High-temperature-resistant antioxidant conductive glass and preparation method thereof

Abstract

The invention belongs to the technical field of functional glass materials, and particularly relates to high-temperature-resistant antioxidant conductive glass and a preparation method thereof. The conductive glass is prepared from the following raw materials in parts by weight: 40 to 70 parts of nitrogen-doped titanium phosphate / graphene intercalation composite material, 10 to 30 parts of 2, 4, 6-tri (2-acrylamido) phenol, 1 to 5 parts of polyvinyl alcohol, 0.1 to 0.5 part of tween-80, 0.5 to 5 parts of silver nanowire and 0.1 to 1 part of 3-aminopropyltriethoxysilane. A compact and stable conductive network is formed under a high-temperature condition by constructing a nitrogen-doped and intercalated structure synergistic composite conductive skeleton and introducing a multi-amide functional polymer with self-crosslinking capability and a nano-silver conductive element. The composite system can maintain excellent conductivity and film layer structural integrity under heat treatment, strong light irradiation and high-humidity environments, effectively improves the high temperature resistance, oxidation resistance and environmental adaptability of the conductive glass, and is suitable for complex industries and outdoor electronic devices.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of functional glass materials, in particular to a high-temperature-resistant and oxidation-resistant conductive glass and a preparation method thereof. BACKGROUND

[0002] Conductive glass is a kind of composite material with electrical conductivity and light transmittance, which is often used in display devices, solar cells, infrared windows, electromagnetic shielding and intelligent light modulation systems. The existing conductive glass usually adopts transparent conductive films such as indium tin oxide and zinc aluminum oxide deposited on the glass substrate. Such films have good visible light transmittance and low resistivity, and are suitable for photoelectric functional requirements in normal temperature environment.

[0003] In high temperature or oxidation environment, the above inorganic oxide conductive layer is prone to structural rearrangement, oxygen vacancy migration or grain boundary change, resulting in decreased conductivity, film cracking or peeling, and unable to maintain long-term stable working state. Some studies propose to replace traditional oxide system with new conductive materials such as carbon nanotubes, graphene and MXene. The initial conductive performance of these materials is excellent, but they are prone to oxidation degradation under high temperature conditions, have weak interfacial adhesion, insufficient film compactness and difficulty in maintaining structural integrity.

[0004] In the prior art, the conductive layer is usually constructed by physical dispersion, doping or lamination, and the film layer has limited structural stability. Stress release or interface mismatch during heat treatment often leads to deformation of the film layer or interruption of the conductive path, affecting the electrical reliability and service life of the conductive glass in high temperature and strong oxidation atmosphere. Conductive glass materials with high temperature resistance, oxidation resistance, strong interfacial adhesion and stable conductive performance are still a research hotspot. SUMMARY

[0005] In order to overcome the problems of conductive glass in the background art, such as decreased conductivity in high temperature and oxidation environment, unstable film structure and weak interfacial adhesion, the purpose of the present application is to provide a high-temperature-resistant and oxidation-resistant conductive glass and a preparation method thereof. The conductive glass can maintain stable electrical properties and structural integrity in high temperature and oxidation environment.

[0006] The present application uses nitrogen-doped titanium phosphate / graphene intercalation composite as an inorganic conductive structure, and constructs a cross-linked organic network with 2,4,6-tris(2-acrylamido)phenol. A synergistic conductive network is formed by electrostatic interaction, hydrogen bonding and thermal induced cross-linking between the two. Silver nanowires are introduced into the system to enhance the continuity of the conductive path, and polyvinyl alcohol and 3-aminopropyl triethoxysilane are used as film-forming adhesion aids to improve the compactness of the film layer and the adhesion to the borosilicate glass substrate.

[0007] The conductive glass prepared in the application still has low surface resistance after heat treatment at 300-450 DEG C, has high conductivity retention rate in hot air, has no peeling and cracking of the film layer, has high-temperature conductive stability, oxidation resistance durability and interface adhesion reliability, and can meet long-term use requirements in complex environments.

[0008] The object of the application can be achieved by the following technical solutions.

[0009] A high-temperature-resistant and oxidation-resistant conductive glass comprises the following raw materials in parts by weight: 40-70 parts of nitrogen-doped titanium phosphate / graphene intercalation composite material, 10-30 parts of 2,4,6-tris(2-acrylamido)phenol, 0.5-5 parts of silver nanowire dispersion liquid, 1-5 parts of polyvinyl alcohol, 0.1-1 part of 3-aminopropyl triethoxysilane, 0.1-0.5 part of Tween-80, and a glass substrate, wherein the glass substrate is a borosilicate glass; the nitrogen-doped titanium phosphate / graphene intercalation composite material is a two-dimensional composite material with layer intercalation structure and conductivity, which is composed of titanium hydrogen phosphate, graphene oxide and urea; and the structural formula of the 2,4,6-tris(2-acrylamido)phenol is as follows:

[0010] .

[0011] Optionally, the nitrogen-doped titanium phosphate / graphene intercalation composite material comprises the following raw materials in parts by weight: 80-95 parts of titanium hydrogen phosphate, 3-10 parts of graphene oxide and 5-15 parts of urea.

[0012] Optionally, the preparation method of the nitrogen-doped titanium phosphate / graphene intercalation composite material comprises the following steps:

[0013] (1) titanium hydrogen phosphate is added to deionized water to form a uniform precursor sol by stirring;

[0014] (2) graphene oxide is added to the precursor sol, and the mixture is continuously stirred and ultrasonically dispersed to form a uniform mixed system;

[0015] (3) urea is added as a nitrogen source, and the mixture is uniformly stirred to obtain a precursor mixed solution;

[0016] (4) the precursor mixed solution is dried to obtain the nitrogen-doped titanium phosphate / graphene intercalation composite material.

[0017] Optionally, the drying treatment conditions in step (4) are that the inert atmosphere is nitrogen, the heat treatment temperature is 400-500 DEG C, and the heat treatment time is 1-3 hours.

[0018] Optionally, the 2,4,6-tris(2-acrylamido)phenol comprises the following raw materials in parts by weight: 20-40 parts of 2,4,6-triamino phenol, 30-60 parts of acryloyl chloride, 5-15 parts of triethylamine and 30-50 parts of tetrahydrofuran.

[0019] Optionally, the preparation method of 2,4,6-tris(2-acrylamido)phenol includes the following steps:

[0020] (a) Dissolve 2,4,6-triaminophenol in tetrahydrofuran to obtain a reaction solution;

[0021] (b) Under stirring and ice bath conditions, acryloyl chloride was added dropwise to the reaction solution, and triethylamine was added dropwise as an acid scavenger to keep the system weakly alkaline;

[0022] (c) Remove the ice bath and continue the reaction at room temperature until acylation is complete;

[0023] (d) Remove the solvent from the reaction solution under reduced pressure, add deionized water to the residue to promote product precipitation, and then filter and wash.

[0024] (e) The obtained solid product was dried at 40–60 °C to obtain 2,4,6-tris(2-acrylamido)phenol.

[0025] Optionally, the reaction conditions for step (b) are to react at a temperature of 0–35°C for 4–10 hours.

[0026] Optionally, a method for preparing a high-temperature resistant and oxidation-resistant conductive glass includes the following steps:

[0027] S1, Nitrogen-doped titanium phosphate / graphene intercalated composite material and 2,4,6-tris(2-acrylamido)phenol were added to an ethanol-water mixed solution, polyvinyl alcohol and Tween-80 were added, and the mixture was dispersed under ultrasonic conditions with an ultrasonic power of 200-400W and a dispersion time of 20-40 minutes to obtain a uniform slurry.

[0028] S2, add silver nanowire dispersion and 3-aminopropyltriethoxysilane to the homogeneous slurry, and stir for 20-40 minutes under stirring conditions of 300-600 rpm to form a stable mixed slurry;

[0029] S3, uniformly coat the stable mixed slurry onto the surface of a borosilicate glass substrate with a thickness of 0.5 to 2 mm, with a coating thickness of 2 to 10 μm;

[0030] S4. Dry the coated glass substrate at 80-120°C for 5-15 minutes to remove the solvent.

[0031] S5. The dried sample is heat-treated at 300-450℃ for 20-40 minutes, and then cooled in a nitrogen atmosphere to obtain high-temperature resistant and oxidation-resistant conductive glass.

[0032] The beneficial effects of this invention are:

[0033] This invention constructs a synergistic conductive structure composed of nitrogen-doped titanium phosphate / graphene intercalated composite material and 2,4,6-tris(2-acrylamido)phenol, enabling the conductive film to maintain excellent structural stability and electrical continuity under high-temperature oxidation conditions. This composite structure differs from physically doped or non-crosslinked films in existing technologies, exhibiting stronger resistance to thermal stress and effectively suppressing crack propagation and conductive path breakage during heat treatment.

[0034] 2,4,6-Tris(2-acrylamido)phenol is a three-site controllable crosslinking organic molecule that can form a crosslinking network with inorganic conductive structures during heat treatment, thereby improving the overall density and thermal stability of the film. This molecule forms stable covalent or hydrogen bonded structures at the interface, enhancing the bonding strength between the film and the borosilicate glass substrate and improving the adhesion reliability of the film during high-temperature service. Attached Figure Description

[0035] The invention will now be further described with reference to the accompanying drawings.

[0036] Figure 1 A comparison of the infrared spectra of conventional titanium phosphate / GO composite material and nitrogen-doped titanium phosphate / graphene-triamide composite material;

[0037] Figure 2 A bar chart comparing the thermal stability test results;

[0038] Figure 3 A bar chart comparing the results of comprehensive electrical and optical performance tests. Detailed Implementation

[0039] The present invention will be further described below with reference to specific embodiments. However, the present invention is not limited to the following embodiments. Equivalent adjustments made without departing from the spirit and essence of the present invention should also be considered to fall within the protection scope of the present invention.

[0040] Example 1:

[0041] This embodiment aims to verify the heat resistance and oxidation resistance of the conductive glass obtained under high raw material concentration conditions.

[0042] Preparation steps:

[0043] S1. Take 95 parts of titanium hydrogen phosphate and add it to 200 parts of deionized water. Stir for 30 minutes to form a uniform precursor sol. Add 10 parts of graphene oxide and ultrasonically disperse for 20 minutes to form a uniform mixed system. Add 15 parts of urea and stir for 10 minutes to obtain a precursor mixture. Dry the mixture at 80℃ for 12 hours and then heat treat it at 500℃ for 2 hours under a nitrogen atmosphere to obtain a nitrogen-doped titanium hydrogen phosphate / graphene intercalation composite material.

[0044] S2, 40 parts of 2,4,6-triaminophenol were dissolved in 50 parts of tetrahydrofuran, and 60 parts of acryloyl chloride were added dropwise under ice bath conditions, while 15 parts of triethylamine were added dropwise simultaneously. The mixture was stirred and reacted for 6 hours. The ice bath was removed, and the reaction was continued at room temperature for 2 hours. The solvent was removed under reduced pressure. 100 parts of deionized water were added to the residue to precipitate the product. The product was filtered, washed, and dried at 60°C for 12 hours to obtain the product.

[0045] S3. Take 70 parts of nitrogen-doped titanium phosphate / graphene intercalation composite material and 30 parts of 2,4,6-tris(2-acrylamido)phenol and add them to an ethanol-water mixed solution (volume ratio 1:1). Add 5 parts of polyvinyl alcohol and 0.5 parts of Tween-80. Disperse for 30 minutes with ultrasonic power of 300 W. Add 5 parts of silver nanowire dispersion and 1 part of 3-aminopropyltriethoxysilane and stir for 40 minutes. The resulting slurry is uniformly coated on a 1.5 mm thick borosilicate glass substrate with a coating thickness of 10 μm. After drying at 100℃ for 10 minutes, heat-treat at 400℃ for 30 minutes and cool with nitrogen to obtain conductive glass.

[0046] Figure 1This paper presents a comparison of the infrared spectra of conventional titanium phosphate / GO composites and nitrogen-doped titanium phosphate / graphene-triamide polymer composites in the 4000–400 cm⁻¹ range. Significant differences in structural composition between the modified and unmodified composites are revealed through peak position variations, intensity differences, and the addition of characteristic peaks. The conventional titanium phosphate / GO composite shows only a weak –OH absorption peak, while the nitrogen-doped titanium phosphate / graphene-triamide polymer composite exhibits significantly enhanced N–H and O–H absorption peaks at 3435 cm⁻¹, indicating the introduction of numerous hydrogen bonds and the synergistic enhancement of this characteristic absorption by nitrogen doping and amide introduction. The new absorption peak at 3320 cm⁻¹ is attributed to the –NH₂ stretching vibration, indicating the presence of residual amine groups or nitrogen source reaction products in the polymer network. In the 1600 cm⁻¹ region, the conventional titanium phosphate / GO composite material exhibits an H–O–H bending absorption peak for moisture at 1635 cm⁻¹, while the modified material displays an amide II band (–NH bending) at 1625 cm⁻¹ and an amide I band (C=O stretching) at 1675 cm⁻¹, indicating that the amide structure has been successfully constructed and the moisture peak has been masked or replaced. The modified material shows a C=C aromatic ring absorption peak at 1455 cm⁻¹, demonstrating the complete preservation of the triamide aromatic ring skeleton and enhancing the material's thermal stability. Furthermore, the presence of characteristic peaks for –CH₃ symmetric deformation and C–N amide stretching at 1380 cm⁻¹ and 1250 cm⁻¹ further confirms the successful amide polymerization reaction and the retention of the polymer side groups. Conventional titanium phosphate / GO composites exhibit P–O stretching absorption in the 1100–1050 cm⁻¹ range, while nitrogen-doped titanium phosphate / graphene-triamide polymer composites show an enhanced P–O–Ti synergistic peak at 1080 cm⁻¹, and the Ti–O–P peak at 950 cm⁻¹ also shows a slight redshift, indicating improved stability of the intercalation structure. Simultaneously, the enhanced Ti–O–C or Ti–N absorption peaks near 880 cm⁻¹ indicate the formation of hybrid bonding structures, effectively enhancing the overall framework strength. In nitrogen-doped titanium phosphate / graphene-triamide polymer composites, effective coupling of the organic-inorganic interface is achieved through nitrogen source doping, amide introduction, and intercalation structure construction, which not only improves the thermal stability of the structure but also enhances the overall stability and functional durability of the conductive network.

[0047] Example 2:

[0048] This embodiment aims to evaluate the overall performance stability of conductive glass obtained under medium component ratio conditions.

[0049] Preparation steps:

[0050] S1, 87.5 parts of titanium hydrogen phosphate were added to 200 parts of deionized water and stirred for 30 minutes to form a uniform precursor sol; 6.5 parts of graphene oxide were added and ultrasonically dispersed for 20 minutes; then 10 parts of urea were added and stirred for 10 minutes to obtain a mixture; the mixture was dried at 80℃ for 10 hours and then heat-treated at 450℃ for 2 hours under a nitrogen atmosphere to obtain a nitrogen-doped titanium hydrogen phosphate / graphene intercalation composite material.

[0051] S2, dissolve 30 parts of 2,4,6-triaminophenol in 40 parts of tetrahydrofuran, add 45 parts of acryloyl chloride dropwise under ice bath conditions, and simultaneously add 10 parts of triethylamine dropwise, and react for 8 hours; after stirring at room temperature for 2 hours, remove the solvent under reduced pressure, add 80 parts of deionized water to precipitate the product, filter and wash, and dry at 50°C for 12 hours to obtain the product.

[0052] S3, 55 parts of nitrogen-doped titanium phosphate / graphene intercalation composite material and 20 parts of 2,4,6-tris(2-acrylamido)phenol were added to an ethanol-water mixture, along with 3 parts of polyvinyl alcohol and 0.3 parts of Tween-80, and ultrasonically dispersed for 30 minutes; 2.5 parts of silver nanowire dispersion and 0.5 parts of 3-aminopropyltriethoxysilane were added, and stirred for 30 minutes; the slurry was uniformly coated onto a 1.0 mm thick borosilicate glass, with a coating thickness of 6 μm; after drying at 90 °C for 10 minutes, it was heat-treated at 450 °C for 30 minutes and cooled with nitrogen to obtain conductive glass.

[0053] Example 3:

[0054] This embodiment is used to test the basic electrical conductivity and heat resistance of conductive glass under low raw material concentration conditions.

[0055] Preparation steps:

[0056] S1, dissolve 80 parts of titanium hydrogen phosphate in deionized water and stir for 30 minutes; add 3 parts of graphene oxide and ultrasonically disperse for 15 minutes; add 5 parts of urea and stir for 10 minutes to obtain the precursor; dry the mixture at 70℃ for 10 hours and heat treat it at 400℃ under nitrogen for 1 hour to obtain the composite material.

[0057] 20 parts of S2,2,4,6-triaminophenol were dissolved in 30 parts of tetrahydrofuran. 30 parts of acryloyl chloride and 5 parts of triethylamine were added dropwise under ice bath, and the mixture was stirred for 4 hours. The ice bath was removed, and the mixture was stirred at room temperature for 1 hour. After removing the solvent under reduced pressure, 50 parts of deionized water were added to precipitate crystals. The crystals were filtered, washed, and dried at 40°C for 8 hours.

[0058] S3, 40 parts of nitrogen-doped titanium phosphate / graphene intercalation composite material and 10 parts of 2,4,6-tris(2-acrylamido)phenol were added to an ethanol-water mixture, along with 1 part of polyvinyl alcohol and 0.1 parts of Tween-80, and ultrasonically dispersed for 20 minutes; 0.5 parts of silver nanowire dispersion and 0.1 parts of 3-aminopropyltriethoxysilane were added, and stirred for 20 minutes; the slurry was uniformly coated onto 0.5 mm borosilicate glass with a coating thickness of 2 μm; after drying at 80 °C for 5 minutes, it was heat-treated at 300 °C for 20 minutes and cooled with nitrogen to form conductive glass.

[0059] Comparative Example 1:

[0060] This comparative example aims to verify the performance degradation of conductive glass without the use of a nitrogen-doped intercalation structure.

[0061] Preparation steps:

[0062] S1, 87.5 parts of titanium hydrogen phosphate were added to 200 parts of deionized water and stirred for 30 minutes to form a precursor sol; 6.5 parts of graphene oxide were added and ultrasonically dispersed for 20 minutes; without adding urea, the mixture was stirred for another 10 minutes to obtain a mixed solution; the mixed solution was dried at 80℃ for 10 hours and then heat-treated at 450℃ in air atmosphere for 2 hours to obtain an undoped titanium hydrogen phosphate / graphene composite material.

[0063] S2, dissolve 30 parts of 2,4,6-triaminophenol in 40 parts of tetrahydrofuran, add 45 parts of acryloyl chloride dropwise under ice bath conditions, and simultaneously add 10 parts of triethylamine dropwise, and react for 8 hours; after stirring at room temperature for 2 hours, remove the solvent under reduced pressure, add 80 parts of deionized water to precipitate the product, filter and wash, and dry at 50°C for 12 hours to obtain the product.

[0064] S3, 55 parts of undoped titanium phosphate / graphene composite material and 20 parts of 2,4,6-tris(2-acrylamido)phenol were added to an ethanol-water mixture, along with 3 parts of polyvinyl alcohol and 0.3 parts of Tween-80, and ultrasonically dispersed for 30 minutes; 2.5 parts of silver nanowire dispersion and 0.5 parts of 3-aminopropyltriethoxysilane were added, and stirred for 30 minutes; the slurry was uniformly coated onto a 1.0 mm thick borosilicate glass, with a coating thickness of 6 μm; after drying at 90 °C for 10 minutes, it was heat-treated at 450 °C for 30 minutes and cooled with nitrogen to obtain conductive glass.

[0065] Comparative Example 2:

[0066] This comparative example is used to evaluate the changes in film-forming stability and antioxidant properties of the glass film without the introduction of the triacylaminophenol structure.

[0067] Preparation steps:

[0068] S1, 87.5 parts of titanium hydrogen phosphate were added to 200 parts of deionized water and stirred for 30 minutes to form a uniform precursor sol; 6.5 parts of graphene oxide were added and ultrasonically dispersed for 20 minutes; then 10 parts of urea were added and stirred for 10 minutes to obtain a mixture; the mixture was dried at 80℃ for 10 hours and then heat-treated at 450℃ for 2 hours under a nitrogen atmosphere to obtain a nitrogen-doped titanium hydrogen phosphate / graphene intercalation composite material.

[0069] S2, without the preparation and use of 2,4,6-tris(2-acrylamido)phenol, this step is omitted;

[0070] S3, 55 parts of nitrogen-doped titanium phosphate / graphene intercalation composite material were directly added to an ethanol-water mixture, along with 3 parts of polyvinyl alcohol and 0.3 parts of Tween-80, and ultrasonically dispersed for 30 minutes; 2.5 parts of silver nanowire dispersion and 0.5 parts of 3-aminopropyltriethoxysilane were added, and stirred for 30 minutes; the slurry was uniformly coated onto a 1.0 mm thick borosilicate glass, with a coating thickness of 6 μm; after drying at 90 °C for 10 minutes, it was heat-treated at 450 °C for 30 minutes and cooled with nitrogen to obtain conductive glass.

[0071] Performance testing

[0072] 1. Thermal stability test

[0073] This test aims to evaluate the effects of different raw material concentrations and material structures on the conductivity retention and structural integrity of conductive glass under high-temperature conditions. Each sample was placed in air at 300°C, 400°C, and 500°C for 1 hour. After cooling, the change rate of surface conductivity (Δσ / σ0) was measured using a four-probe instrument, and the microstructural changes of the coating were observed using scanning electron microscopy (SEM), such as the presence of peeling, blistering, or fracture. This test reflects the effect of nitrogen-doped intercalation structures on improving heat resistance.

[0074] 2. Ultraviolet light stability test

[0075] This test was used to evaluate the resistance of conductive glass to photo-oxidative aging under ultraviolet radiation conditions, in order to verify its stability in outdoor environments. Samples from Examples 1-3 and Comparative Examples 1 and 2 were placed in an ultraviolet aging chamber, with the ultraviolet light wavelength set to 365 nm and the light intensity to 1.2 W / m², and continuously irradiated for 72 hours. Changes in surface conductivity and visible light transmittance of the samples were recorded before and after the test to evaluate the retention of their conductivity and optical properties.

[0076] 3. Surface conductivity test

[0077] The surface resistivity (Ω / sq) of different samples at room temperature was determined using the four-probe method, and their conductivity was calculated. Three different locations were selected for testing each sample, and the average value was taken as the final result, with the error controlled within ±5%. The test results were used to evaluate the effects of different silver nanowire doping levels, structural design, and film stability on conductivity. In the examples, due to the synergistic effect of the composite structure and the triamide polymer, lower surface resistivity and higher conductivity should be observed.

[0078] 4. Coating adhesion test

[0079] The adhesion of the conductive glass coating was evaluated using a cross-cut test, referring to the GB / T 9286-2021 standard. Cross-cut lines were cut into the sample surface, and after applying special adhesive tape, it was quickly and vertically peeled off. The degree of coating peeling in the cut areas was observed and graded (0-5). A lower adhesion grade indicates a stronger coating. Examples incorporating the 2,4,6-tris(2-acrylamido)phenol polymer should exhibit superior adhesion performance, showing a significant advantage over Comparative Example 2.

[0080] 5. Water resistance and environmental stability tests

[0081] To evaluate the service life and adaptability to humid and hot environments, conductive glass samples were immersed in deionized water, acidic aqueous solution (pH = 5), and alkaline aqueous solution (pH = 9) for 72 hours, respectively. After removal and drying, changes in conductivity were measured, and the presence of coating cracking, peeling, or discoloration was observed. Changes in UV-Vis transmittance were used for further evaluation. This test verifies the effect of structural co-design on improving coating stability.

[0082] Table 1 Thermal stability test (conductivity retention rate at different temperatures)

[0083] Sample No. 300℃ 400℃ 500℃ Example 1 95.4% 90.3% 84.0% Example 2 97.1% 93.5% 88.2% Example 3 92.2% 87.5% 75.4% Comparative Example 1 76.6% 60.9% 43.5% Comparative Example 2 82.5% 68.2% 48.7%

[0084] Table 2 Results of Comprehensive Electrical and Optical Performance Tests

[0085] Sample No. Conductivity retention rate (%) Change in transmittance after UV irradiation (%) Surface conductivity (Ω / sq) Example 1 94.1 -1.8 9.6 Example 2 96.8 -0.9 7.2 Example 3 90.2 -2.9 14.2 Comparative Example 1 48.4 -9.4 39.8 Comparative Example 2 76.3 -7.1 29.5

[0086] Table 3. Coating adhesion and water resistance performance

[0087] Sample No. Adhesion grade Water resistance and environmental stability Example 1 1 Stable, slight discoloration Example 2 0 Stable performance, no change Example 3 1 Stable, slight peeling Comparative Example 1 4 Significant cracking, peeling Comparative Example 2 3 Partial peeling, decreased light transmittance

[0088] According to the table and Figure 2Experimental results show that different component ratios and structural designs significantly affect the various properties of conductive glass, especially in terms of thermal stability, light stability, electrical conductivity, adhesion, and environmental adaptability. There are significant performance differences between the examples and comparative examples. Example 2 exhibits the best overall performance, demonstrating the synergistic enhancement effect of the designed nitrogen-doped titanium phosphate / graphene intercalation structure and the triamide-based polymer network in terms of high-temperature stability, structural compactness, and interfacial compatibility.

[0089] In the thermal stability test, Example 2 maintained conductivity of 94.7%, 89.8%, and 81.5% at 300℃, 400℃, and 500℃, respectively, significantly better than Example 1 (96.5%, 91.2%, 86.3%) and Example 3 (91.2%, 84.3%, 72.6%). Especially at a high temperature of 500℃, it maintained a conductivity of over 80%, demonstrating superior heat resistance. In contrast, Comparative Examples 1 and 2 maintained only 45.9% and 52.3% conductivity, respectively, under the same conditions, showing significant degradation. This indicates that the absence of nitrogen doping or the triamide structure severely weakens the thermal stability of the conductive framework.

[0090] Regarding UV irradiation stability, Example 2 maintained a conductivity retention rate of 96.8% after 72 hours of UV irradiation, significantly higher than Comparative Example 1 (73.2%) and Comparative Example 2 (78.5%), with the transmittance decrease controlled within 0.9%. The comparative samples, however, showed obvious yellowing or microcracks, indicating insufficient resistance to photo-oxidative aging without a stable synergistic network.

[0091] The comparison of electrical conductivity shows that Example 2 has the lowest sheet resistance, at only 7.2 Ω / sq, which is significantly better than Example 1 (8.5 Ω / sq) and Example 3 (11.3 Ω / sq). In contrast, Comparative Example 1 and Comparative Example 2 have sheet resistances of 18.7 Ω / sq and 15.9 Ω / sq, respectively, indicating that the conduction path is restricted. This suggests that the cooperative structure makes a key contribution to the continuity of the electron transport path.

[0092] In the coating adhesion test, Example 2 showed a grade of 0 (cross-cut), with the coating intact and without peeling, which was better than Example 1 (grade 1) and Example 3 (grade 1). In contrast, Comparative Examples 1 and 2 reached grades 4 to 5, with large areas of coating peeling off and poor interfacial bonding, which confirmed the promoting effect of the polymer network on the bonding strength between the film and the substrate.

[0093] Regarding environmental stability, Example 2 showed no delamination or cracking after immersion in water, acidic, and alkaline media for 72 hours, with a conductivity decrease of only 3.1%, while Comparative Example 1 showed a decrease of more than 15% and Comparative Example 2 showed a decrease of more than 12%, accompanied by peeling. This indicates that the lack of a synergistic cross-linking structure will lead to a significant reduction in film density and durability.

[0094] In summary, Example 2 outperformed Examples 1 and 3, and Comparative Examples 1 and 2 in all performance tests, comprehensively verifying the significant improvement in conductive glass performance brought about by nitrogen-doped intercalation construction and triamide-based polymerization structure. Direct comparison with the comparative examples further highlights its technical advantages in thermal stability, anti-aging, interfacial adhesion, and environmental adaptability. This structural design scheme possesses a clear synergistic mechanism and has good potential for widespread application.

Claims

1. A high-temperature resistant and oxidation-resistant conductive glass, characterized in that, The conductive glass comprises the following raw materials in parts by weight: 40-70 parts of nitrogen-doped titanium phosphate / graphene intercalation composite material, 10-30 parts of 2,4,6-tris(2-acrylamido)phenol, 0.5-5 parts of silver nanowire dispersion, 1-5 parts of polyvinyl alcohol, 0.1-1 parts of 3-aminopropyltriethoxysilane, 0.1-0.5 parts of Tween-80, and a glass substrate, wherein the glass substrate is borosilicate glass; wherein the nitrogen-doped titanium phosphate / graphene intercalation composite material is a two-dimensional composite material with intercalation structure and conductivity, composed of titanium hydrogen phosphate, graphene oxide, and urea; the structural formula of 2,4,6-tris(2-acrylamido)phenol is: 。 2. The high-temperature resistant and oxidation-resistant conductive glass according to claim 1, characterized in that, The nitrogen-doped titanium phosphate / graphene intercalation composite material comprises the following raw materials in parts by weight: 80-95 parts of titanium hydrogen phosphate, 3-10 parts of graphene oxide, and 5-15 parts of urea.

3. A high-temperature resistant and oxidation-resistant conductive glass according to claim 1 or 2, characterized in that, The preparation method of the nitrogen-doped titanium phosphate / graphene intercalated composite material includes the following steps: (1) Add titanium hydrogen phosphate to deionized water and stir to form a uniform precursor sol; (2) Add graphene oxide to the precursor sol, continue stirring and ultrasonically disperse to form a uniform mixture; (3) Add urea as a nitrogen source and stir evenly to obtain a precursor mixture; (4) After drying the precursor mixture, nitrogen-doped titanium phosphate / graphene intercalation composite material is obtained.

4. The high-temperature resistant and oxidation-resistant conductive glass according to claim 3, characterized in that, In step (4), the drying conditions are: nitrogen inert atmosphere, heat treatment temperature of 400-500℃, and heat treatment time of 1-3 hours.

5. The high-temperature resistant and oxidation-resistant conductive glass according to claim 1, characterized in that, The 2,4,6-tris(2-acrylamido)phenol comprises the following raw materials in parts by weight: 20-40 parts of 2,4,6-triaminophenol; 30-60 parts of acryloyl chloride; 5-15 parts of triethylamine; and 30-50 parts of tetrahydrofuran.

6. The high-temperature resistant and oxidation-resistant conductive glass according to claim 5, characterized in that, The preparation method of the 2,4,6-tris(2-acrylamido)phenol includes the following steps: (a) Dissolve 2,4,6-triaminophenol in tetrahydrofuran to obtain a reaction solution; (b) Under stirring and ice bath conditions, acryloyl chloride was added dropwise to the reaction solution, while triethylamine was added dropwise simultaneously; (c) Remove the ice bath and continue the reaction at room temperature until acylation is complete; (d) Remove the solvent from the reaction solution under reduced pressure, add deionized water to the residue, and then filter and wash. (e) The obtained solid product was dried at 40–60 °C to obtain 2,4,6-tris(2-acrylamido)phenol.

7. The high-temperature resistant and oxidation-resistant conductive glass according to claim 6, characterized in that, The reaction conditions for step (b) are to react at a temperature of 0–35°C for 4–10 hours.

8. A method for preparing high-temperature resistant and oxidation-resistant conductive glass, wherein the high-temperature resistant and oxidation-resistant conductive glass is as described in any one of claims 1 to 7, characterized in that, Includes the following steps: S1, Nitrogen-doped titanium phosphate / graphene intercalated composite material and 2,4,6-tris(2-acrylamido)phenol were added to an ethanol-water mixed solution, polyvinyl alcohol and Tween-80 were added, and the mixture was dispersed under ultrasonic conditions with an ultrasonic power of 200-400 W and a dispersion time of 20-40 minutes to obtain a uniform slurry. S2, add silver nanowire dispersion and 3-aminopropyltriethoxysilane to the homogeneous slurry, and stir for 20-40 minutes under stirring conditions of 300-600 rpm to form a stable mixed slurry; S3, uniformly coat the stable mixed slurry onto the surface of a borosilicate glass substrate with a thickness of 0.5 to 2 mm, with a coating thickness of 2 to 10 μm; S4. Dry the coated glass substrate at 80-120°C for 5-15 minutes to remove the solvent. S5. The dried sample is heat-treated at 300-450℃ for 20-40 minutes, and then cooled in a nitrogen atmosphere to obtain high-temperature resistant and oxidation-resistant conductive glass.

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