left side of the mold, and injection pump No. 2 was located on the right side of the mold. The three injection pumps simultaneously injected solutions into the mold at an injection rate of 3 mL / s, forming a high-speed fluid counter-current environment to synthesize the dual-network gel.

[0068] (2) Figure 6 As shown, a polymer / hollow nanoparticle composite porous thermal barrier membrane was synthesized inside a gel via in-situ nanopolymerization: Allyl histidine monomers were modified inside hollow vanadium carbide (VC) nanoparticles through surface grafting modification. 0.16 g of the vanadium carbide (VC) nanoparticle / allyl histidine monomer composite was weighed and prepared into a solution, which was stored in syringe #1. 0.08 g of the catalyst naphthalimide solution was weighed and stored in syringe #2. Both syringes were simultaneously injected into the center of the gel at a high-speed injection rate of 1 mL / s to form the polymer / hollow vanadium carbide (VC) nanoparticle composite porous thermal barrier membrane via in-situ nanopolymerization.

[0069] (3) Figure 7As shown, a layer-by-layer permeation method was used to dope the interior of a double-network organic gel with P-type and N-type thermoelectric ions: 0.6 g of P-type thermoelectric ion Na₂SO₄ / Na₂SO₃ was weighed and prepared into a homogeneous solution, which was stored in syringe No. 1. Starting from the bottom layer of the gel, the thermoelectric ion solution was slowly injected layer by layer into the gel at an injection layer height of 0.03 cm and an injection speed of 0.5 mL / s, so that the ions were dispersed uniformly within the gel to the greatest extent possible, thus obtaining a P-type thermoelectric gel. 0.6 g of N-type thermoelectric ion MnCl₃ / MnCl₂ was weighed and prepared into a homogeneous solution, which was stored in syringe No. 2. Starting from the bottom layer of the gel, the thermoelectric ion solution was slowly injected layer by layer into the gel at an injection layer height of 0.03 cm and an injection speed of 0.5 mL / s, so that the ions were dispersed uniformly within the gel to the greatest extent possible, thus obtaining an N-type thermoelectric gel.

[0070] (4) P-type and N-type thermogels are connected in series via flexible electrode titanium wires to form a PN combined thermogel. Twelve PN combined thermogels are connected in series via flexible electrodes and encapsulated in a flexible substrate polydimethylsiloxane to form a flexible energy supply device, such as... Figure 4 As shown.

[0071] Example 4

[0072] (1) As Figure 5 As shown, a dual-network gel based on inorganic ultralong nanofibers was synthesized via a high-speed fluid counter-current method: ① 1.2 g of lanthanum nanofibers (La) were weighed and prepared into an aqueous solution, 1.2 g of dysprosium triselenide nanofibers (Dy2Se3) were weighed and prepared into an aqueous solution, and 0.8 g of samarium nanoclusters (Sm) were weighed and prepared into an aqueous solution. All solutions were subjected to magnetic stirring for 2 hours and ultrasonic degassing for 10 minutes. ② The dual-network gel was synthesized using a high-speed fluid counter-current method in a sealed mold. The lanthanum nanofiber (La) aqueous solution was stored in injection pump No. 1, the dysprosium triselenide nanofiber (Dy2Se3) aqueous solution was stored in injection pump No. 2, and the samarium nanoclusters (Sm) aqueous solution was stored in injection pump No. 3. Injection pumps No. 1 and No. 3 were placed on the left side of the mold, and injection pump No. 2 was placed on the right side of the mold. The three injection pumps simultaneously injected solutions into the mold at an injection rate of 3 mL / s, forming a high-speed fluid counter-current environment to synthesize the dual-network gel.

[0073] (2) Figure 6As shown, a polymer / hollow nanoparticle composite porous thermal barrier membrane was synthesized inside a gel via in-situ nanopolymerization: propenylserine monomers were modified into hollow manganese sulfide (MnS) nanoparticles through surface grafting modification. 0.2 g of the manganese sulfide (MnS) nanoparticle / propenylserine monomer composite was weighed and prepared into a solution, which was stored in syringe #1. 0.08 g of the catalyst naphthalimide solution was weighed and stored in syringe #2. Both syringes were simultaneously injected into the center of the gel at a high injection rate of 1.5 mL / s to form the polymer / hollow manganese sulfide (MnS) nanoparticle composite porous thermal barrier membrane via in-situ nanopolymerization.

[0074] (3) Figure 7 As shown, a layer-by-layer permeation method was used to dope the interior of a double-network organic gel with P-type and N-type thermoelectric ions: 1.2 g of P-type thermoelectric ion Na₂PO₄ / Na₂PO₃ was weighed and prepared into a homogeneous solution, which was stored in syringe No. 1. Starting from the bottom layer of the gel, the thermoelectric ion solution was slowly injected into the gel layer by layer at an injection layer height of 0.04 cm and an injection speed of 0.5 mL / s, so that the ions were dispersed uniformly within the gel to the greatest extent possible, thus obtaining a P-type thermoelectric gel. Similarly, 1.2 g of N-type thermoelectric ion Mn₂(SO₄)₃ / MnSO₄ was weighed and prepared into a homogeneous solution, which was stored in syringe No. 2. Starting from the bottom layer of the gel, the thermoelectric ion solution was slowly injected into the gel layer by layer at an injection layer height of 0.04 cm and an injection speed of 0.5 mL / s, so that the ions were dispersed uniformly within the gel to the greatest extent possible, thus obtaining an N-type thermoelectric gel.

[0075] (4) P-type and N-type thermoelectric gels are connected in series via flexible electrode conductive grease to form a PN combined thermoelectric gel. Twelve PN combined thermoelectric gels are connected in series via flexible electrodes and encapsulated in a flexible substrate Ecoflex elastomer to form a flexible energy supply device, such as... Figure 4 As shown.

[0076] Example 5

[0077] (1) As Figure 5As shown, a dual-network gel based on inorganic ultralong nanofibers was synthesized via a high-speed fluid counter-current method: ① 1.8 g of cerium nanofibers (Ce), 1.8 g of bismuth disulfide nanofibers (BiS2), and 1.2 g of iridium nanoclusters (Ir) were weighed and prepared into an aqueous solution. All solutions were subjected to magnetic stirring for 3 hours and ultrasonic degassing for 15 minutes. ② The dual-network gel was synthesized using a high-speed fluid counter-current method in a sealed mold. The cerium nanofiber (Ce) aqueous solution was stored in injection pump No. 1, the bismuth disulfide nanofiber (BiS2) aqueous solution was stored in injection pump No. 2, and the iridium nanoclusters (Ir) aqueous solution was stored in injection pump No. 3. Injection pumps No. 1 and No. 3 were located on the left side of the mold, and injection pump No. 2 was located on the right side of the mold. The three injection pumps simultaneously injected solutions into the mold at an injection rate of 5 mL / s, forming a high-speed fluid counter-current environment to synthesize the dual-network gel.

[0078] (2) Figure 6 As shown, a polymer / hollow nanoparticle composite porous heat-resistant membrane was synthesized inside a gel via in-situ nanopolymerization: Allyl tyrosine monomers were modified into hollow chromium trisulfide (Cr2S3) nanoparticles through surface grafting modification. 0.24 g of the chromium trisulfide (Cr2S3) nanoparticle / allyl tyrosine monomer composite was weighed and prepared into a solution, which was stored in syringe No. 1. 0.05 g of a phenanthreneimide catalyst solution was weighed and stored in syringe No. 2. Both syringes were simultaneously injected into the center of the gel at a high injection rate of 3 mL / s to form the polymer / hollow chromium trisulfide (Cr2S3) nanoparticle composite porous heat-resistant membrane via in-situ nanopolymerization.

[0079] (3) Figure 7 As shown, a layer-by-layer permeation method was used to dope the interior of a double-network organic gel with P-type and N-type thermoelectric ions: 1.5 g of P-type thermoelectric ions Na₂PO₄ / Na₂PO₃ were weighed and prepared into a homogeneous solution, which was stored in syringe No. 1. Starting from the bottom layer of the gel, the thermoelectric ion solution was slowly injected layer by layer into the gel at an injection layer height of 0.05 cm and an injection speed of 0.5 mL / s, so that the ions were dispersed uniformly within the gel to the greatest extent possible, thus obtaining a P-type thermoelectric gel. Similarly, 1.5 g of N-type thermoelectric ions Mn(NO₃)₃ / Mn(NO₃)₂ were weighed and prepared into a homogeneous solution, which was stored in syringe No. 2. Starting from the bottom layer of the gel, the thermoelectric ion solution was slowly injected layer by layer into the gel at an injection layer height of 0.05 cm and an injection speed of 0.5 mL / s, so that the ions were dispersed uniformly within the gel to the greatest extent possible, thus obtaining an N-type thermoelectric gel.

[0080] (4) P-type and N-type thermogels are connected in series via flexible electrode conductive grease to form a PN combined thermogel. Twelve PN combined thermogels are connected in series via flexible electrodes and encapsulated in a flexible polyimide substrate to form a flexible energy supply device, such as... Figure 4 As shown.

[0081] Example 6

[0082] (1) As Figure 5 As shown, a dual-network gel based on inorganic ultralong nanofibers was synthesized via a high-speed fluid counter-current method: ① 2.5 g of praseodymium nanofibers (Pr) were weighed and prepared into an aqueous solution, 2.5 g of europium trisulfide nanofibers (Eu2S3) were weighed and prepared into an aqueous solution, and 1.5 g of terbium nanoclusters (Tb) were weighed and prepared into an aqueous solution. All solutions were subjected to magnetic stirring for 3 hours and ultrasonic degassing for 20 minutes. ② The dual-network gel was synthesized using a high-speed fluid counter-current method in a sealed mold. The praseodymium nanofiber (Pr) aqueous solution was stored in injection pump No. 1, the europium trisulfide nanofiber (Eu2S3) aqueous solution was stored in injection pump No. 2, and the terbium nanoclusters (Tb) aqueous solution was stored in injection pump No. 3. Injection pumps No. 1 and No. 3 were located on the left side of the mold, and injection pump No. 2 was located on the right side of the mold. The three injection pumps simultaneously injected solutions into the mold at an injection rate of 6 mL / s, forming a high-speed fluid counter-current environment to synthesize the dual-network gel.

[0083] (2) Figure 6 As shown, a polymer / hollow nanoparticle composite porous thermal barrier membrane was synthesized inside a gel via in-situ nanopolymerization: Allyl lysine monomer was modified into hollow titanium carbide (TiC) nanoparticles through surface grafting modification. 0.3 g of the titanium carbide (TiC) nanoparticle / allyl lysine monomer composite was weighed and prepared into a solution, which was stored in syringe #1. 0.05 g of anthraimide catalyst solution was weighed and stored in syringe #2. Both syringes were simultaneously injected into the center of the gel at a high-speed injection rate of 3 mL / s to form the polymer / hollow titanium carbide (TiC) nanoparticle composite porous thermal barrier membrane via in-situ nanopolymerization.

[0084] (3) Figure 7As shown, a layer-by-layer permeation method was used to dope the interior of a double-network organic gel with P-type and N-type thermoelectric ions: 1.8 g of P-type thermoelectric ion Na₂PO₄ / Na₂PO₃ was weighed and prepared into a homogeneous solution, which was stored in syringe No. 1. Starting from the bottom layer of the gel, the thermoelectric ion solution was slowly injected layer by layer into the gel at an injection layer height of 0.06 cm and an injection speed of 0.5 mL / s, so that the ions were dispersed uniformly within the gel to the greatest extent possible, thus obtaining a P-type thermoelectric gel. Similarly, 1.8 g of N-type thermoelectric ion MnCl₃ / MnCl₂ was weighed and prepared into a homogeneous solution, which was stored in syringe No. 2. Starting from the bottom layer of the gel, the thermoelectric ion solution was slowly injected layer by layer into the gel at an injection layer height of 0.06 cm and an injection speed of 0.5 mL / s, so that the ions were dispersed uniformly within the gel to the greatest extent possible, thus obtaining an N-type thermoelectric gel.

[0085] (4) P-type and N-type thermogels are connected in series via flexible electrode platinum wire to form a PN combined thermogel. Twelve PN combined thermogels are connected in series via flexible electrodes and encapsulated in a flexible polyurethane substrate to form a flexible energy supply device, such as... Figure 4 As shown.

[0086] Example 7

[0087] (1) As Figure 5 As shown, a dual-network gel based on inorganic ultralong nanofibers was synthesized via a high-speed fluid counter-current method: ① 2.5 g of cerium nanofibers (Ce) were weighed and prepared into an aqueous solution, 2.5 g of terbium triselenide nanofibers (Tb₂Se₃) were weighed and prepared into an aqueous solution, and 1.8 g of dysprosium nanoclusters (Dy) were weighed and prepared into an aqueous solution. All solutions were subjected to magnetic stirring for 4 hours and ultrasonic degassing for 20 minutes. ② The dual-network gel was synthesized using a high-speed fluid counter-current method in a sealed mold. The cerium nanofiber (Ce) aqueous solution was stored in injection pump No. 1, the terbium triselenide nanofiber (Tb₂Se₃) aqueous solution was stored in injection pump No. 2, and the dysprosium nanoclusters (Dy) aqueous solution was stored in injection pump No. 3. Injection pumps No. 1 and No. 3 were located on the left side of the mold, and injection pump No. 2 was located on the right side of the mold. The three injection pumps simultaneously injected solutions into the mold at an injection rate of 8 mL / s, forming a high-speed fluid counter-current environment to synthesize the dual-network gel.

[0088] (2) Figure 6As shown, a polymer / hollow nanoparticle composite porous thermal barrier membrane was synthesized inside a gel via in-situ nanopolymerization: Allyl arginine monomer was modified into hollow zirconium carbide (ZrC) nanoparticles through surface grafting modification. 0.18 g of the zirconium carbide (ZrC) nanoparticle / allyl arginine monomer composite was weighed and prepared into a solution, which was stored in syringe No. 1. 2.8 g of the catalyst naphthalimide solution was weighed and stored in syringe No. 2. Both syringes were simultaneously injected into the center of the gel at a high injection rate of 4 mL / s to form the polymer / hollow zirconium carbide (ZrC) nanoparticle composite porous thermal barrier membrane via in-situ nanopolymerization.

[0089] (3) Figure 7 As shown, a layer-by-layer permeation method was used to dope the interior of a double-network organic gel with P-type and N-type thermoelectric ions: 2.4 g of P-type thermoelectric ion NaClO4 / NaClO3 was weighed and prepared into a homogeneous solution, which was stored in syringe No. 1. Starting from the bottom layer of the gel, the thermoelectric ion solution was slowly injected layer by layer into the gel at an injection layer height of 0.07 cm and an injection speed of 1 mL / s, ensuring maximum uniform dispersion of ions within the gel, thus obtaining a P-type thermoelectric gel. Similarly, 2.4 g of N-type thermoelectric ion Mn2(SO4)3 / MnSO4 was weighed and prepared into a homogeneous solution, which was stored in syringe No. 2. Starting from the bottom layer of the gel, the thermoelectric ion solution was slowly injected layer by layer into the gel at an injection layer height of 0.07 cm and an injection speed of 1 mL / s, ensuring maximum uniform dispersion of ions within the gel, thus obtaining an N-type thermoelectric gel.

[0090] (4) P-type and N-type thermogels are connected in series via flexible electrode titanium wires to form a PN combined thermogel. Twelve PN combined thermogels are connected in series via flexible electrodes and encapsulated in a flexible substrate polydimethylsiloxane to form a flexible energy supply device, such as... Figure 4 As shown.

[0091] Example 8

[0092] (1) As Figure 5As shown, a dual-network gel based on inorganic ultralong nanofibers was synthesized via a high-speed fluid counter-current method: ① 3.6 g of praseodymium nanofibers (Pr) and 3.6 g of dysprosium triselenide nanofibers (Dy2Se3) and 1.8 g of samarium nanoclusters (Sm) were weighed and prepared into an aqueous solution. All solutions were subjected to magnetic stirring for 4 hours and ultrasonic degassing for 25 minutes. ② The dual-network gel was synthesized using a high-speed fluid counter-current method in a sealed mold. The praseodymium nanofiber (Pr) aqueous solution was stored in injection pump No. 1, the dysprosium triselenide nanofiber (Dy2Se3) aqueous solution was stored in injection pump No. 2, and the samarium nanoclusters (Sm) aqueous solution was stored in injection pump No. 3. Injection pumps No. 1 and No. 3 were located on the left side of the mold, and injection pump No. 2 was located on the right side of the mold. The three injection pumps simultaneously injected solutions into the mold at an injection rate of 8 mL / s, forming a high-speed fluid counter-current environment to synthesize the dual-network gel.

[0093] (2) Figure 6 As shown, a polymer / hollow nanoparticle composite porous thermal barrier membrane was synthesized inside a gel via in-situ nanopolymerization: Allyl histidine monomers were modified inside hollow vanadium carbide (VC) nanoparticles through surface grafting modification. 0.36 g of the vanadium carbide (VC) nanoparticle / allyl histidine monomer composite was weighed and prepared into a solution, which was stored in syringe #1. 0.08 g of the catalyst phenanthreneimide solution was weighed and stored in syringe #2. Both syringes were simultaneously injected into the center of the gel at a high-speed injection rate of 4 mL / s to form the polymer / hollow vanadium carbide (VC) nanoparticle composite porous thermal barrier membrane via in-situ nanopolymerization.

[0094] (3) Figure 7 As shown, a layer-by-layer permeation method was used to dope the interior of a double-network organic gel with P-type and N-type thermoelectric ions: 2.8 g of P-type thermoelectric ion NaClO4 / NaClO3 was weighed and prepared into a homogeneous solution, which was stored in syringe No. 1. Starting from the bottom layer of the gel, the thermoelectric ion solution was slowly injected layer by layer into the gel at an injection layer height of 0.08 cm and an injection speed of 2 ml / s, ensuring maximum uniform dispersion of ions within the gel, thus obtaining a P-type thermoelectric gel. Similarly, 2.8 g of N-type thermoelectric ion Mn(NO3)3 / Mn(NO3)2 was weighed and prepared into a homogeneous solution, which was stored in syringe No. 2. Starting from the bottom layer of the gel, the thermoelectric ion solution was slowly injected layer by layer into the gel at an injection layer height of 0.08 cm and an injection speed of 2 ml / s, ensuring maximum uniform dispersion of ions within the gel, thus obtaining an N-type thermoelectric gel.

[0095] (4) P-type and N-type thermogels are connected in series via flexible electrode titanium wires to form a PN combined thermogel. Twelve PN combined thermogels are connected in series via flexible electrodes and encapsulated in a flexible substrate Ecoflex elastomer to form a flexible energy supply device, such as... Figure 4 As shown.

[0096] Example 9

[0097] (1) As Figure 5 As shown, a dual-network gel based on inorganic ultralong nanofibers was synthesized via a high-speed fluid counter-current method: ① 4.2 g of lanthanum nanofibers (La) were weighed and prepared into an aqueous solution, 4.2 g of bismuth disulfide nanofibers (BiS2) were weighed and prepared into an aqueous solution, and 2.4 g of europium nanoclusters (Eu) were weighed and prepared into an aqueous solution. All solutions were subjected to magnetic stirring for 5 hours and ultrasonic degassing for 30 minutes. ② The dual-network gel was synthesized using a high-speed fluid counter-current method in a sealed mold. The lanthanum nanofiber (La) aqueous solution was stored in injection pump No. 1, the bismuth disulfide nanofiber (BiS2) aqueous solution was stored in injection pump No. 2, and the europium nanoclusters (Eu) aqueous solution was stored in injection pump No. 3. Injection pumps No. 1 and No. 3 were located on the left side of the mold, and injection pump No. 2 was located on the right side of the mold. The three injection pumps simultaneously injected solutions into the mold at an injection rate of 9 mL / s, forming a high-speed fluid counter-current environment to synthesize the dual-network gel.

[0098] (2) Figure 6 As shown, a polymer / hollow nanoparticle composite porous thermal barrier membrane was synthesized inside a gel via in-situ nanopolymerization: propenylserine monomers were modified into hollow manganese sulfide (MnS) nanoparticles through surface grafting. 0.4 g of the manganese sulfide (MnS) nanoparticle / propenylserine monomer composite was weighed and prepared into a solution, which was stored in syringe #1. 0.1 g of anthraimide catalyst solution was weighed and stored in syringe #2. Both syringes were simultaneously injected into the center of the gel at a high injection rate of 5 mL / s to form the polymer / hollow manganese sulfide (MnS) nanoparticle composite porous thermal barrier membrane via in-situ nanopolymerization.

[0099] (3) Figure 7As shown, a layer-by-layer permeation method was used to dope the interior of a double-network organic gel with P-type and N-type thermoelectric ions: 3g of P-type thermoelectric ion NaClO4 / NaClO3 was weighed and prepared into a homogeneous solution, which was stored in syringe No. 1. Starting from the bottom layer of the gel, the thermoelectric ion solution was slowly injected layer by layer into the gel at an injection layer height of 0.09 cm and an injection speed of 3 ml / s, ensuring maximal uniform dispersion of ions within the gel, thus obtaining a P-type thermoelectric gel. Similarly, 3g of N-type thermoelectric ion MnCl3 / MnCl2 was weighed and prepared into a homogeneous solution, which was stored in syringe No. 2. Starting from the bottom layer of the gel, the thermoelectric ion solution was slowly injected layer by layer into the gel at an injection layer height of 0.09 cm and an injection speed of 3 ml / s, ensuring maximal uniform dispersion of ions within the gel, thus obtaining an N-type thermoelectric gel.

[0100] (4) P-type and N-type thermogels are connected in series via flexible electrode conductive grease to form a PN combined thermogel. Twelve PN combined thermogels are connected in series via flexible electrodes and encapsulated in a flexible polyimide substrate to form a flexible energy supply device, such as... Figure 4 As shown.

[0101] Example 10

[0102] (1) As Figure 5 As shown, a dual-network gel based on inorganic ultralong nanofibers was synthesized via a high-speed fluid counter-current method: ① 5g of lanthanum nanofibers (La) and 5g of terbium triselenide nanofibers (Dy2Se3) were weighed and prepared into an aqueous solution, and 3g of iridium nanoclusters (Ir) were weighed and prepared into an aqueous solution. All solutions were subjected to magnetic stirring for 5 hours and ultrasonic degassing for 30 minutes. ② The dual-network gel was synthesized using a high-speed fluid counter-current method in a sealed mold. The lanthanum nanofiber (La) aqueous solution was stored in injection pump No. 1, the terbium triselenide nanofiber (Dy2Se3) aqueous solution was stored in injection pump No. 2, and the iridium nanoclusters (Ir) aqueous solution was stored in injection pump No. 3. Injection pumps No. 1 and No. 3 were located on the left side of the mold, and injection pump No. 2 was located on the right side of the mold. The three injection pumps simultaneously injected solutions into the mold at an injection rate of 10 mL / s, forming a high-speed fluid counter-current environment to synthesize the dual-network gel.

[0103] (2) Figure 6As shown, a polymer / hollow nanoparticle composite porous heat-resistant membrane was synthesized inside a gel via in-situ nanopolymerization: Allyl tyrosine monomers were modified into hollow chromium trisulfide (Cr2S3) nanoparticles through surface grafting modification. 0.4 g of the chromium trisulfide (Cr2S3) nanoparticle / allyl tyrosine monomer composite was weighed and prepared into a solution, which was stored in syringe No. 1. 0.1 g of the catalyst naphthalimide solution was weighed and stored in syringe No. 2. Both syringes were simultaneously injected into the center of the gel at a high injection rate of 5 mL / s to form the polymer / hollow chromium trisulfide (Cr2S3) nanoparticle composite porous heat-resistant membrane via in-situ nanopolymerization.

[0104] (3) Figure 7 As shown, a layer-by-layer permeation method was used to dope the interior of a double-network organic gel with P-type and N-type thermoelectric ions: 3g of P-type thermoelectric ion Na₂SO₄ / Na₂SO₃ was weighed and prepared into a homogeneous solution, which was stored in syringe No. 1. Starting from the bottom layer of the gel, the thermoelectric ion solution was slowly injected layer by layer into the gel at an injection layer height of 0.1 cm and an injection speed of 3 ml / s, ensuring maximum uniform dispersion of ions within the gel to obtain a P-type thermoelectric gel. Similarly, 3g of N-type thermoelectric ion MnCl₃ / MnCl₂ was weighed and prepared into a homogeneous solution, which was stored in syringe No. 2. Starting from the bottom layer of the gel, the thermoelectric ion solution was slowly injected layer by layer into the gel at an injection layer height of 0.1 cm and an injection speed of 3 ml / s, ensuring maximum uniform dispersion of ions within the gel to obtain an N-type thermoelectric gel.

[0105] (4) P-type and N-type thermogels are connected in series via flexible electrode conductive grease to form a PN combined thermogel. Twelve PN combined thermogels are connected in series via flexible electrodes and encapsulated in a flexible polyimide substrate to form a flexible energy supply device, such as... Figure 4 As shown.

[0106] The above description is merely a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any modifications, equivalent substitutions, and improvements made by those skilled in the art within the scope of the technology disclosed in the present invention, and within the spirit and principles of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A method for preparing a dual-network thermoelectric gel based on inorganic nanofibers, characterized in that, Includes the following steps: (1) Synthesis of a dual-network gel based on inorganic nanofibers by high-speed fluid counter-current method: Prepare an aqueous solution of inorganic nanofiber No. 1 and store it in injection pump No.

1. Prepare an aqueous solution of inorganic nanofiber No. 2 and store it in injection pump No.

2. Prepare an aqueous solution of metal clusters and store it in injection pump No.

3. All solutions need to be magnetically stirred and ultrasonically degassed. Place injection pump No. 1 and injection pump No. 3 on the left side of the mold and injection pump No. 2 on the right side of the mold. The three injection pumps simultaneously inject the solutions into the mold to form a high-speed fluid collision environment to synthesize a double network gel. The injection speed of the three injection pumps is the same, which is 1-10 ml / s. The first and second cross-linked networks are formed by negatively charged inorganic nanofibers No. 1 and No. 2 and positively charged metal clusters through electrostatic interaction, respectively. In addition, two kinds of inorganic nanofibers with opposite magnetism are entangled with each other through magnetic interaction, ultimately forming a double cross-linked network structure. (2) Synthesis of polymer / hollow nanoparticle composite porous heat-insulating membranes within gels via in-situ nanopolymerization: Prepare a hollow nanoparticle / propylene amino acid monomer complex solution and store it in syringe No.

1. Store the catalyst solution in syringe No.

2. Simultaneously inject the two syringes into the middle of the double network gel obtained in step (1) at high speed. The hollow nanoparticle / propylene amino acid monomer complex and the catalyst form a polymer / hollow nanoparticle composite porous heat-resistant membrane inside the gel through in-situ nanopolymerization. The injection speed of the two syringes is the same, which is 0.5 to 5 ml / s. (3) Doping the gel with P-type and N-type thermoelectric ions through a layer-by-layer permeation method: Prepare a homogeneous P-type thermoelectric ion solution and store it in syringe No.

1. Starting from the bottom layer of the gel obtained in step (2), slowly inject the P-type thermoelectric ion solution into the gel layer by layer so that the ions are dispersed uniformly in the gel to the greatest extent, and obtain a P-type thermoelectric gel. Prepare a homogeneous N-type thermoelectric ion solution and store it in a second syringe. Starting from the bottom layer of the gel obtained in step (2), slowly inject the N-type thermoelectric ion solution into the gel layer by layer to make the ions dispersed uniformly in the gel to the greatest extent possible, and obtain an N-type thermoelectric gel. The injection speed of both syringes is the same, which is 0.1 to 3 ml / s; (4) P-type thermogel and N-type thermogel are connected in series through flexible electrodes to form a PN combined thermogel.

2. The method for preparing a dual-network thermoelectric gel based on inorganic nanofibers according to claim 1, characterized in that, In step (1), the first inorganic nanofiber and the second inorganic nanofiber are selected from two combinations of lanthanum nanofiber, cerium nanofiber, praseodymium nanofiber, bismuth disulfide nanofiber, europium trisulfide nanofiber, terbium triselenide nanofiber, and dysprosium triselenide nanofiber. The metal clusters are selected from one of europium nanoclusters, terbium nanoclusters, dysprosium nanoclusters, samarium nanoclusters, and iridium nanoclusters; The mass ratio of the inorganic nanofibers to the metal clusters is (1-5):(0.01-1).

3. The method for preparing a dual-network thermoelectric gel based on inorganic nanofibers according to claim 1, characterized in that, The solution stirring time in step (1) is 1 to 5 hours, and the ultrasonic degassing treatment time is 5 to 30 minutes.

4. The method for preparing a dual-network thermoelectric gel based on inorganic nanofibers according to claim 1, characterized in that, The hollow nanoparticles in step (2) are selected from one of titanium carbide, zirconium carbide, vanadium carbide, manganese sulfide, and dichromium trisulfide; the propylene amino acid monomer is selected from one of propylene lysine, propylene arginine, propylene histidine, propylene serine, and propylene tyrosine; the mass ratio of the hollow nanoparticles to the propylene amino acid monomer is (0.1-2):(1-20).

5. The method for preparing a dual-network thermoelectric gel based on inorganic nanofibers according to claim 1, characterized in that, The catalyst is selected from one of naphthalimide, phenanthreneimide, and anthraquinoneimide.

6. The method for preparing a dual-network thermoelectric gel based on inorganic nanofibers according to claim 1, characterized in that, The P-type thermoelectric ions mentioned in step (3) are selected from one of Na2SO4 / Na2SO3, Na2PO4 / Na2PO3, and NaClO4 / NaClO3; the mass of the P-type thermoelectric ions is 0.1% to 3% of the mass of the double network gel; The N-type thermoelectric ions are selected from one of Mn2(SO4)3 / MnSO4, Mn(NO3)3 / Mn(NO3)2, and MnCl3 / MnCl2; the mass of the N-type thermoelectric ions is 0.1% to 3.0% of the mass of the dual-network gel.

7. The method for preparing a dual-network thermoelectric gel based on inorganic nanofibers according to claim 1, characterized in that, In step (3), the height of the injection layer is 0.01 to 0.1 cm / layer.

8. The method for preparing a dual-network thermoelectric gel based on inorganic nanofibers according to claim 1, characterized in that, The flexible electrode mentioned in step (4) is selected from one of platinum wire, titanium wire, graphite paper, and conductive grease.

9. A dual-network thermoelectric gel based on inorganic nanofibers, characterized in that, It is prepared by the preparation method according to any one of claims 1 to 8.

10. The application of the inorganic nanofiber-based dual-network thermoelectric gel according to claim 9 in the preparation of flexible energy supply devices.

11. The application according to claim 10, characterized in that, Multiple PN-combined thermoelectric gels are connected in series via flexible electrodes and encapsulated in a flexible substrate to form a flexible energy supply device.

12. The application according to claim 11, characterized in that, The flexible electrode is selected from one of platinum wire, titanium wire, graphite paper, and conductive grease; the flexible substrate is selected from one of polyimide, polyurethane, polydimethylsiloxane, and Ecoflex elastomer.

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