CN117702538A - Preparation method of multifunctional bamboo fiber electromagnetic shielding paper - Google Patents
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Abstract
The invention discloses a preparation method of multifunctional bamboo fiber electromagnetic shielding paper, which relates to the technical field of electromagnetic shielding, and comprises the steps of firstly obtaining a light flexible bamboo fiber paper-based framework material, uniformly mixing a functional material MXene, an oxidant ferric trichloride, a doping agent hydrochloric acid and pyrrole monomers, immersing the light flexible bamboo fiber paper-based framework material into a mixed solution of the light flexible bamboo fiber paper-based framework material, carrying out pyrrole polymerization reaction, packaging the functional material MXene in the light flexible bamboo fiber paper-based framework material and on the surface of the light flexible bamboo fiber paper-based framework material, and washing and drying the light flexible bamboo fiber paper-based framework material to obtain polypyrrole/MXene modified bamboo fiber conductive paper; and adding a functional material MXene into the polyimide resin solution, uniformly mixing the functional material MXene and the polyimide resin solution, coating the functional material on the surface of the polypyrrole/MXene modified bamboo fiber conductive paper, and drying to obtain the MXene modified multifunctional bamboo fiber electromagnetic shielding paper. The invention can improve the mechanical property, corrosion resistance and temperature resistance of the bamboo fiber paper and endow the bamboo fiber paper with conductivity.
Description
Technical Field
The invention relates to the technical field of electromagnetic shielding, in particular to a preparation method of multifunctional bamboo fiber electromagnetic shielding paper.
Background
With the deep development of environmental protection concepts and new material industries, bamboo fiber electromagnetic shielding paper is attracting attention as an environmental-friendly and renewable high-performance functional material. Therefore, the development of the bamboo fiber paper-based electromagnetic shielding material meets the urgent need of the high-performance electromagnetic shielding material, and is expected to become an important innovation direction of new material industry in the future.
However, the presently reported bamboo fiber electromagnetic shielding papers present a series of technical challenges that limit their practical application in complex and demanding environments. The primary problem is that the bamboo fiber electromagnetic shielding paper has poor high temperature resistance, which limits the use of the paper in high temperature environments. Secondly, the mechanical property of the bamboo fiber electromagnetic shielding paper is relatively weak, and the bamboo fiber electromagnetic shielding paper is difficult to meet certain application scenes with high strength requirements. Furthermore, the moisture and corrosion resistance of bamboo fiber electromagnetic shielding paper are relatively poor, limiting the service life and performance effects of the paper in wet or corrosive environments. In addition, the reported bamboo fiber electromagnetic shielding paper is generally used as an electromagnetic shielding material, has single function and has a narrow application range. For example: CN106589938A chinese patent application discloses a biomass composite material based on functional improvement of bamboo fiber and a preparation method thereof; CN108794790a chinese patent application discloses a bamboo fiber doped polyaniline electromagnetic shielding material and a preparation method thereof; the common points of the bamboo fiber electromagnetic shielding paper are short service life, poor corrosion resistance and poor mechanical property, and the bamboo fiber electromagnetic shielding paper is only applied to the field of electromagnetic shielding and can not meet the current requirements of multifunctional electromagnetic shielding materials.
In order to cope with the high-frequency electromagnetic pollution of the fifth generation mobile network (5G) and simultaneously adapt to the miniaturization development trend of electronic equipment, the electromagnetic shielding paper-based material is expected to realize the high-efficiency shielding of electromagnetic waves, and also has the functions of high temperature resistance, corrosion resistance, flame retardance, heating, frost resistance, winter removal and the like, so that the high-value utilization of the high-performance electromagnetic shielding paper is realized. Therefore, the defects of the existing bamboo fiber materials are overcome, the deep research on the preparation of the bamboo fiber paper-based electromagnetic shielding material is enhanced, the defects of the bamboo fiber paper-based electromagnetic shielding material in mechanical property, corrosion resistance and high temperature resistance are overcome, and the bamboo fiber paper-based electromagnetic shielding material has great significance in the application of the bamboo fiber paper-based electromagnetic shielding material in the high-tech fields of intelligent manufacturing, national defense, aerospace and the like. Based on the design, the preparation method of the multifunctional bamboo fiber electromagnetic shielding paper can realize the basic electromagnetic shielding function, has the functions of conducting electricity, flame retarding, heating, frost resistance, defrosting and the like, and can realize the multifunctional efficient utilization of the bamboo fiber electromagnetic shielding paper.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of multifunctional bamboo fiber electromagnetic shielding paper, which encapsulates a functional material MXene by polypyrrole, greatly improves the mechanical property of the bamboo fiber paper, simultaneously endows the bamboo fiber paper with functionality (electric conduction), and realizes the diversified utilization of environment-friendly renewable bamboo fiber resources.
The aim of the invention is realized by the following technical scheme: a method for preparing multifunctional bamboo fiber electromagnetic shielding paper, which comprises the following steps:
s1, dispersing bamboo fibers and carbon fibers in water, uniformly mixing, sheet making, squeezing and drying to obtain the light flexible bamboo fiber paper-based framework material, wherein the mass ratio of the bamboo fibers to the carbon fibers is (1:1) - (4:1), and the light flexible bamboo fiber paper-based framework material is quantitative60g/m 2 The squeezing pressure is 0.3-0.5 Mpa, and the drying temperature is 100-120 ℃.
S2, uniformly mixing a functional material MXene, an oxidant ferric trichloride, a doping agent hydrochloric acid and pyrrole monomers, immersing a light flexible bamboo fiber paper-based framework material into the mixed solution, carrying out pyrrole polymerization reaction in an ice-water bath, packaging the functional material MXene in the light flexible bamboo fiber paper-based framework material and on the surface of the light flexible bamboo fiber paper-based framework material, washing and drying to obtain polypyrrole/MXene modified bamboo fiber conductive paper, and adopting a liquid phase polymerization method to generate a conductive polymer (namely polypyrrole) in situ to package the MXene in the light flexible bamboo fiber paper-based framework material. The molar concentration ratio of the functional material MXene, the oxidant ferric trichloride, the doping agent hydrochloric acid and the pyrrole monomer is 1:31:14:6, the temperature of the polymerization reaction is 0 ℃, and the reaction time is 6-18 h.
S3, adding a functional material MXene into the polyimide resin solution, uniformly mixing the functional material MXene and the polyimide resin solution, coating the functional material on the surface of the polypyrrole/MXene modified bamboo fiber conductive paper, and drying to obtain the MXene modified multifunctional bamboo fiber electromagnetic shielding paper.
In the step S3, a functional material MXene is added into a polyimide resin solution, and after the functional material MXene and the polyimide resin solution are uniformly mixed, the functional material MXene and the polyimide resin solution are coated on the surface of the polypyrrole/MXene modified bamboo fiber conductive paper by using a coating machine.
In the step S3, the mass concentration of the polyimide resin solution is 50-150 g/L.
In the step S3, the mass ratio of the functional material MXene to the polyimide resin solution is (0.1:100) to (1:100).
The beneficial effects of the invention are as follows:
1. the multifunctional bamboo fiber electromagnetic shielding paper modified by the MXene is prepared by packaging the functional material MXene by polypyrrole, so that the mechanical property of the bamboo fiber paper is greatly improved, the functionality (conductivity) of the bamboo fiber paper is endowed, and the environment-friendly renewable bamboo fiber resource is utilized in a diversified manner.
2. The multifunctional bamboo fiber electromagnetic shielding paper modified by the MXene has higher specific surface area due to the encapsulation of the polypyrrole on the functional material MXene, and is beneficial to the absorption of electromagnetic waves.
3. The MXene-modified multifunctional bamboo fiber electromagnetic shielding paper provided by the invention has the functions of conducting, flame retarding, heating, frost resistance, defrosting and the like besides the basic electromagnetic shielding function under the condition of keeping the flexibility and light weight, and can be used for realizing the multifunctional high-efficiency utilization of the bamboo fiber electromagnetic shielding paper.
4. The invention is based on the traditional wet papermaking technology, combines in-situ generation and coating processes to prepare the corrosion-resistant, high-temperature-resistant and moisture-resistant MXene modified multifunctional bamboo fiber electromagnetic shielding paper, has the advantages of simple process, mature technology, lower cost and high production efficiency, and is suitable for industrial production.
Drawings
FIGS. 1A and 1B are digital photographs of an MXene-modified multifunctional bamboo fiber electromagnetic shielding paper prepared in example 1 of the present invention, wherein FIG. 1A is a physical image of the MXene-modified multifunctional bamboo fiber electromagnetic shielding paper, and FIG. 1B is a thickness display view of the MXene-modified multifunctional bamboo fiber electromagnetic shielding paper;
FIG. 2 is an electromagnetic shielding performance spectrum of the MXene-modified multifunctional bamboo fiber electromagnetic shielding paper prepared in example 1 and comparative example 1 of the present invention;
FIG. 3 is a graph showing the conductivity of the MXene-modified multifunctional bamboo fiber electromagnetic shielding paper prepared in example 1 of the present invention;
FIG. 4 is a test of the fire resistance of the MXene-modified multifunctional bamboo fiber electromagnetic shielding paper prepared in example 1 of the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. The components of the embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations. Thus, the following detailed description of the embodiments of the invention, as presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention is further described with reference to the drawings and specific examples.
Example 1:
dispersing 1.51g of bamboo fiber (3 mm) and 0.37g of carbon fiber (3 mm) in 400g of water, stirring for 5min, carrying out sheet making on a sheet making device, then pressing for 5min under the pressure of 0.4MPa, and drying for 10min at 105 ℃ to obtain the light flexible bamboo fiber paper-based framework material.
Adding 0.3g MXene, 9.3g ferric trichloride serving as an oxidant, 4.3g hydrochloric acid serving as a doping agent, 1.7g pyrrole monomer and 50ml water into a beaker, uniformly mixing, immersing a light flexible bamboo fiber paper-based framework material (5X 5 cm) into the mixed solution, reacting for 12h in an ice water bath (0 ℃), washing for 3 times, and drying at 65 ℃ to obtain the polypyrrole/MXene modified bamboo fiber conductive paper.
Adding 0.3g MXene into 50mL polyimide resin (SG 120L) solution (100 g/L), uniformly mixing, and coating on the surface of polypyrrole/MXene modified bamboo fiber conductive paper by using a coating machine with the coating amount of 10g/m 2 Finally, drying at 105 ℃ to obtain the MXene modified multifunctional bamboo fiber electromagnetic shielding paper.
1. Tensile index:
according to GB/T453-2002, the tensile strength of MXene-modified multifunctional bamboo fiber electromagnetic shielding paper is tested by using a universal material machine, and the tensile strength is measured for multiple times to obtain an average value.
2. Conductivity test:
and (3) testing the conductivity of the MXene modified multifunctional bamboo fiber electromagnetic shielding paper by adopting a ST 2263-four-probe tester.
3. Electromagnetic shielding performance test:
a DR-S type vector network analyzer is adopted, and a waveguide method is selected to measure the shielding effect of MXene modified multifunctional bamboo fiber electromagnetic shielding paper on electromagnetic waves in an X wave band.
4. Anti-frost and anti-freeze test:
firstly, placing an ice block on the surface of the MXene modified multifunctional bamboo fiber electromagnetic shielding paper, and then observing the state of the ice block under the voltage of 4V.
5. Thermal stability test:
and using a TGA2 full-automatic thermogravimetric analyzer to test the temperature index of the sample at 10% of thermal weight loss to characterize the thermal stability of the MXene modified multifunctional bamboo fiber electromagnetic shielding paper.
6. Flame retardant rating test:
and using an British FTT0082 vertical combustor to test the flame retardant grade of the MXene modified multifunctional bamboo fiber electromagnetic shielding paper, and testing the flame retardant property of the multifunctional bamboo fiber electromagnetic shielding paper.
7. Fire resistance behavior test:
the prepared MXene-modified multifunctional bamboo fiber electromagnetic shielding paper is exposed to ethanol flame for fire resistance performance test, and a digital camera is used for recording the burning process.
Through testing, the obtained MXene modified multifunctional bamboo fiber electromagnetic shielding paper has the thickness of 0.30mm, the tensile index of 56.32 N.m/g, the elongation at break of 1.664%, the surface conductivity of 8.36S/cm, and the electromagnetic interference Shielding Effect (SE) is obtained in the X-band T ) 62.30-60.69 dB. As shown in FIG. 2, the prepared MXene-modified multifunctional bamboo fiber electromagnetic shielding paper has good conductive performance and can be used as a conductive material. The prepared MXene modified multifunctional bamboo fiber electromagnetic shielding paper can be applied with 4V voltage to remove the surface freezing in a short time, so that the multifunctional bamboo fiber electromagnetic shielding paper can be used as a heating material in a low-temperature environment (figure 3). In addition, the shape of the prepared MXene modified multifunctional bamboo fiber electromagnetic shielding paper is almost unchanged after open flame treatment (figure 4), the electromagnetic shielding efficiency is still kept above 85%, and the performance requirement (more than or equal to 20 dB) of the commercial electromagnetic shielding material can be still met. The flame retardant property test result shows that the limiting oxygen index of the prepared MXene modified multifunctional bamboo fiber electromagnetic shielding paper is more than 39, and the MXene modified multifunctional bamboo fiber electromagnetic shielding paper belongs to flame retardant grade 1 materials.
Example 2:
the molar concentration ratio of the oxidant ferric trichloride, the dopant hydrochloric acid and the pyrrole monomer in the embodiment 1 is adjusted, and other parameters are consistent with the embodiment 1, so that the MXene modified multifunctional bamboo fiber electromagnetic shielding paper is obtained.
The performance of the obtained MXene modified multifunctional bamboo fiber electromagnetic shielding paper is tested, and the test results are shown in Table 1. As can be seen from table 1, the molar concentration ratio of the oxidizing agent ferric trichloride, the doping agent hydrochloric acid, and the pyrrole monomer is 0.38:2:1 (example 1), the prepared MXene modified multifunctional bamboo fiber electromagnetic shielding paper has better comprehensive performance from the analysis of mechanical performance, electric conductivity, temperature resistance and electromagnetic shielding performance.
TABLE 1 Performance test results of multifunctional bamboo fiber electromagnetic shielding papers obtained by molar concentration ratios of different oxidants of ferric trichloride, doping agent of hydrochloric acid and pyrrole monomer
Example 3:
the mass ratio of the MXene to the polyimide resin in the example 1 was adjusted, and other parameters were kept the same as those in the example 1, to obtain a MXene-modified multifunctional bamboo fiber electromagnetic shielding paper.
The performance of the obtained MXene modified multifunctional bamboo fiber electromagnetic shielding paper is tested, and the test results are shown in Table 2. As can be seen from table 2, the mass ratio of MXene to polyimide resin solution was 0.6:100 In the case of (example 1), the prepared MXene-modified multifunctional bamboo fiber electromagnetic shielding paper has better comprehensive performance from the analysis of mechanical performance, electric conductivity, temperature resistance and electromagnetic shielding performance.
Table 2, performance test results of multifunctional bamboo fiber electromagnetic shielding paper obtained with different MXene addition amounts example 4:
and (3) preparing the MXene modified multifunctional bamboo fiber electromagnetic shielding paper by using different bamboo fiber paper-based framework materials. Referring to example 1, the mass ratio of the bamboo fiber to the carbon fiber was adjusted by changing the addition amount of the carbon fiber, and the other was unchanged, so as to prepare a corresponding MXene-modified multifunctional bamboo fiber electromagnetic shielding paper. The specific results are shown in Table 3:
TABLE 3 Performance results of MXene-modified multifunctional bamboo fiber electromagnetic shielding papers obtained from different mass ratios of bamboo fibers to carbon fibers
The result shows that: the mechanical property and electromagnetic shielding efficiency of the multifunctional bamboo fiber electromagnetic shielding paper modified by the MXene are known, and the mass ratio of the bamboo fiber to the carbon fiber is 8:2, the performance of the obtained MXene modified multifunctional bamboo fiber electromagnetic shielding paper is optimal.
Comparative example 1:
the MXene modification at step 2 of example 1 was omitted and other conditions or parameters were consistent with example 1.
Dispersing 1.51g of bamboo fiber and 0.37g of carbon fiber in 400g of water, stirring for 5min, carrying out sheet making on a sheet making device, then pressing for 5min under the pressure of 0.4MPa, and drying for 10min at 105 ℃ to obtain the light flexible bamboo fiber paper-based framework material.
4.3g of oxidant ferric trichloride, 9.3g of doping agent HCl, 1.7g of pyrrole monomer and 50ml of water are added into a beaker, after being uniformly mixed, bamboo fiber paper-based framework material (5X 5 cm) is immersed into the mixed solution, reacted for 12 hours in ice water bath (0 ℃), and polypyrrole modified bamboo fiber conductive paper is obtained after 3 times of washing and drying at 65 ℃.
Adding 0.3g of MXene into 50mL of polyimide resin solution (100 g/L), and mixingThe coating machine is used for coating the surface of the polypyrrole modified bamboo fiber conductive paper, and the coating amount is 10g/m 2 Finally, drying at 105 ℃ to obtain the polypyrrole-modified bamboo fiber electromagnetic shielding paper.
The bamboo fiber electromagnetic shielding paper (unmodified MOF) obtained in comparative example 1 was tested for mechanical properties, electrical conductivity, deicing time, flame retardant rating, and electromagnetic shielding properties, and the obtained results are shown in table 4.
Comparative example 2:
the encapsulation of MXene by polypyrrole in example 1 was omitted and other conditions or parameters were consistent with example 1.
Dispersing 1.51g of bamboo fiber and 0.37g of carbon fiber in 400g of water, stirring for 5min, carrying out sheet making on a sheet making device, then pressing for 5min under the pressure of 0.4MPa, and drying for 10min at 105 ℃ to obtain the light flexible bamboo fiber paper-based framework material.
Adding 0.3g of MXene and 50ml of water into a beaker, uniformly mixing, immersing a bamboo fiber paper-based framework material (5X 5 cm) into the mixed solution, reacting for 12h in an ice water bath (0 ℃), washing for 3 times, and drying at 65 ℃ to obtain the MXene modified bamboo fiber conductive paper.
Adding 0.3g of MXene into 50mL of polyimide resin solution (100 g/L), uniformly mixing the two, and coating the mixture on the surface of the MXene modified bamboo fiber conductive paper by using a coating machine, wherein the coating amount is 10g/m 2 Finally, drying at 105 ℃ to obtain the bamboo fiber electromagnetic shielding paper modified by the MOF material.
The bamboo fiber electromagnetic shielding paper (not polypyrrole encapsulated) obtained in comparative example 2 was tested for mechanical properties, electrical conductivity, deicing time, flame retardant rating, and electromagnetic shielding properties, and the obtained results are shown in table 4.
Comparative example 3:
the introduction of the PI/MXene protective coating in example 1 was omitted and other conditions or parameters were consistent with example 1.
Dispersing 1.51g of bamboo fiber and 0.37g of carbon fiber in 400g of water, stirring for 5min, carrying out sheet making on a sheet making device, then pressing for 5min under the pressure of 0.4MPa, and drying for 10min at 105 ℃ to obtain the light flexible bamboo fiber paper-based framework material.
0.3g MXene, 9.3g ferric trichloride serving as an oxidant, 4.3g hydrochloric acid serving as a doping agent, 1.7g pyrrole monomer and 50ml water are added into a beaker, after being uniformly mixed, a bamboo fiber paper-based framework material (5X 5 cm) is immersed into a mixed solution of the materials, the materials react for 12 hours in an ice water bath (0 ℃), and polypyrrole/MXene modified bamboo fiber conductive paper is obtained after 3 times of washing and drying at 65 ℃.
The polypyrrole/MXene modified bamboo fiber conductive paper (uncoated) obtained in comparative example 3 was tested for mechanical properties, conductivity, deicing time, flame retardant rating, and electromagnetic shielding properties, and the obtained results are shown in table 4.
Table 4, results of the product Performance test obtained in comparative examples 1 to 3
In combination with comparative examples 1 and 2 and example 1, the modification of the MXene material and the encapsulation of the polypyrrole on the MXene enable the multifunctional bamboo fiber electromagnetic shielding paper to be obviously superior to the electromagnetic shielding performance of the bamboo fiber electromagnetic shielding paper modified by a single material, in addition, in combination with comparative example 3 and example 1, the mechanical performance and the corrosion resistance of the multifunctional bamboo fiber electromagnetic shielding paper can be enhanced by introducing the MXene/PI protective coating, and the multifunctional bamboo fiber electromagnetic shielding paper can also be used as a heating material, a frost resistance, a defrosting material and the like.
The foregoing is merely a preferred embodiment of the invention, and it is to be understood that the invention is not limited to the form disclosed herein but is not to be construed as excluding other embodiments, but is capable of numerous other combinations, modifications and environments and is capable of modifications within the scope of the inventive concept, either as taught or as a matter of routine skill or knowledge in the relevant art. And that modifications and variations which do not depart from the spirit and scope of the invention are intended to be within the scope of the appended claims.
Claims (9)
1. A preparation method of multifunctional bamboo fiber electromagnetic shielding paper is characterized in that: the method comprises the following steps:
s1, dispersing bamboo fibers and carbon fibers in water, uniformly mixing, sheet making, squeezing and drying to obtain a light flexible bamboo fiber paper-based framework material;
s2, uniformly mixing a functional material MXene, an oxidant ferric trichloride, a doping agent hydrochloric acid and pyrrole monomers, immersing a light flexible bamboo fiber paper-based framework material into the mixed solution, carrying out pyrrole polymerization reaction, packaging the functional material MXene in the light flexible bamboo fiber paper-based framework material and on the surface of the light flexible bamboo fiber paper-based framework material, and washing and drying to obtain polypyrrole/MXene modified bamboo fiber conductive paper;
s3, adding a functional material MXene into the polyimide resin solution, uniformly mixing the functional material MXene and the polyimide resin solution, coating the functional material on the surface of the polypyrrole/MXene modified bamboo fiber conductive paper, and drying to obtain the MXene modified multifunctional bamboo fiber electromagnetic shielding paper.
2. The method for preparing the multifunctional bamboo fiber electromagnetic shielding paper according to claim 1, which is characterized in that: in the step S1, the mass ratio of the bamboo fiber to the carbon fiber is 1:1, up to 4:1, the ration of the light flexible bamboo fiber paper-based framework material is 60g/m 2 。
3. The method for preparing the multifunctional bamboo fiber electromagnetic shielding paper according to claim 2, which is characterized in that: the squeezing pressure is 0.3-0.5 Mpa, and the drying temperature is 100-120 ℃.
4. The method for preparing the multifunctional bamboo fiber electromagnetic shielding paper according to claim 1, which is characterized in that: in the step S2, the molar concentration ratio of the functional material MXene, the oxidizing agent ferric trichloride, the doping agent hydrochloric acid and the pyrrole monomer is 1:31:14:6.
5. the method for preparing the multifunctional bamboo fiber electromagnetic shielding paper according to claim 1, which is characterized in that: in the step S2, the polymerization of pyrrole is performed in an ice-water bath.
6. The method for preparing the multifunctional bamboo fiber electromagnetic shielding paper according to claim 5, which is characterized in that: the temperature of the polymerization reaction is 0 ℃, and the reaction time is 6-18 h.
7. The method for preparing the multifunctional bamboo fiber electromagnetic shielding paper according to claim 1, which is characterized in that: in the step S3, a functional material MXene is added into a polyimide resin solution, and after the functional material MXene and the polyimide resin solution are uniformly mixed, the functional material MXene and the polyimide resin solution are coated on the surface of the polypyrrole/MXene modified bamboo fiber conductive paper by using a coating machine.
8. The method for preparing the multifunctional bamboo fiber electromagnetic shielding paper according to claim 1, which is characterized in that: in the step S3, the mass concentration of the polyimide resin solution is 50-150 g/L.
9. The method for preparing the multifunctional bamboo fiber electromagnetic shielding paper according to claim 1, which is characterized in that: in the step S3, the mass ratio of the functional material MXene to the polyimide resin solution is at least 0.1:100, up to 1:100.
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| CN (1) | CN117702538A (en) |
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2023
- 2023-12-20 CN CN202311767524.9A patent/CN117702538A/en active Pending
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