阅读说明：本技术 一种热电池用铝及铝合金与无氧铜封接玻璃粉及其制备方法和应用 (Aluminum and aluminum alloy and oxygen-free copper sealing glass powder for thermal battery and preparation method and application thereof ) 是由 华斯嘉 王哲 冯庆 乔星 徐绍华 郗雪艳 刘卫红 杨文波 于 2020-12-29 设计创作，主要内容包括：本发明属于玻璃-金属封接技术领域,涉及一种热电池用铝及铝合金与无氧铜封接玻璃粉及其制备方法和应用。本发明的目的在于提供一种热电池用铝及铝合金与无氧铜封接玻璃粉及其制备方法和应用,本发明既保证了封接产品外观的一致性及稳定性,又提高了产品的气密性和机械强度,且制备工艺简单,封接及热处理工艺适合于工业化生产。(The invention belongs to the technical field of glass-metal sealing, and relates to aluminum and aluminum alloy and oxygen-free copper sealing glass powder for a thermal battery, and a preparation method and application thereof. The invention aims to provide aluminum and aluminum alloy and oxygen-free copper sealing glass powder for a thermal battery, and a preparation method and application thereof.)

1. The aluminum and aluminum alloy and oxygen-free copper sealing glass powder for the thermal battery is characterized by being prepared from the following raw materials in percentage by weight:

P₂O₅：50％-70％；Na₂O：5％-10％；K₂O：5％-10％；Al₂O₃：0％-10％；B₂O₃：1％-15％；MgO：0％-10％；CaO：0％-10％；BaO：0％-10％；Bi₂O₃：3％-7％；Nb₂O₅:2％-4％；TiO₂：1％-5％；ZrO₂:1％-5％；ZnO：1％-5％；La₂O₃:1％-5％；Co₂O₃：0％-3％。

2. the aluminum and aluminum alloy and oxygen-free copper sealing glass powder for thermal battery as claimed in claim 1, wherein the sealing glass powder has a thermal expansion coefficient α ═ 155-^-7/° c; the softening temperature Tg of the sealing glass powder is 370 ℃ and 475 ℃, and the sealing reference system of the sealing glass powder is 490 ℃ and 540 ℃/15-30 min.

3. A preparation method of aluminum and aluminum alloy and oxygen-free copper sealing glass powder for a thermal battery is characterized by comprising the following steps:

step 1), taking the following raw materials in percentage by weight:

P₂O₅：50％-70％；Na₂O：5％-10％；K₂O：5％-10％；Al₂O₃：0％-10％；B₂O₃：1％-15％；MgO：0％-10％；CaO：0％-10％；BaO：0％-10％；Bi₂O₃：3％-7％；Nb₂O₅:2％-4％；TiO₂：1％-5％；ZrO₂:1％-5％；ZnO：1％-5％；La₂O₃:1％-5％；Co₂O₃：0％-3％。

step 2), ball-milling the raw materials, uniformly mixing, and heating and melting in a high-temperature furnace to obtain clear glass liquid;

step 3), quenching the obtained clear glass liquid in cold distilled water to obtain glass slag;

and 4) baking the obtained glass slag for 12-24 hours at 75-100 ℃, then grinding the baked glass slag, and sieving with a 80-mesh sieve to obtain the aluminum and aluminum alloy and oxygen-free copper sealing glass material for the thermal battery.

4. The method for preparing a sealing glass powder of aluminum and aluminum alloy with oxygen-free copper for a thermal battery as claimed in claim 3, wherein the raw materials in step 2) are ball-milled in a planetary ball mill to mix the ingredients uniformly.

5. The method as claimed in claim 4, wherein the grinding speed is 280-320r/min and the grinding time is 30-60 min.

6. The method for preparing aluminum and aluminum alloy and oxygen-free copper sealing glass powder for a thermal battery according to claim 3, wherein the ball-milled mixed material is placed in a crucible in the step 3), the crucible is placed in a high-temperature lifting furnace, and the furnace is heated until the glass is completely melted and clarified to obtain molten glass.

7. The method for preparing the aluminum and aluminum alloy and oxygen-free copper sealing glass powder for the thermal battery according to claim 6, wherein the crucible is a corundum crucible or a platinum crucible.

8. The method for preparing a sealing glass powder of aluminum, aluminum alloy and oxygen-free copper for a thermal battery as claimed in claim 6, wherein the step 3) comprises placing the ball-milled mixed material in a crucible, placing the crucible in a high temperature furnace, raising the temperature at room temperature from room temperature to 650-; stirring for several times during the process to enable the molten material to be uniform, obtaining molten glass after the molten material is completely melted and clarified, and grinding the roasted glass broken slag in a zirconia ball grinding tank for 8-12 hours at the rotating speed of 200-400 r/min.

9. The method as claimed in claim 3, wherein the sealing glass powder has a thermal expansion coefficient α of 155-^-7/° c; softening temperature T of sealing glass powder_fThe sealing reference system of the sealing glass powder is 490-540 ℃/15-30 min.

10. A sealing process for preparing sealing glass by using aluminum and aluminum alloy and oxygen-free copper sealing glass powder for a thermal battery is characterized by comprising the following steps:

step 1), 100 parts of sealing glass powder, 55-70 parts of water and 0.5-1.5 parts of dispersing agent are placed in a ball milling tank and mixed for 2 hours;

step 2), taking out the ball milling tank, adding 20-30 parts of binder into the slurry, and continuing ball milling and mixing for 2 hours to obtain glass powder slurry with D50 being 5-10 mu m;

step 3), preparing the glass powder slurry into 150-micron granulated powder D50 ═ 100-;

step 4), preparing the granulation powder by a pneumatic compaction machine to obtain a glass green body, then completely discharging the gel at room temperature to 300 ℃, heating to 370-475 ℃, and preserving the temperature for 10-30min to prepare a glass cooked blank without the dispersant and the binder;

step 5), assembling the sealed metal shell, the core column and the glass clinker obtained in the step 4) into a component to be sealed, and slowly heating to 490-540 ℃ along with a furnace for heat preservation for 15-30min for sealing to obtain a sealing component;

and 6) annealing the sealing assembly obtained in the step 5) along with a furnace for 2-3h to room temperature to obtain the sealing cover group of the thermal battery.

Technical Field

The invention belongs to the technical field of glass-metal sealing, and relates to aluminum and aluminum alloy and oxygen-free copper sealing glass powder for a thermal battery, and a preparation method and application thereof.

Background

The thermal battery is also called as a molten salt battery, has the characteristics of long storage time, short activation time, large current density, high specific energy and the like, and is mainly used as a detonation power supply of shells and a working power supply of weaponry such as missiles and the like. As the cover group of the thermal battery is required to meet the characteristics of high reliability, high temperature resistance and the like, the cover group of the thermal battery adopts a glass sealing structure, and the sealing glass in the cover group of the thermal battery is used for sealing and connecting the metal core column and the metal shell, so that the thermal battery plays a role in sealing and insulating, is a key component of the thermal battery, and the quality of the thermal battery directly influences the comprehensive performance of the thermal battery.

In recent years, as weight reduction of manufacturing equipment is required, the lighter the weight of the thermal battery is, the better, and therefore, aluminum metal and its alloy have low density (2.7 g/cm)³) The composite material has the advantages of high specific strength, wide working range, corrosion resistance and the like, and becomes a novel base material of the thermal battery. The oxygen-free copper has the advantages of high purity, low oxygen content, high conductivity, good processability and the like, and is a good electrode material. Aluminum and an alloy material thereof are used as a shell, oxygen-free copper is used as a core column, the aluminum and the alloy material are sealed by melting special glass to prepare a sealing cover group, and the cover group is used for assembling a thermal battery, has the advantages of high oxygen-free copper output current, high electric signal propagation efficiency, light weight, high specific strength and the like, and is a brand new development direction of a glass-metal sealing component for the thermal battery.

However, special sealing of aluminum and its alloy has many problems all over the world, such as very low melting point of aluminum and its alloy, too high sealing temperature of most glasses, very poor wettability of aluminum and its alloy with traditional sealing glass, difficult wetting, and only german schottky company develops this new glass material, but this technology and related materials and products are strictly blocked to china. Therefore, research and development are needed to develop aluminum and aluminum alloy and oxygen-free copper sealing glass materials which can be applied to thermal batteries, so that the sealing process and the heat treatment process are suitable for industrial production, the product yield is high, the stability is good, and the air tightness, the mechanical strength and the chemical stability are good.

Disclosure of Invention

The invention aims to provide aluminum and aluminum alloy and oxygen-free copper sealing glass powder for a thermal battery, and a preparation method and application thereof.

In order to achieve the purpose, the invention adopts the following technical scheme:

the aluminum and aluminum alloy and oxygen-free copper sealing glass powder for the thermal battery is prepared from the following raw materials in percentage by weight:

P₂O₅：50％-70％；Na₂O：5％-10％；K₂O：5％-10％；Al₂O₃：0％-10％；B₂O₃：1％-15％；MgO：0％-10％；CaO：0％-10％；BaO：0％-10％；Bi₂O₃：3％-7％；Nb₂O₅:2％-4％；TiO₂：1％-5％；ZrO₂:1％-5％；ZnO：1％-5％；La₂O₃:1％-5％；Co₂O₃：0％-3％。

furthermore, the thermal expansion coefficient alpha of the sealing glass powder is 155-^-7/° c; softening temperature T of sealing glass powder_fThe sealing reference system of the sealing glass powder is 490-540 ℃/15-30 min.

A preparation method of aluminum and aluminum alloy and oxygen-free copper sealing glass powder for a thermal battery comprises the following steps:

step 1), taking the following raw materials in percentage by weight:

P₂O₅：50％-70％；Na₂O：5％-10％；K₂O：5％-10％；Al₂O₃：0％-10％；B₂O₃：1％-15％；MgO：0％-10％；CaO：0％-10％；BaO：0％-10％；Bi₂O₃：3％-7％；Nb₂O₅:2％-4％；TiO₂：1％-5％；ZrO₂:1％-5％；ZnO：1％-5％；La₂O₃:1％-5％；Co₂O₃：0％-3％。

step 2), ball-milling the raw materials, uniformly mixing, and heating and melting in a high-temperature furnace to obtain clear glass liquid;

step 3), quenching the obtained clear glass liquid in cold distilled water to obtain glass slag;

and 4) baking the obtained glass slag for 12-24 hours at 75-100 ℃, then grinding the baked glass slag, and sieving with a 80-mesh sieve to obtain the aluminum and aluminum alloy and oxygen-free copper sealing glass material for the thermal battery.

Further, the raw materials in the step 2) are placed in a planetary ball mill for ball milling, so that the ingredients are uniformly mixed.

Furthermore, the polishing speed is 280-320r/min, and the polishing time is 30-60 min.

Further, in the step 3), the ball-milled and mixed material is placed in a crucible, the crucible is placed in a high-temperature lifting furnace, and the furnace is heated until the material is completely melted and clarified to obtain glass liquid.

Further, the crucible is a corundum crucible or a platinum crucible.

Further, in the step 3), the ball-milled mixed material is placed in a crucible, the crucible is placed in a high-temperature lifting furnace, the temperature is raised from room temperature to 650 plus material 850 ℃ at the temperature raising rate of 8-12 ℃/min at room temperature, the temperature is maintained at 650 plus material 850 ℃ for 20-40min, then the temperature is raised to 1000 plus material 1500 ℃ at the temperature raising rate of 8-12 ℃/min, and the temperature is maintained at 1000 plus material 1500 ℃ for 1-2 h; stirring for several times during the process to make the molten material uniform, and obtaining molten glass after the molten material is completely melted and clarified.

Further, in the step 4), the roasted glass broken slag is put into a zirconia ball grinding tank to be ground for 8-12 hours at the rotating speed of 200-400 r/min.

A sealing process for preparing sealing glass by using sealing glass powder comprises the following steps:

step 1), 100 parts of sealing glass powder, 55-70 parts of water and 0.5-1.5 parts of dispersing agent are placed in a ball milling tank and mixed for 2 hours;

step 2), taking out the ball milling tank, adding 20-30 parts of binder into the slurry, and continuing ball milling and mixing for 2 hours to obtain glass powder slurry with D50 being 5-10 mu m;

step 3), preparing the glass powder slurry into 150-micron granulated powder D50 ═ 100-;

step 4), preparing the granulation powder by a pneumatic compaction machine to obtain a glass green body, then completely discharging the gel at room temperature to 300 ℃, heating to 370-475 ℃, and preserving the temperature for 10-30min to prepare a glass cooked blank without the dispersant and the binder;

step 5), assembling the sealed metal shell, the core column and the glass clinker obtained in the step 4) into a component to be sealed, and slowly heating to 490-540 ℃ along with a furnace for heat preservation for 15-30min for sealing to obtain a sealing component;

and 6) annealing the sealing assembly obtained in the step 5) along with a furnace for 2-3h to room temperature to obtain the sealing cover group of the thermal battery.

The beneficial effects brought by the invention are as follows:

a glass material for sealing the Al and Al alloy and oxygen-free copper used for thermal battery is prepared from P₂O₅-B₂O₃-Al₂O₃The glass system is a main body, and the performances of the glass, such as the thermal expansion coefficient, the glass softening temperature, the chemical stability and the like, are adjusted by adding various metal oxides. By introducing Na₂O and K₂O increases the coefficient of thermal expansion of the glass, lowers the softening temperature of the glass, but suffers from chemical stability, where K is₂O：Na₂When O is 1.5, the chemical stability is best; by introducing small amounts of Nb₂O₅、Bi₂O₃The glass can enter a glass network structure to play a role of connecting P-O-P, so that the chemical stability of the glass can be improved; by introducing Co₂O₃CuO can improve the wettability and the sealing strength between glass and metal. The thermal expansion coefficient is 155-235 multiplied by 10 by adding various oxides^-7The phosphate glass with the glass softening temperature of 370-475 ℃ can be applied to glass sealing of aluminum and aluminum alloy and oxygen-free copper in thermal battery products.

Drawings

FIG. 1 is a diagram of a sample after assembly and sintering by using the glass frit of the present invention.

Detailed Description

The invention is described in further detail below with reference to the accompanying drawings:

an aluminum and aluminum alloy and oxygen-free copper sealing glass material for a thermal battery is prepared from the following raw materials in percentage by weight:

P₂O₅：50％-70％；Na₂O：5％-10％；K₂O：5％-10％；Al₂O₃：0％-10％；B₂O₃：1％-15％；MgO：0％-10％；CaO：0％-10％；BaO：0％-10％；Bi₂O₃：3％-7％；Nb₂O₅:2％-4％；TiO₂：1％-5％；ZrO₂:1％-5％；ZnO：1％-5％；La₂O₃:1％-5％；Co₂O₃：0％-3％。

the coefficient of thermal expansion alpha of the sealing glass powder is 155-^-7/° c; softening temperature T of sealing glass powder_fThe sealing reference system of the sealing glass powder is 490-540 ℃/15-30 min.

A method for preparing aluminum and aluminum alloy and oxygen-free copper sealing glass powder for a thermal battery,

step 1), taking the following raw materials in percentage by weight:

P₂O₅：50％-70％；Na₂O：5％-10％；K₂O：5％-10％；Al₂O₃：0％-10％；B₂O₃：1％-15％；MgO：0％-10％；CaO：0％-10％；BaO：0％-10％；Bi₂O₃：3％-7％；Nb₂O₅:2％-4％；TiO₂：1％-5％；ZrO₂:1％-5％；ZnO：1％-5％；La₂O₃:1％-5％；Co₂O₃：0％-3％。

step 2), ball-milling the raw materials, uniformly mixing, and heating and melting in a high-temperature furnace to obtain clear glass liquid;

step 3), quenching the obtained clear glass liquid in cold distilled water to obtain glass slag;

and 4) baking the obtained glass slag for 12-24 hours at 75-100 ℃, then grinding the baked glass slag, and sieving with a 80-mesh sieve to obtain the aluminum and aluminum alloy and oxygen-free copper sealing glass material for the thermal battery.

Step 2), placing the raw materials in a planetary ball mill for ball milling to uniformly mix the ingredients;

the grinding speed in the step 2) is 280-320r/min, and the grinding time is 30-60 min;

placing the ball-milled and mixed material in a crucible in the step 3), placing the crucible in a high-temperature lifting furnace, heating the crucible along with the furnace until the material is completely melted and clarified to obtain glass liquid, wherein the crucible is a corundum crucible or a platinum crucible;

specifically, the ball-milled mixed material is placed in a crucible in the step 3), the crucible is placed in a high-temperature lifting furnace, the temperature is raised from room temperature to 650 plus material 850 ℃ at the temperature raising rate of 8-12 ℃/min at room temperature, the temperature is maintained at 650 plus material 850 ℃ for 20-40min, then the temperature is raised to 1000 plus material 1500 ℃ at the temperature raising rate of 8-12 ℃/min, and the temperature is maintained at 1000 plus material 1500 ℃ for 1-2 h; stirring for several times during the process to enable the molten materials to be uniform, and obtaining molten glass after the molten materials are completely melted and clarified;

and 4) putting the roasted glass cullet into a zirconia ball grinding tank, and grinding for 8-12 hours at the rotating speed of 200-400 r/min.

A sealing process for preparing sealing glass based on the obtained sealing glass powder comprises the following steps:

step 1), 100 parts of sealing glass powder, 55-70 parts of water and 0.5-1.5 parts of dispersing agent are placed in a ball milling tank and mixed for 2 hours;

step 2), taking out the ball milling tank, adding 20-30 parts of binder into the slurry, and continuing ball milling and mixing for 2 hours to obtain glass powder slurry with D50 being 5-10 mu m;

step 3), preparing the glass powder slurry into 150-micron granulated powder D50 ═ 100-;

step 4), preparing the granulation powder by a pneumatic compaction machine to obtain a glass green body, then completely discharging the gel at room temperature to 300 ℃, heating to 370-475 ℃, and preserving the temperature for 10-30min to prepare a glass cooked blank without the dispersant and the binder;

step 5), assembling the sealed metal shell, the core column and the glass clinker obtained in the step 4) into a component to be sealed, and slowly heating to 490-540 ℃ along with a furnace for heat preservation for 15-30min for sealing to obtain a sealing component;

and 6) annealing the sealing assembly obtained in the step 5) along with a furnace for 2-3h to room temperature to obtain the sealing cover group of the thermal battery.

Example 1

A preparation method of an aluminum and aluminum alloy and oxygen-free copper sealing glass material for a thermal battery specifically comprises the following steps:

1) selecting the following chemical components in percentage by weight:

P₂O₅：50％；Na₂O：8％；K₂O：8％；Al₂O₃：10％；B₂O₃：7％；MgO：2％；CaO：3％；BaO：3％；Bi₂O₃：3％；Nb₂O₅:2％；TiO₂：1％；ZrO₂:1％；ZnO：1％；La₂O₃:1％。

2) ball-milling the prepared raw materials in a ball mill at a grinding speed of 300r/min for 30min to uniformly mix the ingredients;

3) placing the material subjected to ball milling and mixing in the step (2) into a corundum crucible or a platinum crucible, placing the crucible into a high-temperature lifting furnace, heating to 700 ℃ at a heating rate of 10 ℃/min under an air atmosphere, preserving heat for 40min, heating to 1350 ℃ at a heating rate of 10 ℃/min, preserving heat for 1.5 hours, stirring for a plurality of times during the period to enable the molten material to be uniform, pouring the molten glass into cold distilled water after the molten glass is completely melted and clarified, and performing water quenching to obtain glass cullet;

4) putting the glass cullet obtained in the step (3) into a baking oven at 100 ℃, baking for 12 hours, putting into a zirconia ball grinding tank, and grinding for 12 hours at the rotating speed of 300 r/min;

5) and (4) sieving the glass powder subjected to ball milling treatment in the step (4) by using a 80-mesh sieve to obtain the aluminum and aluminum alloy and oxygen-free copper sealing glass material for the thermal battery.

The sealing glass of the invention was subjected to basic performance tests using the following method:

(1) testing the thermal expansion coefficient: the coefficient of thermal expansion α of the glass was measured by an expansion coefficient measuring instrument at 170 × 10^-7/℃；

(2) And (3) softening temperature test: determination of the softening temperature T of glass Using an expansion coefficient measuring apparatus_f＝460℃；

(3) And (3) testing a sealing reference system: the wetting angle and the high-temperature physical property of the glass are measured by using a high-temperature physical property instrument, and the sealing reference system of the glass is judged to be 530 ℃/30 min.

A sealing process method for the sealing glass comprises the following steps:

1) mixing 100 parts of sealing glass powder, 55-70 parts of water and 0.5-1.5 parts of dispersing agent in a ball milling tank for 2 hours;

2) taking out the ball milling tank, adding 20-30 parts of binder into the slurry, and continuing ball milling and mixing for 2 hours to obtain D₅₀Glass frit paste of 5-10 μm;

3) preparing the glass powder slurry into D in a spray granulation mode₅₀150 μm of granulated powder (100-;

4) preparing the granulated powder into a glass green body by a pneumatic briquetting machine, then completely discharging the glue at room temperature-300 ℃, heating to 460 ℃, and preserving the heat for 10-30min to prepare a glass green body without a dispersing agent and a binder;

5) assembling the sealed metal shell, the glass blank and the core column together into a component to be sealed, placing the component into a chain type sealing furnace, slowly heating to 530 ℃ along with the furnace, preserving heat for 30min, and sealing to obtain a sealing component;

6) and annealing the sealing component along with the furnace for 2-3h to room temperature to obtain the thermal battery cover group sealed by aluminum, aluminum alloy and oxygen-free copper.

The basic performance test of the thermal battery cover group of the invention is carried out by adopting the following method:

(1) and (3) air tightness test: the air tightness of the sealed product is measured to be less than or equal to 1.0 multiplied by 10 by using a helium mass spectrometer leak detector^-10Pa·m³·s^-1；

(2) And (3) testing compressive strength: the compression strength test is carried out on a universal mechanical testing machine, and the core column does not fall off after 500N of pressure is applied on the core column, namely the compression strength test meets the compression requirement;

(3) and (3) testing the insulation resistance: the insulation property of the sealed product is measured by an ultra-high resistance tester, and the insulation resistance is more than 10G omega/500 VDC, namely the insulation property requirement of the product is met.

Example 2

A preparation method of an aluminum and aluminum alloy and oxygen-free copper sealing glass material for a thermal battery specifically comprises the following steps:

1) selecting the following chemical components in percentage by weight:

P₂O₅：60％；Na₂O：6％；K₂O：6％；Al₂O₃：4％；B₂O₃：3％；BaO：5％；Bi₂O₃：6％；Nb₂O₅:3％；TiO₂：2％；ZrO₂:2％；ZnO：1％；La₂O₃:1％；Co₂O₃:1％。

2) ball-milling the prepared raw materials in a ball mill at a grinding speed of 300r/min for 30min to uniformly mix the ingredients;

3) placing the material subjected to ball milling and mixing in the step (2) into a corundum crucible or a platinum crucible, placing the crucible into a high-temperature lifting furnace, heating to 700 ℃ at a heating rate of 10 ℃/min under an air atmosphere, preserving heat for 40min, heating to 1350 ℃ at a heating rate of 10 ℃/min, preserving heat for 1.5 hours, stirring for a plurality of times during the period to enable the molten material to be uniform, pouring the molten glass into cold distilled water after the molten glass is completely melted and clarified, and performing water quenching to obtain glass cullet;

4) putting the glass cullet obtained in the step (3) into a baking oven at 100 ℃, baking for 12 hours, putting into a zirconia ball grinding tank, and grinding for 12 hours at the rotating speed of 300 r/min;

5) and (4) sieving the glass powder subjected to ball milling treatment in the step (4) by using a 80-mesh sieve to obtain the aluminum and aluminum alloy and oxygen-free copper sealing glass material for the thermal battery.

The sealing glass of the invention was subjected to basic performance tests using the following method:

(1) testing the thermal expansion coefficient: measurement of thermal expansion coefficient α of glass by using an expansion coefficient measuring instrument (210 × 10)^-7/℃；

(2) And (3) softening temperature test: determination of the softening temperature T of glass Using an expansion coefficient measuring apparatus_f＝420℃；

(3) And (3) testing a sealing reference system: the wetting angle and the high-temperature physical property of the glass are measured by using a high-temperature physical property instrument, and the sealing reference system of the glass is judged to be 510 ℃/30 min.

A sealing process method for the sealing glass comprises the following steps:

1) mixing 100 parts of sealing glass powder, 55-70 parts of water and 0.5-1.5 parts of dispersing agent in a ball milling tank for 2 hours;

2) taking out the ball milling tank, adding 20-30 parts of binder into the slurry, and continuing ball milling and mixing for 2 hours to obtain D₅₀Glass frit paste of 5-10 μm;

3) preparing the glass powder slurry into D in a spray granulation mode₅₀150 μm of granulated powder (100-;

4) preparing the granulated powder into a glass green body by a pneumatic briquetting machine, then completely discharging the glue at room temperature to 300 ℃, heating to 420 ℃, and preserving the heat for 10-30min to prepare a glass green body without a dispersing agent and a binder;

5) assembling the sealed metal shell, the glass blank and the core column together into a component to be sealed, placing the component into a chain type sealing furnace, slowly heating to 510 ℃ along with the furnace, and preserving heat for 30min for sealing to obtain a sealing component;

6) and annealing the sealing component along with the furnace for 2-3h to room temperature to obtain the thermal battery cover group sealed by aluminum, aluminum alloy and oxygen-free copper.

The basic performance test of the thermal battery cover group of the invention is carried out by adopting the following method:

(1) and (3) air tightness test: the air tightness of the sealed product is measured to be less than or equal to 1.0 multiplied by 10 by using a helium mass spectrometer leak detector^-10Pa·m³·s^-1；

(2) And (3) testing compressive strength: the compression strength test is carried out on a universal mechanical testing machine, and the core column does not fall off after 500N of pressure is applied on the core column, namely the compression strength test meets the compression requirement;

(3) and (3) testing the insulation resistance: the insulation property of the sealed product is measured by an ultra-high resistance tester, and the insulation resistance is more than 10G omega/500 VDC, namely the insulation property requirement of the product is met.

Example 3

A preparation method of an aluminum and aluminum alloy and oxygen-free copper sealing glass material for a thermal battery specifically comprises the following steps:

1) selecting the following chemical components in percentage by weight:

P₂O₅：70％；Na₂O：5％；K₂O：5％；Al₂O₃：2％；B₂O₃：1％；MgO：1％；CaO：1％；BaO：1％；Bi₂O₃：3％；Nb₂O₅:4％；TiO₂：1％；ZrO₂:1％；La₂O₃:3％；Co₂O₃:2％。

2) ball-milling the prepared raw materials in a ball mill at a grinding speed of 300r/min for 30min to uniformly mix the ingredients;

3) placing the material subjected to ball milling and mixing in the step (2) into a corundum crucible or a platinum crucible, placing the crucible into a high-temperature lifting furnace, heating to 700 ℃ at a heating rate of 10 ℃/min under an air atmosphere, preserving heat for 40min, heating to 1350 ℃ at a heating rate of 10 ℃/min, preserving heat for 1.5 hours, stirring for a plurality of times during the period to enable the molten material to be uniform, pouring the molten glass into cold distilled water after the molten glass is completely melted and clarified, and performing water quenching to obtain glass cullet;

4) putting the glass cullet obtained in the step (3) into a baking oven at 100 ℃, baking for 12 hours, putting into a zirconia ball grinding tank, and grinding for 12 hours at the rotating speed of 300 r/min;

5) and (4) sieving the glass powder subjected to ball milling treatment in the step (4) by using a 80-mesh sieve to obtain the aluminum and aluminum alloy and oxygen-free copper sealing glass material for the thermal battery.

The sealing glass of the invention was subjected to basic performance tests using the following method:

(1) testing the thermal expansion coefficient: measurement of coefficient of thermal expansion α of glass by using expansion coefficient measuring instrument 235 × 10^-7/℃；

(2) And (3) softening temperature test: determination of the softening temperature T of glass Using an expansion coefficient measuring apparatus_f＝370℃；

(3) And (3) testing a sealing reference system: the wetting angle and the high-temperature physical property of the glass are measured by using a high-temperature physical property instrument, and the sealing reference system of the glass is judged to be 490 ℃/30 min.

A sealing process method for the sealing glass comprises the following steps:

1) mixing 100 parts of sealing glass powder, 55-70 parts of water and 0.5-1.5 parts of dispersing agent in a ball milling tank for 2 hours;

2) taking out the ball milling tank, adding 20-30 parts of binder into the slurry, and continuing ball milling and mixing for 2 hours to obtain D₅₀Glass frit paste of 5-10 μm;

3) preparing the glass powder slurry into D in a spray granulation mode₅₀150 μm of granulated powder (100-;

4) preparing the granulated powder into a glass green body by a pneumatic briquetting machine, then completely discharging the glue at room temperature to 250 ℃, heating to 370 ℃, and preserving the heat for 10-30min to prepare a glass green body without a dispersing agent and a binder;

5) assembling the sealed metal shell, the glass blank and the core column together into a component to be sealed, placing the component into a chain type sealing furnace, and then slowly heating to 490 ℃ along with the furnace, preserving the heat for 30min, and sealing to obtain a sealing component;

6) and annealing the sealing component along with the furnace for 2-3h to room temperature to obtain the thermal battery cover group sealed by aluminum, aluminum alloy and oxygen-free copper.

The basic performance test of the thermal battery cover group of the invention is carried out by adopting the following method:

(1) and (3) air tightness test: the air tightness of the sealed product is measured to be less than or equal to 1.0 multiplied by 10 by using a helium mass spectrometer leak detector^-10Pa·m³·s^-1；

(2) And (3) testing compressive strength: the compression strength test is carried out on a universal mechanical testing machine, and the core column does not fall off after 500N of pressure is applied on the core column, namely the compression strength test meets the compression requirement;

(3) and (3) testing the insulation resistance: the insulation property of the sealed product is measured by an ultra-high resistance tester, and the insulation resistance is more than 10G omega/500 VDC, namely the insulation property requirement of the product is met.

The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are given by way of illustration of the principles of the present invention, and that various changes and modifications may be made without departing from the spirit and scope of the invention, which is intended to be covered by the claims. The scope of the invention is defined by the appended claims and equivalents thereof.