Preparation method, product and application of high-temperature-resistant flexible metallized ceramic nanofiber composite electrode

Abstract

The invention belongs to the related technical field of flexible electrodes, and discloses a preparation method, a product and application of a high-temperature-resistant flexible metallized ceramic nanofiber composite electrode. The method comprises the following steps: carrying out electrostatic spinning on electrostatic spinning sol doped with an organic polymer to obtain a precursor of a flexible ceramic nanofiber membrane; carrying out primary high-temperature calcination on the precursor to remove the doped organic polymer so as to obtain a flexible ceramic nanofiber membrane; growing and coating a metal conductive layer on the surface of the flexible ceramic nanofiber membrane to obtain an electrode precursor; and carrying out secondary high-temperature calcination on the electrode precursor to obtain the required composite electrode. The invention also discloses a product obtained by the preparation method and application. According to the invention, the problem that the flexible sensor is not resistant to high temperature is solved.

Description

Technical Field

[0001] This invention belongs to the field of flexible electrode technology, and more specifically, relates to a method for preparing a high-temperature resistant flexible metallized ceramic nanofiber composite electrode, its product, and its application. Background Technology

[0002] Emerging demands in energy systems, firefighting, and aerospace sectors urgently require sensors capable of continuous and reliable operation at extreme temperatures, often approaching or exceeding 800°C. The safe and reliable operation of flexible sensors at high temperatures heavily relies on the thermal stability of their electrode materials. Traditional polymer-based flexible sensors fail under these conditions due to inherent limitations, including poor thermal stability above 400°C, irreversible softening / degradation, and significant creep under thermal stress. Furthermore, while some work on flexible high-temperature resistant sensors has been reported, they are structurally simple and functionally limited, responding only to a single physical quantity such as temperature, pressure, or strain. Research on flexible high-temperature resistant multifunctional sensors capable of real-time monitoring of two or more physical quantities in situ remains lacking. Therefore, these inherent material failure modes fundamentally limit their use in high-temperature environments, highlighting the need to develop next-generation flexible high-temperature resistant composite electrodes.

[0003] Ceramics are non-metallic inorganic materials with high hardness, wear resistance, high temperature resistance, corrosion resistance, and good electrical insulation, making them widely used in chemical, automotive, and aerospace industries. However, the inherent brittleness of ceramics makes them difficult to apply directly to complex curved surfaces or moving parts. Although techniques such as electrospinning can produce flexible ceramic fibers, these fibers are typically insulating and cannot meet the requirements for high-temperature conductivity. While metallization methods such as magnetron sputtering can impart conductivity to ceramics, metal-ceramic composites are prone to failure at high temperatures due to thermal expansion mismatch and material oxidation, especially at the micro- and nano-scale, where high specific surface area exacerbates this failure. Therefore, how to maintain the excellent high-temperature resistance of ceramics while endowing them with the necessary flexibility and high-temperature conductivity stability has become a key technological bottleneck that urgently needs to be overcome in developing composite electrodes that combine flexibility and high-temperature resistance. Summary of the Invention

[0004] In view of the above-mentioned defects or improvement needs of the existing technology, the present invention provides a method for preparing a high-temperature resistant flexible metallized ceramic nanofiber composite electrode, a product and its application, which solves the problem that traditional composite electrodes cannot maintain high temperature resistance while possessing flexibility and high-temperature conductivity stability.

[0005] To achieve the above objectives, according to one aspect of the present invention, a method for preparing a high-temperature resistant flexible metallized ceramic nanofiber composite electrode is provided, the method comprising the following steps: Electrospinning of an electrospinning sol doped with organic polymers was performed to obtain a precursor for flexible ceramic nanofiber membranes. The precursor is subjected to a high-temperature calcination to remove the doped organic polymer, thereby obtaining a flexible ceramic nanofiber membrane. A metal conductive layer is grown and coated on the surface of the flexible ceramic nanofiber membrane to obtain an electrode precursor. The desired composite electrode is obtained by secondary high-temperature calcination of the electrode precursor.

[0006] More preferably, the organic polymer is one or any combination of polyethylene oxide and polyvinyl alcohol, wherein the organic polymer accounts for 1 to 10 wt% of the total mass of the electrospinning sol.

[0007] More preferably, the temperature of the first high-temperature calcination is 600℃~1100℃, followed by holding at that temperature for 30 min~120 min.

[0008] More preferably, the metal conductive layer is one or a combination of platinum, gold, and rhodium.

[0009] More preferably, the temperature of the secondary high-temperature calcination is 200℃~800℃, and the holding time is 30 min~120 min.

[0010] More preferably, the parameters for electrospinning are set as follows: the collecting roller speed is 80 r / min to 240 r / min, the voltage is 10 kV to 20 kV, and the receiving distance is 10 cm to 25 cm.

[0011] More preferably, a metal conductive layer is grown and coated on the surface of the flexible ceramic nanofiber membrane by magnetron sputtering, with the sputtering parameters set as follows: sputtering power of 50 W to 200 W and sputtering time of 10 min to 30 min.

[0012] According to another aspect of the present invention, a composite electrode prepared by the preparation method described above is provided.

[0013] According to another aspect of the present invention, a method for preparing a high-temperature resistant in-situ temperature-pressure dual-function sensor using the composite electrode described above is provided, the method comprising the following steps: The composite electrode is patterned and then attached to a mica sheet. A mica sheet with a metal conductive layer attached to its surface is placed opposite another mica sheet with a patterned composite electrode attached to it, thereby encapsulating the patterned composite electrode between the mica sheets to obtain the desired sensor.

[0014] According to another aspect of the present invention, a sensor prepared using the method described above is provided.

[0015] In summary, the technical solutions conceived by this invention have the following beneficial effects compared with the prior art: 1. This invention utilizes an electrospinning sol doped with organic polymers for electrospinning, followed by calcination to remove organic matter, and then growth of a conductive metal layer on the surface. A second calcination is then performed to obtain a composite electrode. This process first yields a flexible fiber film framework primarily composed of oxide ceramics after the decomposition of organic matter, which possesses flexibility, high-temperature resistance, and electrical insulation properties. The subsequent surface growth of the conductive metal layer allows for the fabrication of a flexible, high-temperature resistant composite electrode with adjustable electrical properties on only one side of the film. This provides a solid foundation for manufacturing flexible, high-temperature resistant thin-film sensors, achieving a balance between high-temperature resistance, flexibility, and high-temperature conductivity stability.

[0016] 2. The first calcination temperature of this invention is 600℃~1100℃, followed by a holding time of 30min~120min. The second calcination temperature is 200℃~800℃, with a holding time of 30min~120min. The purpose of the two high-temperature calcinations is to remove organic polymer components from the fiber and to regulate the continuity and distribution of the microstructure of the metal conductive layer on the fiber, thereby adjusting the macroscopic resistivity of the material. Specifically, the temperature of the first calcination is generally set higher than the decomposition temperature of the polymer used in the electrospinning process to ensure complete polymer decomposition. The temperature of the second calcination depends on the melting point of the metal conductive layer, generally between 0.5 and 0.7 times the melting point, and is used to promote the crystalline phase stability and interconnection of the metal conductive layer, thereby achieving bidirectional enhancement of the mechanical and electrical properties of the fiber composite electrode under high-temperature conditions.

[0017] 3. This invention grows a continuous micro / nano-scale conductive metal layer on the surface of flexible ceramic nanofibers, enhancing the bonding strength between fibers and between metal and ceramic, and improving the structural damage problem of the material under high temperature and large deformation. Furthermore, by selecting different types of metal targets and power ratios, ceramic fibers with different metal compositions are prepared using magnetron sputtering technology, and high-temperature calcination is used to control the microstructure of the metal-ceramic fiber interface, thereby achieving control over the high-temperature thermal stability and conductivity of the composite electrode material.

[0018] 4. The flexible ceramic nanofiber membrane and micro / nano-scale metal conductive layer prepared by this invention are tightly composited, exhibiting excellent mechanical properties, thermal stability, and conductivity. Furthermore, the material's performance can be customized by adjusting the metal composition and high-temperature calcination parameters to meet the application requirements of operating temperature and resistance. For example, we selected a high-melting-point, oxidation-resistant, and low-resistivity gold-platinum binary noble metal alloy, combined with appropriate high-temperature calcination process parameters, to obtain a high-temperature resistant flexible metallized ceramic nanofiber composite electrode. The final assembled thin-film piezoresistive flexible high-temperature sensor can achieve real-time in-situ temperature-pressure sensing over a wide temperature range from room temperature to above 800°C. Attached Figure Description

[0019] Figure 1 This is a flowchart of a method for preparing a high-temperature resistant flexible metallized ceramic nanofiber composite electrode according to a preferred embodiment of the present invention.

[0020] Figure 2 This is a shape diagram of the flexible metal-ceramic composite nanofiber membrane obtained according to a preferred embodiment of the present invention. Figure 3 This is a scanning electron microscope image of a flexible metal-ceramic composite nanofiber membrane obtained according to a preferred embodiment of the present invention.

[0021] Figure 4 This is a schematic diagram of the structure of a flexible, high-temperature resistant, in-situ temperature-pressure dual-function sensor obtained according to a preferred embodiment of the present invention.

[0022] Figure 5 This is a view of the external shape of a flexible, high-temperature resistant, in-situ temperature-pressure dual-function sensor obtained according to a preferred embodiment of the present invention. Detailed Implementation

[0023] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention. Furthermore, the technical features involved in the various embodiments of this invention described below can be combined with each other as long as they do not conflict with each other.

[0024] A method for preparing a high-temperature resistant flexible metallized ceramic nanofiber composite electrode includes the following steps: S1. First, an organic polymer-doped electrospinning sol is prepared based on the sol-gel method, and then the electrospinning sol is used to prepare a flexible ceramic nanofiber membrane precursor doped with organic polymers by electrospinning.

[0025] Preferably, the organic polymer includes one or any combination of polyethylene oxide, polyvinyl alcohol, and polyvinylpyrrolidone, wherein the organic polymer accounts for 1 to 10 wt% of the total mass of the electrospinning sol.

[0026] Preferably, the inorganic sol in the electrospinning sol includes one or any combination of aluminum source, zirconium source, silicon source, and titanium source, wherein the inorganic sol accounts for 10 to 50 wt% of the total mass of the electrospinning sol.

[0027] Preferably, the electrospinning parameters are set as follows: spinning speed is 1-5 mL / h, collecting drum speed is 80-240 r / min, voltage is 10-25 kV, receiving distance is 10-25 cm, humidity is 20-40%, and temperature is 20-30 ℃.

[0028] S2. The flexible ceramic nanofiber membrane precursor is placed in a muffle furnace and the doped organic polymer is removed by high-temperature calcination to obtain the flexible ceramic nanofiber membrane.

[0029] Preferably, the high-temperature calcination parameters are set as follows: first, the temperature is raised from room temperature to 600~1100℃ in an air atmosphere at a rate of 2~10℃ / min, then held for 30~120min, and then cooled naturally.

[0030] S3. A metal conductive layer is grown on the surface of a flexible ceramic nanofiber membrane using magnetron sputtering technology to obtain a flexible metal-ceramic nanofiber precursor electrode.

[0031] Preferably, the metal conductive layer comprises one or any combination of platinum, gold, silver, rhodium, palladium, and the metal composition ratio is varied by selecting the type of target and the power during co-sputtering.

[0032] Preferably, the magnetron sputtering parameters are set as follows: vacuum degree is 1×10⁻⁶. -3 The sputtering parameters are: Pa, argon flow rate 50 sccm, pressure 0.8–1.2 Pa, substrate temperature 20–100 ℃, sputtering power 50–200 W, and sputtering time 10–20 min.

[0033] S4. The flexible metal-ceramic composite nanofiber precursor membrane is placed in a muffle furnace for high-temperature calcination. The calcination temperature and duration are controlled to obtain flexible metal-ceramic composite nanofiber membranes with different electrical properties.

[0034] Preferably, the high-temperature calcination parameters are set as follows: first, the temperature is raised from room temperature to 800℃ in an air atmosphere at a rate of 2-10℃ / min, and held for 30-120 min, followed by natural cooling.

[0035] This invention also discloses a method for fabricating a flexible, high-temperature resistant, in-situ temperature-pressure dual-function sensor using the aforementioned composite electrode, the method comprising the following steps: Flexible metal-ceramic composite nanofiber membranes were processed into patterned flexible metal-ceramic composite nanofiber electrodes using laser cutting technology, and then encapsulated with fluorine crystal mica sheets with the same metal conductive layer grown on them to obtain a flexible, high-temperature resistant, in-situ temperature-pressure dual-function sensor.

[0036] Preferably, the laser cutting parameters are as follows: cutting speed 250~1000 mm / s, laser frequency 200~400 kHz, laser power 1~15W, number of cuttings 1~10, and the patterned electrode line width obtained by cutting is 0.2~1 mm.

[0037] Preferably, the encapsulation process is as follows: First, a layer of high-temperature resistant adhesive is applied to a fluorine crystal mica sheet, and a patterned flexible metal-ceramic nanofiber composite electrode is attached. Then, another fluorine crystal mica sheet with the same metal layer grown on it is used for encapsulation.

[0038] like Figure 4 As shown, the flexible, high-temperature resistant, in-situ temperature-pressure dual-function sensor prepared according to the above method includes two sensing electrode circuits: a resistance temperature sensor and a piezoresistive pressure sensor, with a total of four pins. The specific decoupled temperature and pressure dual-function sensing principle is as follows: Temperature sensors operate based on the thermal resistance effect of metals, as shown in the formula:

[0039] In the formula, , To represent the current temperature T Reference temperature T The resistance of the temperature sensor at 0 degrees Celsius. The response signal of the temperature sensor is numerically equal to the rate of change of resistance. Depending on the metal material, it can generally be fitted as a univariate function of temperature T using a first- or second-order polynomial.

[0040] Although the temperature sensor is also subjected to pressure when pressure is applied, the piezoresistive effect is almost negligible because the electrode circuit and the counter electrode are not connected. Therefore, the temperature... T Can be directly from The solution is obtained.

[0041] The pressure sensor operates based on the piezoresistive effect of the interdigitated structure, as shown in the formula:

[0042] In the formula, , For temperature TApply current pressure P Reference pressure P The resistance value of the pressure sensor at 0. The response signal of the pressure sensor is numerically equal to the rate of change of resistance, and is a function of temperature. T ,pressure P A bivariate function.

[0043] When the pressure P is large enough ( P (→+∞), the piezoresistive effect of the pressure sensor reaches its limit. At this point, the contact resistance of the pressure sensor is approximately 0, and the change in resistance is entirely due to the thermal resistance effect of the pressure sensor's electrode circuit itself, which can be expressed by the following equation:

[0044]

[0045] The relevant experimental results show that It can be fitted with a first- or second-order polynomial as a function of temperature. T It is a univariate function. Therefore, it can be solved sequentially. , Finally, the current pressure is calculated. P This enables the decoupled real-time sensing function of a flexible, high-temperature resistant, in-situ temperature-pressure dual-function sensor.

[0046] like Figure 5 As shown, the flexible, high-temperature resistant, in-situ temperature-pressure dual-function sensor assembled by S5 has good flexibility.

[0047] The present invention will be further described below with reference to specific embodiments and comparative examples.

[0048] Example 1 S1 uses aluminum chloride hexahydrate and aluminum isopropoxide as aluminum sources, zirconium acetate as zirconium source, water and ethanol as solvents, acetic acid as catalyst, and polyethylene oxide (Mv = 300000 g / mol) as spinning aid.

[0049] A mixed solvent of water, ethanol, and acetic acid was rapidly stirred in a beaker at a volume ratio of 6:2:1. Then, 0.18 mmol / L aluminum chloride hexahydrate and 0.42 mmol / L aluminum isopropoxide were dissolved sequentially and the mixture was sealed. The mixture was then rapidly stirred at room temperature for 24 h to obtain a clear and transparent alumina sol. The alumina sol was then mixed with a zirconium acetate solution to achieve a molar ratio of aluminum to zirconium of 1:2. Finally, 1 wt% polyethylene oxide was added, and the mixture was rapidly stirred at room temperature for 24 h to obtain a zirconium oxide-alumina composite electrospinning sol.

[0050] After filtering the prepared electrospinning sol, it was loaded into the electrospinning machine using a syringe. The electrospinning parameters were set as follows: spinning speed 1.2 mL / h, collecting drum rotation speed 80 r / min, voltage 15 kV, receiving distance 20 cm, humidity 25%, and temperature 25 ℃. Following these electrospinning parameters, a flexible ceramic nanofiber membrane precursor was obtained on the collecting drum device.

[0051] S2 The flexible ceramic nanofiber membrane precursor was placed in a muffle furnace for high-temperature calcination. The temperature was increased from room temperature to 800℃ at a rate of 10℃ / min, held for 120 min, and then allowed to cool naturally to obtain the flexible ceramic nanofiber membrane.

[0052] S3. The flexible ceramic nanofiber film is placed in a magnetron sputtering apparatus. High-purity platinum and high-purity gold are selected as sputtering targets. The magnetron sputtering parameters are set as follows: vacuum degree is 1×10⁻⁶. -3 The sputtering conditions were as follows: argon flow rate of 50 sccm, pressure of 0.9 Pa, substrate temperature of 100 ℃, sputtering power of platinum target of 50 W, sputtering power of gold target of 150 W, and sputtering time of 20 min. After magnetron sputtering, a flexible metal-ceramic composite nanofiber precursor film was obtained.

[0053] S4 The flexible metal-ceramic nanofiber precursor membrane was placed in a muffle furnace for high-temperature calcination. The temperature was increased from room temperature to 800 ℃ at a rate of 10 ℃ / min, held for 120 min, and then cooled naturally to obtain the flexible metallized ceramic nanofiber composite.

[0054] S5 uses laser cutting technology to process a flexible metal-ceramic composite nanofiber membrane into a patterned flexible metal-ceramic composite nanofiber electrode, which is then encapsulated with a fluorine crystal mica sheet with the same metal conductive layer grown on it, resulting in a flexible, high-temperature resistant, in-situ temperature-pressure dual-function sensor. The laser cutting parameters are set as follows: cutting speed 500 mm / s, laser frequency 400 kHz, laser power 10 W, cutting times 10 times, and the resulting patterned electrode linewidth is 0.8 mm.

[0055] Example 2 S1 uses aluminum chloride hexahydrate and aluminum isopropoxide as aluminum sources, zirconium acetate as zirconium source, water and ethanol as solvents, acetic acid as catalyst, and polyethylene oxide (Mv = 300000 g / mol) as spinning aid.

[0056] A mixed solvent of water, ethanol, and acetic acid was rapidly stirred in a beaker at a volume ratio of 6:2:1. Then, 0.18 mmol / L aluminum chloride hexahydrate and 0.42 mmol / L aluminum isopropoxide were dissolved sequentially and the mixture was sealed. The mixture was then rapidly stirred at room temperature for 24 h to obtain a clear and transparent alumina sol. The alumina sol was then mixed with a zirconium acetate solution to achieve a molar ratio of aluminum to zirconium of 1:4. Finally, 2 wt% polyethylene oxide was added, and the mixture was rapidly stirred at room temperature for 24 h to obtain a zirconium oxide-alumina composite electrospinning sol.

[0057] After filtering the prepared electrospinning sol, it was loaded into the electrospinning machine using a syringe. The electrospinning parameters were set as follows: spinning speed 1 mL / h, collecting drum rotation speed 240 r / min, voltage 10 kV, receiving distance 10 cm, humidity 25%, and temperature 25 ℃. Following these electrospinning parameters, a flexible ceramic nanofiber membrane precursor was obtained on the collecting drum device.

[0058] S2 The flexible ceramic nanofiber membrane precursor was placed in a muffle furnace for high-temperature calcination. The temperature was increased from room temperature to 700℃ at a rate of 10℃ / min, held for 60 min, and then cooled naturally to obtain the flexible ceramic nanofiber membrane.

[0059] S3. The flexible ceramic nanofiber film is placed in a magnetron sputtering apparatus. High-purity platinum and high-purity gold are selected as sputtering targets. The magnetron sputtering parameters are set as follows: vacuum degree is 1×10⁻⁶. -3 The sputtering conditions were as follows: argon flow rate of 50 sccm, pressure of 0.9 Pa, substrate temperature of 100 ℃, sputtering power of platinum target of 50 W, sputtering power of gold target of 150 W, and sputtering time of 20 min. After magnetron sputtering, a flexible metal-ceramic composite nanofiber precursor film was obtained.

[0060] S4 The flexible metal-ceramic nanofiber precursor membrane was placed in a muffle furnace for high-temperature calcination. The temperature was increased from room temperature to 800 ℃ at a rate of 10 ℃ / min, held for 120 min, and then cooled naturally to obtain the flexible metallized ceramic nanofiber composite.

[0061] S5 uses laser cutting technology to process a flexible metal-ceramic composite nanofiber membrane into a patterned flexible metal-ceramic composite nanofiber electrode, which is then encapsulated with a fluorine crystal mica sheet with the same metal conductive layer grown on it, resulting in a flexible, high-temperature resistant, in-situ temperature-pressure dual-function sensor. The laser cutting parameters are set as follows: cutting speed 500 mm / s, laser frequency 400 kHz, laser power 10 W, cutting times 10 times, and the resulting patterned electrode linewidth is 0.8 mm.

[0062] Example 3 S1 uses tetraethyl orthosilicate as the silicon source, water and ethanol as solvents, oxalic acid as a catalyst, and polyvinyl alcohol (type 1788) as a spinning aid.

[0063] First, tetraethyl orthosilicate, water, ethanol, and oxalic acid were mixed in a beaker at a molar ratio of 0.15:1:0.2:0.001 and stirred for 24 hours to obtain a silica sol. Then, a 10 wt% polyvinyl alcohol aqueous solution was prepared, and the two were mixed in equal mass and stirred for 24 hours to obtain a silica electrospinning sol.

[0064] After filtering the prepared electrospinning sol, it was loaded into the electrospinning machine using a syringe. The electrospinning parameters were set as follows: spinning speed 1.5 mL / h, collecting drum rotation speed 120 r / min, voltage 20 kV, receiving distance 25 cm, humidity 30%, and temperature 30 ℃. Following these electrospinning parameters, a flexible ceramic nanofiber membrane precursor was obtained on the collecting drum device.

[0065] S2 The flexible ceramic nanofiber membrane precursor was placed in a muffle furnace for high-temperature calcination. The temperature was increased from room temperature to 600℃ at a rate of 10℃ / min, held for 30 min, and then cooled naturally to obtain the flexible ceramic nanofiber membrane.

[0066] S3. The flexible ceramic nanofiber film is placed in a magnetron sputtering apparatus. High-purity platinum and high-purity gold are selected as sputtering targets. The magnetron sputtering parameters are set as follows: vacuum degree is 1×10⁻⁶. -3 The sputtering parameters were: argon flow rate 50 sccm, pressure 0.9 Pa, substrate temperature 100 ℃, platinum target sputtering power 50 W, gold target sputtering power 150 W, and sputtering time 10 min. After magnetron sputtering, a flexible metal-ceramic composite nanofiber precursor film was obtained.

[0067] S4 The flexible metal-ceramic nanofiber precursor membrane was placed in a muffle furnace for high-temperature calcination. The temperature was increased from room temperature to 800 ℃ at a rate of 10 ℃ / min, held for 120 min, and then cooled naturally to obtain the flexible metallized ceramic nanofiber composite.

[0068] S5 uses laser cutting technology to process a flexible metal-ceramic composite nanofiber membrane into a patterned flexible metal-ceramic composite nanofiber electrode, which is then encapsulated with a fluorine crystal mica sheet with the same metal conductive layer grown on it, resulting in a flexible, high-temperature resistant, in-situ temperature-pressure dual-function sensor. The laser cutting parameters are set as follows: cutting speed 500 mm / s, laser frequency 400 kHz, laser power 10 W, cutting times 10 times, and the resulting patterned electrode linewidth is 0.8 mm.

[0069] Example 4 S1 uses tetraethyl orthosilicate as the silicon source, water and ethanol as solvents, oxalic acid as a catalyst, and polyvinyl alcohol (type 1788) as a spinning aid.

[0070] First, tetraethyl orthosilicate, water, ethanol, and oxalic acid were mixed in a beaker at a molar ratio of 0.15:1:0.2:0.001 and stirred for 24 hours to obtain a silica sol. Then, a 10 wt% polyvinyl alcohol aqueous solution was prepared, and the two were mixed in a mass ratio of 2:1 and stirred for 24 hours to obtain a silica electrospinning sol.

[0071] After filtering the prepared electrospinning sol, it was loaded into the electrospinning machine using a syringe. The electrospinning parameters were set as follows: spinning speed of 2 mL / h, collecting drum rotation speed of 120 r / min, voltage of 20 kV, receiving distance of 25 cm, humidity of 30%, and temperature of 30 ℃. Following these electrospinning parameters, a flexible ceramic nanofiber membrane precursor was obtained on the collecting drum device.

[0072] S2 The flexible ceramic nanofiber membrane precursor was placed in a muffle furnace for high-temperature calcination. The temperature was increased from room temperature to 1000℃ at a rate of 10℃ / min, held for 120 min, and then allowed to cool naturally to obtain the flexible ceramic nanofiber membrane.

[0073] S3. The flexible ceramic nanofiber film is placed in a magnetron sputtering apparatus. High-purity platinum and high-purity gold are selected as sputtering targets. The magnetron sputtering parameters are set as follows: vacuum degree is 1×10⁻⁶. -3 The sputtering conditions were as follows: argon flow rate of 50 sccm, pressure of 0.9 Pa, substrate temperature of 100 ℃, sputtering power of platinum target of 50 W, sputtering power of gold target of 150 W, and sputtering time of 30 min. After magnetron sputtering, a flexible metal-ceramic composite nanofiber precursor film was obtained.

[0074] S4 The flexible metal-ceramic nanofiber precursor membrane was placed in a muffle furnace for high-temperature calcination. The temperature was increased from room temperature to 800 ℃ at a rate of 10 ℃ / min, held for 30 min, and then cooled naturally to obtain the flexible metallized ceramic nanofiber composite.

[0075] S5 uses laser cutting technology to process a flexible metal-ceramic composite nanofiber membrane into a patterned flexible metal-ceramic composite nanofiber electrode, which is then encapsulated with a fluorine crystal mica sheet with the same metal conductive layer grown on it, resulting in a flexible, high-temperature resistant, in-situ temperature-pressure dual-function sensor. The laser cutting parameters are set as follows: cutting speed 500 mm / s, laser frequency 400 kHz, laser power 10 W, cutting times 10 times, and the resulting patterned electrode linewidth is 0.8 mm.

[0076] Example 5 S1 uses tetraethyl orthosilicate as the silicon source, zirconium acetate as the zirconium source, water and ethanol as solvents, oxalic acid as the catalyst, and polyethylene oxide (Mv = 300000 g / mol) as the spinning aid.

[0077] First, tetraethyl orthosilicate, water, ethanol, and oxalic acid were mixed in a beaker at a molar ratio of 5:1:2:0.01 and stirred for 12 hours to obtain a silica sol. Then, polyethylene oxide powder was dissolved in zirconium acetate to obtain a zirconium sol containing 2 wt% polyethylene oxide, and stirred for approximately 12 hours. Subsequently, the silica sol and zirconium sol were mixed at a certain mass ratio, making the silicon:zirconium molar ratio 4:6, and stirred for 12 hours to obtain an electrospinning sol.

[0078] After filtering the prepared electrospinning sol, it was loaded into the electrospinning machine using a syringe. The electrospinning parameters were set as follows: spinning speed 1.5 mL / h, collecting drum rotation speed 120 r / min, voltage 20 kV, receiving distance 15 cm, humidity 30%, and temperature 30 ℃. Following these electrospinning parameters, a flexible ceramic nanofiber membrane precursor was obtained on the collecting drum device.

[0079] S2 The flexible ceramic nanofiber membrane precursor was placed in a muffle furnace for high-temperature calcination. The temperature was increased from room temperature to 1100℃ at a rate of 10℃ / min, held for 120 min, and then cooled naturally to obtain the flexible ceramic nanofiber membrane.

[0080] S3. The flexible ceramic nanofiber film is placed in a magnetron sputtering apparatus. A high-purity platinum-rhodium alloy (platinum:rhodium molar ratio of 9:1) is selected as the sputtering target. The magnetron sputtering parameters are set as follows: vacuum degree is 1×10⁻⁶. -3 The sputtering conditions were as follows: argon flow rate of 50 sccm, pressure of 0.9 Pa, substrate temperature of 100 ℃, platinum-rhodium alloy target power of 100 W, and sputtering time of 15 min. After magnetron sputtering, a flexible metal-ceramic composite nanofiber precursor film was obtained.

[0081] S4 The flexible metal-ceramic nanofiber precursor membrane was placed in a muffle furnace for high-temperature calcination. The temperature was increased from room temperature to 800 ℃ at a rate of 10 ℃ / min, held for 120 min, and then cooled naturally to obtain the flexible metallized ceramic nanofiber composite.

[0082] S5 uses laser cutting technology to process a flexible metal-ceramic composite nanofiber membrane into a patterned flexible metal-ceramic composite nanofiber electrode, which is then encapsulated with a fluorine crystal mica sheet with the same metal conductive layer grown on it, resulting in a flexible, high-temperature resistant, in-situ temperature-pressure dual-function sensor. The laser cutting parameters are set as follows: cutting speed 500 mm / s, laser frequency 400 kHz, laser power 10 W, cutting times 10 times, and the resulting patterned electrode linewidth is 0.8 mm.

[0083] Example 6 The difference from Example 1 is that in step S3, high-purity platinum is selected as the sputtering target, the sputtering power of the platinum target is 200 W, and the sputtering time is 20 min.

[0084] Example 7 The difference from Example 1 is that in step S3, high-purity gold is selected as the sputtering target, the sputtering power of the gold target is 200 W, and the sputtering time is 20 min.

[0085] Example 8 The difference from Example 1 is that in step S3, the sputtering power of the platinum target is 100 W, the sputtering power of the gold target is 100 W, and the sputtering time is 20 min.

[0086] Example 9 The difference from Example 1 is that in step S3, the sputtering power of the platinum target is 150 W, the sputtering power of the gold target is 50 W, and the sputtering time is 20 min.

[0087] Example 10 The difference from Example 1 is that in step S4, the flexible metal-ceramic nanofiber precursor film is placed in a muffle furnace for high-temperature calcination, and the temperature is increased from room temperature to 800 ℃ at a rate of 10 ℃ / min, held for 60 min, and then cooled naturally to finally obtain the flexible metallized ceramic nanofiber composite.

[0088] Example 11 The difference from Example 1 is that in step S4, the flexible metal-ceramic nanofiber precursor film is placed in a muffle furnace for high-temperature calcination, and the temperature is increased from room temperature to 800 ℃ at a rate of 10 ℃ / min, held for 30 min, and then cooled naturally to finally obtain the flexible metallized ceramic nanofiber composite.

[0089] Example 12 The difference from Example 1 is that in step S4, the flexible metal-ceramic nanofiber precursor film is placed in a muffle furnace for high-temperature calcination, and the temperature is increased from room temperature to 200 ℃ at a rate of 10 ℃ / min, held for 120 min, and then cooled naturally to finally obtain the flexible metallized ceramic nanofiber composite.

[0090] Example 13 The difference from Example 1 is that in step S4, the flexible metal-ceramic nanofiber precursor film is placed in a muffle furnace for high-temperature calcination, and the temperature is increased from room temperature to 400 ℃ at a rate of 10 ℃ / min, held for 120 min, and then cooled naturally to finally obtain the flexible metallized ceramic nanofiber composite.

[0091] Example 14 The difference from Example 1 is that in step S4, the flexible metal-ceramic nanofiber precursor film is placed in a muffle furnace for high-temperature calcination, and the temperature is increased from room temperature to 600 ℃ at a rate of 10 ℃ / min, held for 120 min, and then cooled naturally to finally obtain the flexible metallized ceramic nanofiber composite.

[0092] Example 15 The difference from Example 1 is that in step S4, the flexible metal-ceramic nanofiber precursor film is placed in a muffle furnace for high-temperature calcination, and the temperature is increased from room temperature to 700 ℃ at a rate of 10 ℃ / min, held for 120 min, and then cooled naturally to finally obtain the flexible metallized ceramic nanofiber composite.

[0093] Example 16 The difference from Example 1 is that in step S3, the sputtering time is 10 minutes.

[0094] Example 17 The difference from Example 1 is that in step S3, the sputtering time is 30 minutes.

[0095] Test case Table 1. Resistivity test results of the flexible metal-ceramic composite nanofiber membranes obtained in Examples 1-17 before and after high-temperature calcination.

[0096] Table 1 shows that, based on Examples 1-5, the flexible metal-ceramic composite nanofiber membranes obtained according to the preparation method of this invention exhibit good thermal stability and conductivity. They are applicable to ceramic fiber substrates of different materials, and the resistivity can be customized by varying the calcination temperature, metal type, and sputtering parameters, thus making them suitable for practical applications with different temperatures, resistance values, and temperature sensitivity. The results indicate that a higher first calcination temperature leads to more complete decomposition of the organic polymer, better substrate stability, and is more conducive to a second calcination after metal sputtering. For alloys with two or more elements, the type and proportion of metal significantly affect the electrical properties before and after calcination. For example, in Examples 1, 6-9, platinum has a higher melting point and resistivity than gold. When both platinum and gold are sputtered, a higher proportion of platinum in the total sputtering power results in higher resistivity and a greater increase in resistivity before and after high-temperature calcination. Furthermore, the resistivity of the composite electrode obtained with a lower proportion of platinum sputtering power falls between that obtained with only platinum sputtering and that obtained with only gold sputtering, but the increase in resistivity before and after high-temperature calcination is the smallest. As shown in Examples 1 and 10-15, the longer the holding time or the higher the temperature during high-temperature calcination, the greater the increase in resistivity of the resulting composite electrode. This is because the microstructure changes at the metal-ceramic fiber interface under high-temperature conditions reduce the equivalent conductive pathway, thereby increasing the overall resistivity of the composite electrode and potentially leading to failure. Co-sputtering metal in an appropriate proportion can achieve better high-temperature conductivity than sputtering only a single metal. As shown in Examples 1, 16, and 17, the shorter the sputtering time, the smaller the proportion of the metal layer in the overall composite electrode, resulting in decreased electrical performance and high-temperature stability. Appropriate sputtering time is crucial for improving high-temperature performance. The above fully demonstrates the feasibility of the high-temperature conductivity stability control of the high-temperature resistant flexible metallized ceramic nanofiber composite electrode preparation method of this invention.

[0097] Table 2. Test results of the flexible high-temperature resistant in-situ temperature-pressure dual-function sensor obtained in Example 1.

[0098] The flexible metal-ceramic composite nanofiber membrane obtained in Example 1 possesses both low resistivity and a low resistance growth rate before and after calcination, making it ideally suited for manufacturing the flexible high-temperature resistant in-situ temperature-pressure dual-function sensor described in step S5. As shown in Table 2, pressure loading tests were conducted on Example 4 under high-temperature conditions, providing response outputs under different temperatures and pressures, demonstrating the sensing performance of the flexible high-temperature resistant in-situ temperature-pressure dual-function sensor under extreme temperatures.

[0099] like Figure 2As shown, the flexible metal-ceramic composite nanofiber membrane obtained after high-temperature calcination in S4 exhibits a metallic luster on a macroscopic scale, while also possessing good flexibility and high-temperature resistance.

[0100] like Figure 3 As shown, the flexible metal-ceramic composite nanofiber membrane obtained after high-temperature calcination in S4 exhibits good continuity of the metal coating and high fiber bonding tightness at the microscopic level.

[0101] like Figure 5 As shown, the flexible high-temperature resistant in-situ temperature-pressure dual-function sensor assembled by S5 using the flexible metal-ceramic composite nanofiber membrane obtained in Example 1 as the electrode functional material has good flexibility.

[0102] Those skilled in the art will readily understand that the above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for preparing a high-temperature resistant flexible metallized ceramic nanofiber composite electrode, characterized in that, The method includes the following steps: Electrospinning of an electrospinning sol doped with organic polymers was performed to obtain a precursor for flexible ceramic nanofiber membranes. The precursor is subjected to a high-temperature calcination to remove the doped organic polymer, thereby obtaining a flexible ceramic nanofiber membrane. A metal conductive layer is grown and coated on the surface of the flexible ceramic nanofiber membrane to obtain an electrode precursor. The desired composite electrode is obtained by secondary high-temperature calcination of the electrode precursor.

2. The method for preparing a high-temperature resistant flexible metallized ceramic nanofiber composite electrode as described in claim 1, characterized in that, The organic polymer is one or any combination of polyethylene oxide and polyvinyl alcohol, wherein the organic polymer accounts for 1 to 10 wt% of the total mass of the electrospinning sol.

3. The preparation of a high-temperature resistant flexible metallized ceramic nanofiber composite electrode as described in claim 2, characterized in that, The temperature of the first high-temperature calcination is 600℃~1100℃, followed by holding at that temperature for 30 min~120 min.

4. The method for preparing a high-temperature resistant flexible metallized ceramic nanofiber composite electrode as described in claim 1 or 3, characterized in that, The conductive metal layer is one or a combination of platinum, gold, and rhodium.

5. The method for preparing a high-temperature resistant flexible metallized ceramic nanofiber composite electrode as described in claim 4, characterized in that, The secondary high-temperature calcination temperature is 200℃~800℃, and the holding time is 30 min~120 min.

6. The method for preparing a high-temperature resistant flexible metallized ceramic nanofiber composite electrode as described in claim 1, characterized in that, The electrospinning parameters are set as follows: the collecting drum speed is 80 r / min to 240 r / min, the voltage is 10 kV to 20 kV, and the receiving distance is 10 cm to 25 cm.

7. The method for preparing a high-temperature resistant flexible metallized ceramic nanofiber composite electrode as described in claim 1, characterized in that, A metal conductive layer was grown and coated on the surface of the flexible ceramic nanofiber membrane by magnetron sputtering. The sputtering parameters were set as follows: sputtering power of 50 W to 200 W and sputtering time of 10 min to 30 min.

8. A composite electrode prepared by the preparation method according to any one of claims 1-7.

9. A method for fabricating a flexible, high-temperature resistant, in-situ temperature-pressure dual-function sensor using the composite electrode described in claim 8, characterized in that, The method includes the following steps: The composite electrode is patterned and then attached to a mica sheet. A mica sheet with a metal conductive layer attached to its surface is placed opposite another mica sheet with a patterned composite electrode attached to it, thereby encapsulating the patterned composite electrode between the mica sheets to obtain the desired sensor.

10. A sensor prepared using the method of claim 9.

Images