High temperature liquid antimony electrode seal

Abstract

The application provides a high-temperature liquid-state antimony electrode sealing material, which is a glass glue containing one or more of sodium elements, potassium elements, calcium elements, magnesium elements, boron elements, barium elements, iron elements or cerium elements. The sealing material can not only generate a more compact intermediate layer during the operation of the liquid-state antimony anode battery, but also can trigger repair with the leaked antimony, so as to prevent the further leakage of the antimony metal, thereby achieving a better sealing effect and meeting the long-time operation of the liquid metal battery.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of battery materials, and particularly relates to a high-temperature liquid antimony electrode sealing material. BACKGROUND

[0002] Ceramic glue is a common high-temperature sealing material, which is widely used in the sealing of solid oxide fuel cells (SOFC). The main component of ceramic glue is silicate, which has good insulation and corrosion resistance. Although there are many pores in the structure of sintered ceramic glue, the surface tension between liquid antimony metal and the main component of ceramic glue, i.e. silicate, is large, so it is difficult for liquid antimony in the liquid antimony anode SOFC to penetrate into the ceramic glue micropores. Therefore, in the previous liquid antimony anode SOFC, ceramic glue is the first choice as a sealing material.

[0003] With the operation of the battery, the generated antimony oxide causes the surface tension of the antimony metal-ceramic glue to decrease, and then penetrates into the ceramic glue micropores, causing corrosion. Therefore, the use of ceramic glue for sealing can only guarantee the sealing effect of liquid antimony metal for tens of hours, and a more suitable sealing material and sealing structure are needed. SUMMARY

[0004] The inventors found that the conventional glass glue has excellent density as a liquid high-temperature sealing material, but during the operation of the battery, antimony, antimony oxide and glass glue are all in liquid state, and the density of glass glue is the smallest, so under the action of gravity, the density of antimony and antimony oxide is larger, which can penetrate through the glass glue sealing area, resulting in leakage. Therefore, the present application proposes a glass glue with excellent sealing performance for liquid antimony anode battery.

[0005] In a first aspect of the present application, a battery sealing material is provided. According to an embodiment of the present application, the sealing material is glass glue containing one or more of sodium element, potassium element, calcium element, magnesium element, boron element, barium element, iron element or cerium element. The inventors found that the conventional battery sealing material ceramic glue has a large number of voids inside, which is not suitable for long-time operation of high-temperature liquid battery, and the conventional glass glue has the problem of cracking under long-time operation. However, the glass glue containing one or more of sodium element, potassium element, calcium element, magnesium element, boron element, barium element, iron element or cerium element according to the embodiment of the present application not only generates a more dense intermediate layer during the operation of the liquid antimony anode battery, but also triggers a repair with the leaked antimony, preventing further leakage of the antimony metal, so as to achieve better sealing effect and meet the long-time operation of the liquid metal battery.

[0006] According to an embodiment of the present application, the above-mentioned battery sealing material can further include at least one of the following additional technical features:

[0007] According to an embodiment of the present application, the element exists in the form of oxide.

[0008] According to an embodiment of the present application, the sodium element exists in the form of Na2SiO3.

[0009] According to an embodiment of the present application, the potassium element exists in the form of K2SiO3.

[0010] According to an embodiment of the present application, the calcium element exists in the form of CaO.

[0011] According to an embodiment of the present application, the magnesium element exists in the form of MgO.

[0012] According to an embodiment of the present application, the boron element exists in the form of B2O3.

[0013] According to an embodiment of the present application, the barium element exists in the form of BaO. The inventor found that BaO reacts with liquid antimony and generates a solid phase mixture of Ba3Sb4O and Ba3Sb2O6, forming a dense intermediate layer, which blocks the leakage of liquid antimony metal. When liquid antimony leaks, a triggered repair occurs at the leakage, i.e. Sb2O3 invading the crack also causes the BaO in the glass to segregate, generating a solid phase of BaSb2O6 in the pores, thereby achieving a sealing self-repair effect.

[0014] According to an embodiment of the present application, the iron element exists in the form of Fe2O3. The inventor found that Fe2O3 reacts with liquid antimony and generates a solid phase mixture of FeO and FeSb2O4, forming a dense intermediate layer, which blocks the leakage of liquid antimony metal.

[0015] According to an embodiment of the present application, the cerium element exists in the form of CeO2. The inventor found that CeO2 reacts with liquid antimony and generates a solid phase mixture of Ce2O3 and Ce3Sb5O 12 , forming a dense intermediate layer, which blocks the leakage of liquid antimony metal.

[0016] According to an embodiment of the present application, the sealing material is a glass glue containing one or more of barium element, iron element or cerium element.

[0017] According to an embodiment of the present application, the element exists in the form of oxide.

[0018] According to embodiments of the present application, the barium element is in the form of BaO. The inventors have found that BaO reacts with liquid antimony and forms a solid phase mixture of Ba3Sb4O and Ba3Sb2O6, which forms a dense intermediate layer that blocks the leakage of liquid antimony metal. When liquid antimony leaks, a triggered repair occurs at the leakage site, i.e., the invading Sb2O3 also causes the BaO in the glass to segregate, forming solid phase BaSb2O6 in the pores, thereby achieving a self-sealing effect.

[0019] According to embodiments of the present application, the iron element is in the form of Fe2O3. The inventors have found that Fe2O3 reacts with liquid antimony and forms a solid phase mixture of FeO and FeSb2O4, which forms a dense intermediate layer that blocks the leakage of liquid antimony metal.

[0020] According to embodiments of the present application, the cerium element is in the form of CeO2. The inventors have found that CeO2 reacts with liquid antimony and forms a solid phase mixture of Ce2O3 and Ce3Sb5O 12 , which forms a dense intermediate layer that blocks the leakage of liquid antimony metal.

[0021] According to embodiments of the present application, the sealing material is a glass seal containing one or more of BaO, Fe2O3, or CeO2. The inventors have found that BaO, Fe2O3, or CeO2 not only reacts with Sb2O3 but also reacts with Sb, forming a solid phase mixture that forms a dense intermediate layer that blocks the leakage of liquid antimony metal.

[0022] According to embodiments of the present application, the sealing material is a glass seal containing BaO. The inventors have found that BaO reacts with liquid antimony and forms a solid phase mixture of Ba3Sb4O and Ba3Sb2O6, which forms a dense intermediate layer that blocks the leakage of liquid antimony metal. When liquid antimony leaks, a triggered repair occurs at the leakage site, i.e., the invading Sb2O3 also causes the BaO in the glass to segregate, forming solid phase BaSb2O6 in the pores, thereby achieving a self-sealing effect.

[0023] In another aspect of the present application, the application further provides the use of the aforementioned battery sealing material in solid oxide fuel cells. The inventors have found that the conventional battery sealing material ceramic glue has a large number of voids inside, which is not suitable for long-term operation of high-temperature liquid batteries. In addition, the conventional glass glue has a large density of antimony and antimony oxide that can penetrate through the glass glue sealing area during long-term operation, resulting in leakage. However, the battery sealing material according to the embodiments of the present application can not only generate a more dense intermediate layer during the operation of the liquid antimony anode battery, but also can trigger a repair with the leaked antimony to prevent further leakage of the antimony metal, thus achieving a better sealing effect and meeting the long-term operation of the liquid metal battery. Therefore, it can be well applied to solid oxide fuel cells.

[0024] According to the embodiments of the present application, the aforementioned application can further include at least one of the following additional technical features:

[0025] According to the embodiments of the present application, the solid oxide fuel cell is a high-temperature liquid antimony metal battery.

[0026] According to the embodiments of the present application, the aforementioned battery sealing material is filled in the gap between the anode shell and the half-cell plate of the battery. In this way, the gap between the half-cell plate and the anode shell is completely coated with the aforementioned battery sealing material, thereby enhancing the sealing performance of the battery.

[0027] According to the embodiments of the present application, the filling is performed by the following method:

[0028] S1: placing an antimony block on the half-cell plate, placing a cover above the antimony block after smearing the aforementioned battery sealing material on the edge of the anode shell and compacting, further smearing the aforementioned battery sealing material on the contact interface between the anode shell and the half-cell plate to form a single cell. In this way, the gap between the half-cell plate and the anode shell is completely coated with the aforementioned battery sealing material, thereby enhancing the sealing performance of the battery.

[0029] According to the embodiments of the present application, further comprising: S2: vertically stacking the single cells and further compacting with a clamp. Smearing silver paste on the ribs of the single cells can ensure better electrical conductivity between the batteries. The compacting operation can ensure that the aforementioned battery sealing material completely fills the gap at the contact interface between the anode shell and the half-cell plate. In addition, the compacting operation can also make the upper cathode plate and the lower anode shell in close contact, so that the batteries have better electrical conductivity.

[0030] According to the embodiments of the present application, the area of the single cell is 4cm 2 -10000cm 2 .

[0031] According to an embodiment of the present application, the number of the stacks is 2-100.

[0032] According to an embodiment of the present application, further comprising: S3: connecting the ribs of the single cells at the top of the battery stack by metal strips to achieve parallel connection between the stacked single cells.

[0033] According to an embodiment of the present application, the number of the parallel connections is 2-100. BRIEF DESCRIPTION OF DRAWINGS

[0034] The above and / or additional aspects and advantages of the present application will become apparent and be readily understood from the following description, taken in conjunction with the accompanying drawings, in which:

[0035] Figure 1 is a repair mechanism diagram of the preferred glass glue, in which (a) directly contacts Sb2O3, (b) Sb2O3 invades the crack;

[0036] Figure 2 is a schematic diagram of the preferred glass glue battery stack;

[0037] Figure 3 is an SEM image and element distribution diagram of the barium-containing glass glue antimony metal contact interface;

[0038] Figure 4 is an SEM image and element distribution diagram of the ceramic glue antimony metal contact interface; and

[0039] Figure 5 is a typical channel diagram of the high-temperature liquid battery prepared by the steps of Comparative Example 2, which appeared to have leakage of antimony metal in a high-temperature environment of 750°C. DETAILED DESCRIPTION

[0040] The embodiments described below are exemplary and are intended to be illustrative of the present application, and are not to be understood as limiting the present application.

[0041] Example 1

[0042] The trigger agent for the triggered repair of the sealing of the liquid antimony anode battery is Sb and Sb2O3, so it is necessary to screen the sealing material that can react with Sb and Sb2O3. The existing high-temperature insulating sealing material is mainly composed of oxides of elements such as aluminum, silicon, sodium, potassium, calcium, magnesium, boron, barium, etc. However, there is almost no research on the reaction characteristics of the oxides of these elements with Sb / Sb2O3. In order to carry out preliminary screening of the material, the stable composition after the reaction of Sb / Sb2O3 with these oxides was calculated based on the Open Quantum Materials Database (OQMD). The calculation was carried out based on the existing form of the elements commonly used in the sealant, and in the calculation conditions, the atomic ratio of antimony to other elements was set to 1:1, and the calculation results are shown in Table 1 (the unspent reactants are not listed as reaction products). As can be seen from the calculation results, silicon, aluminum and zirconium have the strongest stability and do not react with Sb / Sb2O3, which is an important reason why silicon, aluminum and zirconium become the primary component elements of a variety of sealing materials. In addition to silicon and aluminum, the oxides or silicates of a variety of elements commonly used in sealing materials can react with Sb2O3, among which BaO, Fe2O3 and CeO2 not only can react with Sb2O3 but also can react with Sb to form a solid-phase mixture. This provides a screening range for further optimization of the sealing material system in the future.

[0043] Table 1 Stable existing form of different elements mixed with Sb / Sb2O3

[0044]

[0045] As shown in Figure 1 (a), at the working temperature, BaO preferably reacts with the liquid antimony to form a solid-phase mixture of Ba3Sb4O and Ba3Sb2O6, and a dense intermediate layer is formed to block the leakage of the liquid antimony metal. In addition, as shown in Figure 1 (b), when the liquid antimony leaks, triggered repair will occur at the leakage, that is, the Sb2O3 invading the crack will also cause the BaO in the glass to segregate, and a solid-phase BaSb2O6 is generated in the pores, thereby achieving the effect of self-repairing sealing. Similarly, other preferred glass sealants have the same sealing effect and can effectively prevent the leakage of antimony metal, thereby laying a foundation for the development of high-temperature liquid antimony metal batteries.

[0046] Example 2

[0047] S1: The support body has a length of 100 mm, a width of 100 mm and a thickness of 1.5 mm.

[0048] S2: The solid-state antimony metal anode has a mass of 200 g and a size of 80 mm x 80 mm x 5 mm.

[0049] S3: The main shell of the anode shell is in the shape of a lid, with a length of 88 mm, a width of 88 mm, a height of 11 mm, and a wall thickness of 3 mm.

[0050] S4: The preferred glass glue (purchased from Ningbo Suofu Energy Technology Co., Ltd., model CY-S) is applied at the bottom edge of the anode shell and covers the antimony block, so that the gap between the anode shell and the support is filled with the preferred glass glue.

[0051] S5: A large amount of preferred glass glue is applied outside the contact surface between the anode shell and the support.

[0052] S6: Five single cells are connected in series to form one cell stack, and two cell stacks are connected in parallel.

[0053] S7: The cell stack is pressed using a clamp, so that the glass glue fills the gap between the anode shell and the support, the single cells are in close contact, the electrical conductivity is better, and the glass glue is more evenly distributed. Figure 2

[0054] After experimental testing, the high-temperature liquid battery prepared by the above process steps can stably operate at a high temperature of 750°C, and no blocky antimony metal leakage is found in the glass area as shown in Figure 3

[0055] Example 3

[0056] S1: The support has a length of 200 mm, a width of 200 mm, and a thickness of 1.5 mm.

[0057] S2: The solid-state antimony metal anode has a mass of 400 g and a size of 160 mm x 160 mm x 5 mm.

[0058] S3: The main shell of the anode shell is in the shape of a lid, with a length of 176 mm, a width of 176 mm, a height of 11 mm, and a wall thickness of 3 mm.

[0059] S4: The preferred glass glue (purchased from Shanghai Institute of Silicate, model SG-DB05) is applied at the bottom edge of the anode shell and covers the antimony block, so that the gap between the anode shell and the support is filled with the preferred glass glue.

[0060] S5: A large amount of preferred glass glue is applied outside the contact surface between the anode shell and the support.

[0061] S6: Five single cells are connected in series to form one cell stack, and two cell stacks are connected in parallel.

[0062] S7: The cell stack is pressed using a clamp, so that the glass glue fills the gap between the anode shell and the support, the single cells are in close contact, the electrical conductivity is better, and the glass glue is more evenly distributed. ​​

[0063] The high-temperature liquid battery prepared by the above process steps can stably operate at a high temperature of 750°C without antimony metal leakage.

[0064] Example 4

[0065] S1: The support body has a length of 100 mm, a width of 100 mm, and a thickness of 1.5 mm.

[0066] S2: The solid-state antimony metal anode has a mass of 200 g and a size of 80 mm x 80 mm x 5 mm.

[0067] S3: The main shell of the anode shell has a lid shape, a length of 88 mm, a width of 88 mm, a height of 11 mm, and a wall thickness of 3 mm.

[0068] S4: The preferred glass glue (purchased from Shanghai Silicate Institute, model SG-DB05) is coated at the bottom edge of the anode shell and covers the antimony block, so that the gap between the anode shell and the support body is filled with the preferred glass glue.

[0069] S5: A large amount of preferred glass glue is coated outside the contact surface between the anode shell and the support body.

[0070] S6: 20 single cells are connected in series to form one battery stack, and four battery stacks are connected in parallel, with a distance of 5 mm between the parallel battery stacks.

[0071] S7: The battery stack is pressed by a clamp, so that the glass glue fills the gap between the anode shell and the support body, the gap between the anode shell and the support body is reduced, the single cells are in close contact and have better electrical conductivity, and the glass glue is more evenly distributed.

[0072] The high-temperature liquid battery prepared by the above process steps can stably operate at a high temperature of 750°C without blocky antimony metal leakage in the glass area.

[0073] Comparative Example 1

[0074] S1: The support body has a length of 100 mm, a width of 100 mm, and a thickness of 1.5 mm.

[0075] S2: The solid-state antimony metal anode has a mass of 200 g and a size of 80 mm x 80 mm x 5 mm.

[0076] S3: The main shell of the anode shell has a lid shape, a length of 88 mm, a width of 88 mm, a height of 11 mm, and a wall thickness of 3 mm.

[0077] S4: Ceramic glue (purchased from Aremco, model 552, main component is aluminum oxide) is coated on the bottom edge of the anode shell and covers the antimony block, so that the gap between the anode shell and the support is filled with ceramic glue.

[0078] S5: A large amount of ceramic glue is coated outside the contact surface between the anode shell and the support.

[0079] S6: 5 single cells are connected in series to form 1 cell stack, and 2 cell stacks are connected in parallel.

[0080] S7: The cell stack is pressed using a clamp to reduce the gap between the anode shell and the support.

[0081] After experimental testing, the high-temperature liquid battery prepared by the above process steps has a large amount of metal penetrating into the ceramic glue pores and expanding the size of the ceramic glue pores after 1 hour of cycling at 750°C high temperature environment, indicating that the ceramic glue structure is significantly damaged by the liquid antimony anode, resulting in sealing failure as shown in Figure 4

[0082] Comparative Example 2

[0083] S1: The support has a length of 100 mm, a width of 100 mm, and a thickness of 1.5 mm.

[0084] S2: The solid-state antimony metal anode has a mass of 200 g and a size of 80 mm x 80 mm x 5 mm.

[0085] S3: The main shell of the anode shell is in the shape of a lid, with a length of 88 mm, a width of 88 mm, a height of 11 mm, and a wall thickness of 3 mm.

[0086] S4: Regular glass glue (purchased from Ningbo Suofu Energy Technology Co., Ltd., model CY-S) is coated on the bottom edge of the anode shell and covers the antimony block, so that the gap between the anode shell and the support is filled with regular glass glue.

[0087] S5: A large amount of regular glass glue is coated outside the contact surface between the anode shell and the support.

[0088] S6: 5 single cells are connected in series to form 1 cell stack, and 2 cell stacks are connected in parallel.

[0089] S7: The cell stack is pressed using a clamp to reduce the gap between the anode shell and the support, and the glass glue is distributed more evenly.

[0090] After 20 hours of experimental testing, the high-temperature liquid battery prepared by the above process steps has a typical channel of antimony metal leakage at 750°C high temperature environment as shown in Figure 5 ​​

[0091] In the description of the present specification, the description of the terms "one embodiment", "some embodiments", "an example", "a specific example", or "some examples" and the like means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present application. In the present specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Also, the specific features, structures, materials or characteristics described can be combined in any appropriate manner in any one or more embodiments or examples. Furthermore, the person skilled in the art can combine and combine the different embodiments or examples described in the present specification and the features of the different embodiments or examples, without contradiction.

[0092] Although the embodiments of the present application have been shown and described above, it is understood that the above-described embodiments are exemplary and are not to be construed as limiting the present application, and the person skilled in the art can make changes, modifications, replacements and variations to the above-described embodiments within the scope of the present application.

Claims

1. Use of a battery sealing material to block the leakage of liquid antimony metal in a solid oxide fuel cell, the solid oxide fuel cell being a high temperature liquid antimony metal cell, the use comprising: Filling the gap between the anode shell and the half-cell plate of the battery with a battery sealing material, which is a glass paste containing BaO.

2. Use according to claim 1, characterized in that, The filling is performed by: S1: placing an antimony block on the half-cell plate, placing a cover on the antimony block after smearing the battery sealing material on the edge of the anode shell and compacting, further smearing the battery sealing material on the interface between the anode shell and the half-cell plate to form a single cell.

3. Use according to claim 2, characterized in that, Further comprising: S2: vertically stacking the single cells between the single cells and further compacting with a clamp.

4. Use according to claim 3, characterized in that, The area of the single cell is 4 cm 2 - 10000 cm 2 .

5. Use according to claim 3, characterized in that, The number of the stack is 2-100.

6. Use according to claim 3, characterized in that, Further comprising: S3: connecting the rib of the single cell on the top of the battery stack with a metal strip to achieve parallel connection between the stacked single cells.

7. Use according to claim 6, characterized in that, The number of the parallel connection is 2-100.

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