Modified glass powder based on supercritical fluid treatment as well as modification method and application thereof

Abstract

The invention relates to the technical field of C03C12 / 00, in particular to modified glass powder based on supercritical fluid treatment and a modification method and application thereof.The modified glass powder is at least prepared from a silane coupling agent, a solvent and glass powder, the mass ratio of the silane coupling agent to the solvent to the glass powder is (1-4): (4-7): (3-15), and the modified glass powder is prepared by controlling the mass ratio of the silane coupling agent to the solvent to the glass powder. The optimized solvent is an ethanol-water system, a supercritical fluid treatment process is matched, the application effect of the obtained modified glass powder in the conductive silver paste is guaranteed, the method is good in controllability, the more accurate surface modification effect on the glass powder can be achieved, meanwhile, the reaction rate and efficiency can be effectively improved, and the production efficiency can be improved.

Description

Technical Field

[0001] The present invention relates to the technical field of CO3C12 / 00, and in particular to a modified glass powder based on supercritical fluid treatment, and a modification method and application thereof. Background Art

[0002] Due to the high surface energy, glass powder is easy to agglomerate in the organic carrier and has poor dispersibility, resulting in uneven slurry performance. The silane alkoxy group in the silane coupling agent is reactive to inorganic substances, and the organic functional group is reactive or compatible to organic substances. Therefore, when the silane coupling agent is between the inorganic and organic interfaces, a bonding layer of organic matrix-silane coupling agent-inorganic matrix can be formed, so the silane coupling agent can be used for surface modification of glass powder. However, the modification effect of this method may have certain limitations, and the modification effect is unstable. For example, a Chinese patent (publication number CN108164151A) discloses a method for preparing micron-level surface-modified glass powder for integrated circuit substrates. After alkali-free glass sheets and alkali-free glass sand are ground and classified, they are added to a high-speed mixer and stirred at high speed to increase the temperature. At the same time, a silane coupling agent is added, and then stirred at high speed, kept warm and discharged. Finally, the powder is passed through a high-speed disperser and transported to a high-speed classifier through airflow to cut large particles. The powder is sieved to obtain modified glass powder. However, it is difficult to achieve uniform coverage of the surface of the glass powder, and the stability and consistency of the modification effect cannot be guaranteed. Summary of the invention

[0003] In order to solve the above problems, the present invention provides a modification method for modified glass powder based on supercritical fluid treatment. The method has good controllability and can achieve a more precise surface modification effect on the glass powder. At the same time, it can effectively improve the reaction rate and efficiency and improve production efficiency.

[0004] On one hand, the present invention provides a modified glass powder based on supercritical fluid treatment, wherein the raw materials for preparing the modified glass powder at least include a silane coupling agent, a solvent, and a glass powder, wherein the mass ratio of the silane coupling agent, the solvent, and the glass powder is (1-4): (4-7): (3-15).

[0005] As a preferred technical solution, the mass ratio of the silane coupling agent, the solvent and the glass powder is (2-4):(4-6):(8-12), preferably (2.8-4):(4.3-5.8):10.

[0006] As a preferred technical solution, the silane coupling agent is a vinyl silane coupling agent and / or an amino silane coupling agent. Preferably, the silane coupling agent is one of vinyl triethoxy silane, vinyl trimethoxy silane, and aminomethyl triethoxy silane, preferably vinyl triethoxy silane.

[0007] As a preferred technical solution, the solvent is at least one of ethanol and water. Preferably, the solvent is a combination of ethanol and water, and the mass ratio of ethanol to water is (5-12):1, preferably (8-10):1.

[0008] As a preferred technical solution, the glass powder includes but is not limited to borosilicate glass and lead silicate glass, preferably lead silicate glass.

[0009] As a preferred technical solution, the D50 particle size of the glass powder is 1.0-2.0 μm, and the span range is 0.8-1.4.

[0010] Preferably, the D50 particle size of the glass powder is 1.1-1.5 μm, and the span range is 0.8-1.0.

[0011] In order to match the supercritical fluid treatment process, the present invention controls the mass ratio of the silane coupling agent, the solvent, and the glass powder, optimizes the solvent to be an ethanol-water system, and ensures the application effect of the obtained modified glass powder in the conductive silver paste.

[0012] Another aspect of the present invention provides a method for modifying glass powder based on supercritical fluid treatment, which comprises at least the following steps:

[0013] (1) mixing a silane coupling agent, a solvent and glass powder and placing the mixture in a reactor of a supercritical fluid device;

[0014] (2) adjusting the pressure and temperature of the supercritical fluid device and setting the reaction time so that the reactor reaches a supercritical fluid state and then performs surface modification on the glass powder; after the reaction is completed, taking out the material in the reactor and drying it to obtain modified glass powder.

[0015] As a preferred technical solution, the pressure of the supercritical fluid device is 2.0-5.0 MPa, preferably 2.5-4.5 MPa, and more preferably 2.5-3 MPa.

[0016] As a preferred technical solution, the temperature of the supercritical fluid device is 30-80°C, preferably 35-70°C, and more preferably 40-60°C.

[0017] As a preferred technical solution, the reaction time is 30 min to 120 min, preferably 30 to 90 min, and more preferably 40-50 min.

[0018] The modification method of the glass powder modified by supercritical fluid treatment provided by the present invention can dissolve the silane coupling agent in the supercritical fluid by comprehensively controlling the pressure, temperature and reaction time of the supercritical fluid device, and then the glass powder is treated in the supercritical fluid, so that the silane coupling agent can be uniformly adsorbed on the surface of the glass powder, achieving uniform coverage of the surface of the glass powder, and improving the stability and consistency of the modification effect.

[0019] The modified glass powder treated by supercritical fluid has good dispersibility and stability in an organic carrier, and is applied in a conductive silver paste to enable the battery to have a higher photoelectric conversion efficiency, which is mainly manifested in a lower series resistance.

[0020] In addition, the supercritical fluid treated modified glass powder provided by the present invention can achieve uniform modification in a shorter reaction time at a lower temperature, greatly improving production efficiency while reducing production energy consumption, avoiding the shortcomings of high temperature and high pressure treatment required in traditional methods, and being safer and more environmentally friendly.

[0021] The modification method of modified glass powder based on supercritical fluid treatment provided by the present invention has good controllability, can achieve a more precise surface modification effect on the glass powder, make the glass powder evenly dispersed in the organic carrier, and reduce agglomeration. It is of great significance to the field of conductive silver paste and is expected to have a positive impact on its development.

[0022] The second aspect of the present invention provides an application of modified glass powder based on supercritical fluid treatment, which is applied to the preparation of conductive silver paste.

[0023] As a preferred technical solution, the raw materials for preparing the conductive silver paste include at least 85-90% silver powder, 2-3% modified glass powder, and the balance made up by organic carrier, calculated by mass percentage.

[0024] As a preferred technical solution, the preparation method of the conductive silver paste is: mixing silver powder, modified glass powder, and organic carrier into silver paste; stirring and mixing the silver paste and then grinding it homogenously with a three-roll grinder to obtain the conductive silver paste.

[0025] Preferably, the organic carrier is a combination of a resin and an organic solvent, and the mass ratio of the two is (6-8): (1-2).

[0026] Preferably, the resin includes but is not limited to at least one of acrylic resin and ethyl cellulose, and the organic solvent includes but is not limited to at least one of alcohol ester hexadecene and silicone oil.

[0027] Preferably, the fineness of the conductive silver paste is 3 to 15 μm, preferably 3 to 10 μm.

[0028] Beneficial Effects

[0029] 1. The present invention provides a modification method for modified glass powder based on supercritical fluid treatment. The method has good controllability and can achieve a more precise surface modification effect on the glass powder. At the same time, it can effectively improve the reaction rate and efficiency and improve production efficiency.

[0030] 2. The present invention controls the mass ratio of the silane coupling agent, the solvent, and the glass powder, optimizes the solvent to be an ethanol-water system, and matches the supercritical fluid treatment process to ensure the application effect of the obtained modified glass powder in the conductive silver paste.

[0031] 3. The modification method of the glass powder based on supercritical fluid treatment provided by the present invention can dissolve the silane coupling agent in the supercritical fluid by comprehensively controlling the pressure, temperature and reaction time of the supercritical fluid device, and then the glass powder is treated in the supercritical fluid, so that the silane coupling agent can be uniformly adsorbed on the surface of the glass powder, achieving uniform coverage of the surface of the glass powder, and improving the stability and consistency of the modification effect.

[0032] 4. The modified glass powder treated by supercritical fluid in the present invention has good dispersibility and stability in the organic carrier. When applied to the conductive silver paste, the battery has a higher photoelectric conversion efficiency, which is mainly manifested in lower series resistance.

[0033] 5. The supercritical fluid treated modified glass powder provided by the present invention can achieve uniform modification in a shorter reaction time at a lower temperature, greatly improving production efficiency while reducing production energy consumption, avoiding the disadvantages of high temperature and high pressure treatment required in traditional methods, and is safer and more environmentally friendly. DETAILED DESCRIPTION

[0034] Example 1

[0035] Embodiment 1 of the present invention provides a modified glass powder based on supercritical fluid treatment, wherein the raw materials for preparing the modified glass powder include a silane coupling agent, a solvent, and a glass powder, and the mass ratio of the silane coupling agent, the solvent, and the glass powder is 2.8:4.3:10.

[0036] The silane coupling agent is vinyltriethoxysilane.

[0037] The solvent is a combination of ethanol and water, and the mass ratio of the ethanol to water is 9:1.

[0038] The glass powder is lead-silicon glass JY001 independently developed by Guangdong Nanhai Qiming Everbright Technology Co., Ltd. The D50 particle size of the glass powder is 1.4 μm and the span range is 0.9.

[0039] Embodiment 1 of the present invention provides, on the other hand, a method for modifying glass powder by supercritical fluid treatment, comprising the following steps:

[0040] (1) mixing a silane coupling agent, a solvent and glass powder and placing the mixture in a reactor of a supercritical fluid device;

[0041] (2) adjusting the pressure and temperature of the supercritical fluid device and setting the reaction time so that the reactor reaches a supercritical fluid state and then performs surface modification on the glass powder; after the reaction is completed, taking out the material in the reactor and drying it to obtain modified glass powder.

[0042] The model of the supercritical fluid device is HT-250FC-DB, which was purchased from Shanghai Huotong Experimental Instrument Co., Ltd.

[0043] The pressure of the supercritical fluid device is 2.5 MPa.

[0044] The temperature of the supercritical fluid device is 40°C.

[0045] The reaction time is 40 min.

[0046] Example 2

[0047] Embodiment 2 of the present invention provides a modified glass powder based on supercritical fluid treatment and a modification method thereof, and its specific implementation manner is the same as that of Embodiment 1, except that the mass ratio of the silane coupling agent, the solvent, and the glass powder is 2.8:5.8:10.

[0048] Example 3

[0049] Embodiment 3 of the present invention provides a modified glass powder and a modification method thereof based on supercritical fluid treatment. Its specific implementation method is the same as that of Embodiment 1, except that the mass ratio of the silane coupling agent, the solvent, and the glass powder is 2.8:5.8:10; the pressure of the supercritical fluid device is 3MPa; the temperature of the supercritical fluid device is 60°C; and the reaction time is 50min.

[0050] Example 4

[0051] Embodiment 4 of the present invention provides a modified glass powder and a modification method thereof based on supercritical fluid treatment. Its specific implementation method is the same as that of Embodiment 1, except that the mass ratio of the silane coupling agent, the solvent, and the glass powder is 4.3:5.8:10; the pressure of the supercritical fluid device is 3MPa; the temperature of the supercritical fluid device is 60°C; and the reaction time is 50min.

[0052] Comparative Example 1

[0053] Comparative Example 1 of the present invention provides a common glass powder, which is the same as the glass powder in Example 1, and the glass powder is not modified by silane coupling agent and supercritical fluid treatment.

[0054] Comparative Example 2

[0055] Comparative Example 2 of the present invention provides a modified glass powder based on supercritical fluid treatment and a modification method thereof. Its specific implementation method is the same as Example 1, except that the pressure of the supercritical fluid device is 2MPa; the temperature of the supercritical fluid device is 25°C; and the reaction time is 20min.

[0056] Comparative Example 3

[0057] Comparative Example 3 of the present invention provides a modified glass powder based on supercritical fluid treatment and a modification method thereof. Its specific implementation method is the same as Example 1, except that the pressure of the supercritical fluid device is 5MPa; the temperature of the supercritical fluid device is 85°C; and the reaction time is 130min.

[0058] Application Examples 1-4, Application Comparative Examples 1-3

[0059] Embodiments 1-4 of the present invention and comparative application examples 1-3 provide a conductive silver paste, and the formula is shown in Table 1 in parts by weight.

[0060] Table 1

[0061]

[0062]

[0063] The preparation method of the conductive silver paste comprises: mixing silver powder, modified glass powder and organic carrier into silver paste; stirring and mixing the silver paste and then grinding and homogenizing the silver paste with a three-roll grinder to obtain the conductive silver paste.

[0064] The fineness of the conductive silver paste is 3-10 μm.

[0065] Performance Testing

[0066] The conductive silver paste provided in Application Examples 1-4 and Application Comparative Examples 1-3 was respectively printed on the front side of the N-type TOPCon silicon wafer by screen printing, and the silver paste was uniformly printed on the back side. The wafer was sintered at a peak temperature of 710°C in a sintering furnace and light was injected. The wafer was then passed through a LECO device for laser-assisted sintering to obtain a cell. The open circuit voltage (Uoc), short circuit current (Isc), series resistance (Rs), fill factor (FF) and conversion efficiency (Eta) were obtained by current-voltage performance testing. The test results are shown in Table 2.

[0067] Table 2

[0068] <![CDATA[U oc (V)]]> Isc(A) <![CDATA[R s (Oh)]]> FF(%) Eta(%) Application Comparative Example 1 0.7192 13.865 0.00147 84.95 25.65 Application Comparative Example 2 0.7201 13.872 0.00137 85.02 25.68 Application Comparative Example 3 0.7204 13.871 0.00135 85.03 25.69 Application Example 1 0.7197 13.867 0.00107 85.22 25.72 Application Example 2 0.7201 13.870 0.00105 85.24 25.74 Application Example 3 0.7204 13.873 0.00104 85.27 25.78 Application Example 4 0.7206 13.875 0.00108 85.22 25.75

[0069] By analyzing the above table, it can be seen that the silver paste provided by Application Examples 1-4 has a higher photoelectric conversion efficiency than the silver paste provided by Application Comparative Examples 1-3, which is mainly manifested in a lower series resistance.

Claims

1. A method for treating modified glass powder based on supercritical fluid. It is characterized in that The raw materials for preparing the invention at least include a silane coupling agent, a solvent and glass powder, and the mass ratio of the silane coupling agent, the solvent and the glass powder is (1-4): (4-7): (3-15).

2. The modified glass powder based on supercritical fluid treatment according to claim 1, It is characterized in that The silane coupling agent is a vinyl silane coupling agent and / or an amino silane coupling agent.

3. The modified glass powder based on supercritical fluid treatment according to claim 1, It is characterized in that The solvent is at least one of ethanol and water.

4. The modified glass powder based on supercritical fluid treatment according to claim 1, It is characterized in that The glass powder is selected from at least one of borosilicate glass and lead silicate glass.

5. The glass powder modified by supercritical fluid treatment according to claim 4, It is characterized in that The D50 particle size of the glass powder is 1.0-2.0 μm, and the span range is 0.8-1.

4.

6. A method for modifying glass powder by supercritical fluid treatment according to any one of claims 1 to 5, It is characterized in that At least the following steps are included: (1) mixing a silane coupling agent, a solvent and glass powder and placing the mixture in a reactor of a supercritical fluid device; (2) adjusting the pressure and temperature of the supercritical fluid device and setting the reaction time so that the reaction furnace reaches a supercritical fluid state and then performs surface modification on the glass powder; After the reaction is completed, the material in the reaction furnace is taken out and dried to obtain modified glass powder.

7. The method for modifying glass powder by supercritical fluid treatment according to claim 6, It is characterized in that The pressure of the supercritical fluid device is 2.0-5.0 MPa.

8. The method for modifying glass powder by supercritical fluid treatment according to claim 6, It is characterized in that The temperature of the supercritical fluid device is 30-80°C.

9. The method for modifying glass powder by supercritical fluid treatment according to claim 6, It is characterized in that The reaction time is 30 min to 120 min.

10. An application of the modified glass powder based on supercritical fluid treatment according to any one of claims 1 to 5, It is characterized in that Used in the preparation of conductive silver paste.

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