Crystalline sealing glass powder and method for producing the same, sealing glass, and metal-supported solid oxide fuel cell

Abstract

The application discloses a crystalline sealing glass powder and a preparation method thereof, a sealing glass and a metal-supported solid oxide fuel cell, and relates to the technical field of vehicles. The application is applied to the metal-supported solid oxide fuel cell, and the composition comprises SiO2, B2O3, Al2O3, ZnO, light rare earth oxide and alkaline earth metal oxide. The volatilization of boron in the glass can be effectively inhibited by adding the light rare earth oxide, the generation of holes in the sealing glass is reduced, the air tightness of the sealing glass is improved, the expansion coefficient and the characteristic temperature can be effectively adjusted by simultaneously adding the alkaline earth metal oxide and the light rare earth oxide, the sealing fluidity is better, the expansion coefficient is higher, and the glass has the expansion coefficient and the working temperature which match the sealing requirements of the solid fuel cell. The crystalline sealing glass powder of the application is crystallized during the sealing process, and the thermal expansion coefficient matches other components of the SOFC.

Description

Technical Field

[0001] The present application relates to the field of new energy technology, and in particular to crystalline sealing glass powder and a preparation method thereof, sealing glass, and metal-supported solid oxide fuel cells. Background Art

[0002] The sealing glass used in SOFCs (metal-supported solid oxide fuel cells) primarily consists of four types: silicate, borosilicate, aluminosilicate, and boroaluminosilicate. Borosilicate is the most promising sealing glass. However, under SOFC operating conditions, the volatilization of boron-containing substances in borosilicate glass seriously reduces the thermal stability of the glass itself. Furthermore, this volatilization can lead to the formation of numerous pores in the sealing glass, compromising the sealing material's airtightness.

[0003] Traditional glass is amorphous and is a mixture of various components, which makes it very easy for SOFC stacks sealed with traditional glass to be damaged due to the violent expansion of the sealing glass. Summary of the Invention

[0004] The present application provides a crystalline sealing glass powder and a preparation method thereof, sealing glass and a metal-supported solid oxide fuel cell to solve the existing problems of volatilization of boron-containing substances and violent expansion of sealing glass.

[0005] In the first aspect, the present application provides a crystalline sealing glass powder for use in metal-supported solid oxide fuel cells, the components of which include: SiO2, B2O3, Al2O3, ZnO, light rare earth oxides and alkaline earth metal oxides.

[0006] Glass-ceramics is a new type of glass. Its principle is to adjust the composition so that the components within the glass spontaneously form crystal nuclei, thereby forming relatively uniform glass crystals. Glass-ceramics generally combine the characteristics of both glass and ceramics, and its expansion coefficient changes relatively linearly. This application uses a crystalline sealing glass powder composed of SiO2, B2O3, Al2O3, ZnO, light rare earth oxides, and alkaline earth metal oxides to form glass-ceramics.

[0007] By adding light rare earth oxides, this application effectively inhibits boron volatilization from the glass, reduces the formation of pores in the sealing glass, and improves the airtightness of the sealing glass. Simultaneously, the addition of alkaline earth metal oxides and light rare earth oxides effectively adjusts the thermal expansion coefficient and characteristic temperature, resulting in improved seal fluidity and a higher thermal expansion coefficient, ensuring that the glass has the thermal expansion coefficient and operating temperature required for solid fuel cell sealing. The crystalline sealing glass powder in this application crystallizes during the sealing process, matching the thermal expansion coefficient of other SOFC components.

[0008] Light rare earth elements (LREs) are a class of rare earth elements consisting of seven: lanthanum, cerium, praseodymium, neodymium, promethium, samarium, and europium. LREs are chemically active and react with many elements. They readily combine with oxygen to form stable oxides, such as lanthanum oxide (La2O3) and cerium oxide (CeO2), which exhibit excellent chemical stability.

[0009] In some embodiments, the light rare earth oxide includes at least one of La2O3, CeO2, and Nd2O3. Using at least one of the above light rare earth oxides can inhibit the volatilization of boron in the glass and improve the strength and chemical stability of the glass.

[0010] In some embodiments, the alkaline earth metal oxide includes at least one of MgO, CaO, SrO, and BaO. Using at least one of the alkaline earth metal oxides can reduce the melting temperature and viscosity of the glass and adjust the characteristic temperature and expansion coefficient of the glass.

[0011] In some embodiments, the mass ratios of SiO2, B2O3, Al2O3, ZnO, light rare earth oxide, and alkaline earth metal oxide are (5-15):(10-15):(1-8):(5-10):(30-45):(10-30). By controlling the mass ratios of the raw materials, the expansion coefficient and operating temperature of the encapsulating glass can be adjusted as needed, so that the softening temperature and sealing temperature of the encapsulating glass are as low as possible to reduce production energy consumption. At the same time, the sealing temperature of the encapsulating glass should be higher than the battery operating temperature to avoid damaging the seal. The softening temperature of the encapsulating glass should be as close as possible to the battery operating temperature but slightly higher than the battery operating temperature to avoid significant morphological changes in the sealing glass during battery stack operation.

[0012] In a second aspect, the present application provides a method for preparing a crystalline sealing glass powder, comprising the following steps:

[0013] Mixing raw materials of crystalline sealing glass powder to obtain a mixed material;

[0014] Melting the mixed materials to obtain molten glass;

[0015] The glass liquid is quenched to obtain glass;

[0016] The glass is crushed to obtain crystalline sealing glass powder.

[0017] The raw materials of the glass powder are mixed to obtain a mixture; the mixture is melted to obtain molten glass; the molten glass is quenched to obtain glass; and the glass is crushed to obtain glass powder.

[0018] In some embodiments, the mixed material is melted to obtain molten glass:

[0019] The melting temperature is 1400℃~1600℃. When the melting temperature is within this range, clear glass liquid can be obtained.

[0020] The heating rate during melting is 3°C / min~8°C / min. When the heating rate during melting is within this range, the decomposition and melting process of the glass batch material can be stabilized, thereby reducing the possibility of explosion of the raw materials.

[0021] The holding time during melting is 0.5~2h. When the holding time during melting is within this range, the decomposition and melting process of the glass batch material can be stabilized, and the probability of explosion of the raw materials can be reduced.

[0022] In some embodiments, the glass liquid is quenched to obtain the glass:

[0023] The quenching method includes either water quenching or oil quenching. The quenching method can convert the molten glass into cullet in a very short time. These quenching methods can achieve this goal at a relatively low cost; and / or,

[0024] The quenching temperature is 0°C to 30°C. When the quenching temperature is within this range, the quenching of the glass liquid can be achieved at a low cost.

[0025] In some embodiments, the glass is crushed to obtain a crystalline sealing glass powder:

[0026] The glass powder can be prepared by ball milling or air flow milling. The crystalline sealing glass powder can be obtained by finely grinding the glass slag. The above-mentioned grinding method can be used to obtain glass powder with uniform particle size distribution.

[0027] After obtaining the glass powder, it is sieved through a mesh size of 100-350. Sieving removes coarse particles. Within this mesh size range, a glass powder with a D50 of 5-15 μm can be obtained. The mesh size of the sieve refers to the particle size or coarseness of the material, defined as the number of holes per square inch. The mesh size of the sieve is inversely proportional to the pore size; that is, the higher the mesh size, the smaller the pore size on the sieve.

[0028] In a third aspect, the present application provides a sealing glass formed from the crystalline sealing glass powder of the first aspect, wherein:

[0029] The softening temperature of the sealing glass is 650-700° C.; and / or,

[0030] The sealing temperature of the sealing glass is 830-860° C.; and / or,

[0031] The expansion coefficient of the sealing glass is 8.7~9.5×10 -6 / K.

[0032] In a fourth aspect, the present application provides a metal-supported solid oxide fuel cell, comprising the sealing glass of the third aspect. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the following briefly introduces the drawings required for use in the description of the embodiments. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without any creative work.

[0034] Figure 1 This is a graph showing the expansion coefficient of borosilicate glass in the prior art of this application.

[0035] Figure 2 This is a curve diagram of the expansion coefficient of the crystalline sealing glass powder in Example 1 of the present application.

[0036] Figure 3 This is the XRD measurement diagram of the crystalline sealing glass powder in Example 1 of the present application.

[0037] Figure 4 This is a photo of the encapsulated microcrystalline glass prepared from the crystalline sealing glass powder of Example 1 of the present application. DETAILED DESCRIPTION

[0038] To make the objectives, technical solutions, and advantages of this application more clear, the technical solutions of this application will be clearly and completely described below in conjunction with the embodiments of this application. Obviously, the embodiments described are part of the embodiments of this application, not all of them. Based on the embodiments of this application, all other embodiments obtained by ordinary technicians in this field without making any creative efforts shall fall within the scope of protection of this application.

[0039] The sealing glass used in SOFCs (metal-supported solid oxide fuel cells) primarily consists of four types: silicate, borosilicate, aluminosilicate, and boroaluminosilicate. Borosilicate is the most promising sealing glass. However, under SOFC operating conditions, the volatilization of boron-containing substances in borosilicate glass seriously reduces the thermal stability of the glass itself. Furthermore, this volatilization can lead to the formation of numerous pores in the sealing glass, compromising the sealing material's airtightness.

[0040] Traditional glass is amorphous, that is, it is a mixture of various components. Its thermal expansion characteristics can be seen in Figure 1, has a very significant expansion peak, and the expansion peak is in the working range of medium and high temperature SOFC (600~800℃). Since other components of the stack usually have a linear expansion mode, the SOFC stack sealed with traditional glass is very easy to be damaged by the violent expansion of the sealing glass. Microcrystalline glass is a new type of glass. Its principle is to adjust the components so that the components inside the glass spontaneously form crystal nuclei, and then form glass crystals with relatively uniform components. Microcrystalline glass usually has the characteristics of both glass and ceramics, and its expansion coefficient changes relatively linearly, such as Figure 2 However, it is currently impossible to achieve the same expansion effect of glass-ceramics as other metal and ceramic components. Furthermore, the softening and sealing temperatures must be kept as low as possible to reduce production energy consumption. Furthermore, the sealing temperature must be higher than the operating temperature to avoid damaging the seal, and the softening temperature must be as close to but slightly higher than the operating temperature. This prevents significant morphological changes in the sealing glass during battery stack operation, making SOFC packaging challenging.

[0041] In view of this, the present application provides a crystalline sealing glass powder and a preparation method thereof, sealing glass and a metal-supported solid oxide fuel cell to solve the existing problems of volatilization of boron-containing substances and violent expansion of sealing glass.

[0042] In the first aspect, the present application provides a crystalline sealing glass powder for use in metal-supported solid oxide fuel cells, the components of which include: SiO2, B2O3, Al2O3, ZnO, light rare earth oxides and alkaline earth metal oxides.

[0043] Glass-ceramics is a new type of glass. Its principle is to adjust the composition so that the components within the glass spontaneously form crystal nuclei, thereby forming relatively uniform glass crystals. Glass-ceramics generally combine the characteristics of both glass and ceramics, and its expansion coefficient changes relatively linearly. This application uses a crystalline sealing glass powder composed of SiO2, B2O3, Al2O3, ZnO, light rare earth oxides, and alkaline earth metal oxides to form glass-ceramics.

[0044] By adding light rare earth oxides, this application effectively inhibits boron volatilization from the glass, reduces the formation of pores in the sealing glass, and improves the airtightness of the sealing glass. Simultaneously, the addition of alkaline earth metal oxides and light rare earth oxides effectively adjusts the thermal expansion coefficient and characteristic temperature, resulting in improved seal fluidity and a higher thermal expansion coefficient, ensuring that the glass has the thermal expansion coefficient and operating temperature required for solid fuel cell sealing. The crystalline sealing glass powder in this application crystallizes during the sealing process, matching the thermal expansion coefficient of other SOFC components.

[0045] Light rare earth elements (LREs) are a class of rare earth elements consisting of seven: lanthanum, cerium, praseodymium, neodymium, promethium, samarium, and europium. LREs are chemically active and react with many elements. They readily combine with oxygen to form stable oxides, such as lanthanum oxide (La2O3) and cerium oxide (CeO2), which exhibit excellent chemical stability.

[0046] In conjunction with the first aspect, in some embodiments provided herein, the light rare earth oxide includes at least one of La2O3, CeO2, and Nd2O3. Using at least one of these light rare earth oxides can inhibit boron volatilization in the glass and improve the strength and chemical stability of the glass.

[0047] In conjunction with the first aspect, in some embodiments provided herein, the alkaline earth metal oxide includes at least one of MgO, CaO, SrO, and BaO. Using at least one of these alkaline earth metal oxides can lower the melting temperature and viscosity of the glass and adjust the characteristic temperature and expansion coefficient of the glass.

[0048] In conjunction with the first aspect, in some embodiments provided herein, the mass ratios of SiO2, B2O3, Al2O3, ZnO, light rare earth oxide, and alkaline earth metal oxide are (5-15):(10-15):(1-8):(5-10):(30-45):(10-30). By controlling the mass ratios of the various raw materials, the expansion coefficient and operating temperature of the encapsulating glass can be adjusted as needed, so that the softening temperature and sealing temperature of the encapsulating glass are as low as possible to reduce production energy consumption. At the same time, the sealing temperature of the encapsulating glass should be higher than the battery operating temperature to avoid damaging the seal. The softening temperature of the encapsulating glass should be as close as possible to the battery operating temperature but slightly higher than the battery operating temperature to avoid significant morphological changes in the sealing glass during battery stack operation.

[0049] In a second aspect, the present application provides a method for preparing a crystalline sealing glass powder, comprising the following steps:

[0050] Mixing raw materials of crystalline sealing glass powder to obtain a mixed material;

[0051] Melting the mixed materials to obtain molten glass;

[0052] The glass liquid is quenched to obtain glass;

[0053] The glass is crushed to obtain crystalline sealing glass powder.

[0054] The raw materials of the crystalline sealing glass powder are mixed to obtain a mixed material; the mixed material is melted to obtain a glass liquid; the glass liquid is quenched to obtain glass; and the glass is crushed to obtain the crystalline sealing glass powder.

[0055] It should be noted that the raw material of SiO2 can be SiO2, the raw material of B2O3 can be H3BO3, the raw material of Al2O3 can be Al(OH)3, the raw material of ZnO can be ZnO, the raw material of light rare earth oxide can be La2O3, CeO2, Nd2O3, and the raw material of alkaline earth metal oxide can be CaCO3, SrCO3, Mg(OH)2, BaCO3.

[0056] In combination with the first aspect, in some embodiments provided in the present application, the mixed material is melted to obtain molten glass: the melting temperature is 1400°C to 1600°C. Within this melting temperature range, clear molten glass can be obtained.

[0057] In combination with the first aspect, in some embodiments provided in the present application, the mixed material is melted to obtain the glass liquid: the heating rate during melting is 3°C / min~8°C / min. The heating rate during melting is within this range, which can stabilize the decomposition and melting process of the glass batch material and reduce the possibility of explosion of the raw materials.

[0058] In conjunction with the first aspect, in some embodiments provided herein, the mixed material is melted to obtain molten glass, and the holding time during melting is 0.5 to 2 hours. Within this range, the holding time during melting can stabilize the decomposition and melting process of the glass batch material and reduce the probability of explosive combustion of the raw materials.

[0059] In conjunction with the first aspect, in some embodiments provided herein, the molten glass is quenched to obtain the glass: the quenching method includes either water quenching or oil quenching. The quenching method can form cullet from the molten glass in a very short time. These quenching methods are used to achieve this goal at a low cost, and the quenching temperature is 0°C to 30°C. Within this quenching temperature range, the molten glass can be quenched at a low cost.

[0060] In combination with the first aspect, in some embodiments provided in the present application, the glass slag is finely ground to obtain crystalline sealing glass powder: the fine grinding method includes any one of ball milling and air flow milling. By finely grinding the glass slag to obtain crystalline sealing glass powder and using the above-mentioned grinding method, glass powder with uniform particle size distribution can be obtained.

[0061] In conjunction with the first aspect, in some embodiments provided herein, in the crystalline sealing glass powder obtained by crushing the glass, the crushed glass is sieved through a mesh size of 100 to 350. Sieving can remove coarse particles of glass powder. Within this mesh size range, a glass powder with a particle size D50 of 5 to 15 μm can be obtained. The mesh size of the sieve refers to the particle size or coarseness of the material and is defined as the number of holes per square inch. The mesh size of the sieve is inversely proportional to the pore size; that is, the higher the mesh size, the smaller the pore size on the sieve.

[0062] In a third aspect, the present application provides a sealing glass formed from the crystalline sealing glass powder of the first aspect, wherein:

[0063] The softening temperature of the sealing glass is 650-700° C.; and / or,

[0064] The sealing temperature of the sealing glass is 830-860° C.; and / or,

[0065] The expansion coefficient of the sealing glass is 8.7~9.5×10 -6 / K.

[0066] In a fourth aspect, the present application provides a metal-supported solid oxide fuel cell, comprising the sealing glass of the third aspect.

[0067] The technical solution provided in this application is described in detail below with reference to the embodiments.

[0068] Example 1

[0069] Example 1 of the present application provides a crystalline sealing glass powder, whose composition includes: SiO2, B2O3, Al2O3, ZnO, La2O3, MgO, CaO, BaO, and the mass ratio thereof is 13.5:10:5.5:7:30:16:3.5:12.

[0070] Example 2

[0071] Example 2 of the present application provides a crystalline sealing glass powder, whose composition, in terms of mass percentage, includes: SiO2, B2O3, Al2O3, ZnO, CeO2, MgO, CaO, BaO, and the mass ratio thereof is 11:12:5.5:7:35:12:1.5:10.

[0072] Example 3

[0073] Example 3 of the present application provides a crystalline sealing glass powder, the composition of which includes: SiO2, B2O3, Al2O3, ZnO, Nd2O3, MgO, and BaO, and the mass ratio thereof is 8.5:14:5.5:7:40:10:16.

[0074] Example 4

[0075] Example 4 of the present application provides a crystalline sealing glass powder, the composition of which includes: SiO2, B2O3, Al2O3, ZnO, La2O3, BaO, and the mass ratio thereof is 5:15:1:10:30:30.

[0076] Example 5

[0077] Example 5 of the present application provides a crystalline sealing glass powder, the composition of which includes: SiO2, B2O3, Al2O3, ZnO, La2O3, CaO, and the mass ratio thereof is 15:10:8:5:45:10.

[0078] Example 6

[0079] Example 6 of the present application provides a crystalline sealing glass powder, the composition of which includes: SiO2, B2O3, Al2O3, ZnO, CeO2, SrO, and the mass ratio thereof is 10:13:4:8:40:20.

[0080] Example 7

[0081] Example 7 of the present application provides a method for preparing a crystalline sealing glass powder, comprising the following steps:

[0082] According to the composition of the crystalline sealing glass powder, the raw materials were mixed using a three-dimensional mixer for 30 minutes to obtain a mixture;

[0083] The mixture was placed in a platinum crucible, covered, and placed in an air atmosphere in a box-type resistance furnace. The mixture was heated at 5°C / min to 1490°C and kept at this temperature for 1 h to obtain a glass liquid.

[0084] Pour the glass liquid into 25℃ cold water for water quenching to obtain glass;

[0085] The glass was ball-milled, passed through a 200-mesh sieve, and dried at 85° C. for 240 min to obtain a crystalline sealing glass powder.

[0086] Comparative Example 1

[0087] Comparative Example 1 of the present application provides a sealing glass powder, which is borosilicate glass powder, and its specific composition includes: SiO2, B2O3, Al2O3, TiO2, BaO, CaO, and the mass ratio thereof is 21:10:5:4:55:5.

[0088] The crystalline sealing glass powders of Examples 1 to 6 were prepared according to the preparation method of the crystalline sealing glass powder of Example 7, and the performance of the sealing glass powder of Comparative Example 1 was tested to test the expansion coefficient, sealing temperature, softening temperature and fluidity. The results are shown in Table 1. The expansion coefficient of Example 1 is as follows: Figure 2 As shown, the XRD pattern of Example 1 is as follows Figure 3 As shown, the actual picture of the micro-ceramic glass formed after the micro-ceramic glass powder of Example 1 is as follows Figure 4 As shown ( Figure 4 (white part in the upper right corner).

[0089] The expansion coefficient test method is as follows: the glass is cast into a block, cut into 6mm*6mm*25mm specimens, and tested using an expansion coefficient meter.

[0090] The testing method for sealing temperature is: testing the medium-temperature viscosity of glass by parallel plate method, and determining the sealing temperature by the temperature corresponding to the viscosity of glass.

[0091] The softening temperature is determined by measuring the expansion coefficient using an expansion coefficient meter.

[0092] The fluidity test method is as follows: to determine the diameter of the flow column, the glass powder is pressed into a cylinder with a diameter of 12.5 mm and a height of 8 mm, and then sintered at 850°C for 60 minutes into a button shape, and its diameter is tested.

[0093] Table 1 Properties of the sealing glass powders of Examples 1 to 6 and Comparative Example 1

[0094]

[0095] From Table 1 and Figure 1 It can be seen that the softening temperature and sealing temperature of Examples 1 to 6 are significantly lower than those of the borosilicate glass in Comparative Example 1. At the same time, when sintered under the same temperature and time conditions, the flow diameters of Examples 1 to 6 are also significantly larger than those of Comparative Example 1, and have better sealing fluidity. The sealing glass powder of the present application can achieve good melting at 1490°C. The melting temperature of common silicate glass is usually above 1550°C, which will produce unfavorable factors such as high energy consumption and long time in actual application. Compared with the glass formula of Comparative Example 1 above, the softening temperature of the sealing glass powder for the flat-plate solid oxide fuel cell of Examples 1 to 6 is 650~700°C, the sealing temperature of the sealing glass powder is 830~860°C, and the expansion coefficient after crystallization is 8.7~9.5×10 -6 / K, with high matching degree with metal-metal sealing, realizes the sealing of solid oxide fuel cells at lower cost and shorter time.

[0096] In summary, the addition of light rare earth oxides effectively inhibits boron volatilization from the glass, reduces the formation of pores in the sealing glass, and improves the airtightness of the sealing glass. Simultaneously, the addition of alkaline earth metal oxides and light rare earth oxides effectively adjusts the thermal expansion coefficient and characteristic temperature, resulting in better sealing fluidity and a higher thermal expansion coefficient, allowing the glass to have a thermal expansion coefficient and operating temperature that match the sealing requirements of solid fuel cells. The crystalline sealing glass powder of this application crystallizes during the sealing process, matching the thermal expansion coefficient of other SOFC components.

[0097] In the description of this specification, the description with reference to the terms "one embodiment / method", "some embodiments / methods", "example", "specific example" or "some examples" means that the specific features, structures, materials or characteristics described in conjunction with the embodiment / method or example are included in at least one embodiment / method or example of the present application. In this specification, the schematic expressions of the above terms do not necessarily refer to the same embodiment / method or example. Moreover, the specific features, structures, materials or characteristics described may be combined in an appropriate manner in any one or more embodiments / methods or examples. In addition, those skilled in the art may combine and combine different embodiments / methods or examples described in this specification and the features of different embodiments / methods or examples, unless they are contradictory.

[0098] It should be noted that, in the present application, relational terms such as "first" and "second" are merely used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply the existence of any such actual relationship or order between these entities or operations. Moreover, the terms "comprise", "include" or any other variants thereof are intended to cover non-exclusive inclusion, so that the process, method, article or equipment comprising a series of elements includes not only those elements, but also includes other elements not explicitly listed, or also includes elements inherent to such process, method, article or equipment. In the absence of further restrictions, the elements defined by the sentence "comprise a ..." do not exclude the presence of other identical elements in the process, method, article or equipment comprising the elements. In the present application, the meaning of "plurality" is at least two, such as two, three, etc., unless otherwise clearly specified.

[0099] The foregoing is merely a list of specific embodiments of the present application, intended to enable those skilled in the art to understand or implement the present application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present application. Therefore, the present application is not limited to the embodiments shown herein, but is intended to conform to the broadest scope consistent with the principles and novel features of the present application.

Claims

1. A crystalline sealing glass powder, characterized in that: Applied to metal-supported solid oxide fuel cells, the composition includes: SiO2, B2O3, Al2O3, ZnO, light rare earth oxides and alkaline earth metal oxides, among which: The mass ratio of SiO2, B2O3, Al2O3, ZnO, light rare earth oxide and alkaline earth metal oxide is (5-15): (10-15): (1-8): (5-10): (30-45): (10-30); The light rare earth oxide includes at least one of La2O3, CeO2 and Nd2O3; The alkaline earth metal oxide includes at least one of MgO, CaO, SrO and BaO; In the sealing glass formed by the crystalline sealing glass powder: The softening temperature of the sealing glass is 650-700°C; The sealing temperature of the sealing glass is 830-860°C; The expansion coefficient of the sealing glass is 8.7~9.5×10 -6 / K; The sealing glass is suitable for a medium- and high-temperature SOFC operating range of 600-800°C.

2. A method for preparing the crystalline sealing glass powder according to claim 1, characterized in that: The following steps are involved: Mixing raw materials of crystalline sealing glass powder to obtain a mixed material; Melting the mixed materials to obtain molten glass; The glass liquid is quenched to obtain glass; The glass is crushed to obtain crystalline sealing glass powder.

3. The method for preparing the crystalline sealing glass powder according to claim 2, wherein: The mixed materials are melted to obtain molten glass: The melting temperature is 1400°C to 1600°C; and / or, The heating rate during melting is 3°C / min to 8°C / min; and / or, The holding time during melting is 0.5~2h.

4. The method for preparing the crystalline sealing glass powder according to claim 2, wherein: The glass liquid is quenched to obtain the glass: The quenching method includes water quenching or oil quenching; and / or, The quenching temperature is 0℃~30℃.

5. The method for preparing the crystalline sealing glass powder according to claim 2, wherein: The glass is crushed to obtain the crystalline sealing glass powder: The pulverization method includes any one of ball milling and air flow milling; and / or, The mesh size of the sieve after the glass is crushed is 100~350 mesh.

6. A sealing glass, characterized in that: It is formed from the crystalline sealing glass powder as claimed in claim 1.

7. A metal-supported solid oxide fuel cell, characterized in that: Comprising the sealing glass as claimed in claim 6.

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