CN112645598A - Preparation method and packaging process of sealing glass material for lithium-manganese dioxide battery cover group - Google Patents
Preparation method and packaging process of sealing glass material for lithium-manganese dioxide battery cover group Download PDFInfo
- Publication number
- CN112645598A CN112645598A CN202011572085.2A CN202011572085A CN112645598A CN 112645598 A CN112645598 A CN 112645598A CN 202011572085 A CN202011572085 A CN 202011572085A CN 112645598 A CN112645598 A CN 112645598A
- Authority
- CN
- China
- Prior art keywords
- glass
- lithium
- sealing
- manganese dioxide
- battery cover
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- FBDMJGHBCPNRGF-UHFFFAOYSA-M [OH-].[Li+].[O-2].[Mn+2] Chemical compound [OH-].[Li+].[O-2].[Mn+2] FBDMJGHBCPNRGF-UHFFFAOYSA-M 0.000 title claims abstract description 62
- 239000005394 sealing glass Substances 0.000 title claims abstract description 58
- 239000000463 material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000012858 packaging process Methods 0.000 title abstract description 4
- 239000011521 glass Substances 0.000 claims abstract description 61
- 239000002994 raw material Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000007789 sealing Methods 0.000 claims abstract description 25
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 23
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 14
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 11
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims description 40
- 239000002893 slag Substances 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 20
- 239000012768 molten material Substances 0.000 claims description 20
- 229910045601 alloy Inorganic materials 0.000 claims description 19
- 239000000956 alloy Substances 0.000 claims description 19
- 238000000498 ball milling Methods 0.000 claims description 10
- 239000010431 corundum Substances 0.000 claims description 10
- 238000000354 decomposition reaction Methods 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- 239000001307 helium Substances 0.000 claims description 10
- 229910052734 helium Inorganic materials 0.000 claims description 10
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 239000007769 metal material Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000006060 molten glass Substances 0.000 claims description 10
- GALOTNBSUVEISR-UHFFFAOYSA-N molybdenum;silicon Chemical compound [Mo]#[Si] GALOTNBSUVEISR-UHFFFAOYSA-N 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 238000010791 quenching Methods 0.000 claims description 10
- 230000000171 quenching effect Effects 0.000 claims description 10
- 238000007873 sieving Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000010935 stainless steel Substances 0.000 claims description 8
- 229910001220 stainless steel Inorganic materials 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 229910052681 coesite Inorganic materials 0.000 claims description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims description 3
- 238000005260 corrosion Methods 0.000 abstract description 6
- 230000007797 corrosion Effects 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000009413 insulation Methods 0.000 description 28
- 238000012360 testing method Methods 0.000 description 14
- 238000011056 performance test Methods 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 3
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000015654 memory Effects 0.000 description 2
- 239000005368 silicate glass Substances 0.000 description 2
- 229910002923 B–O–B Inorganic materials 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000013473 artificial intelligence Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000004297 night vision Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C29/00—Joining metals with the aid of glass
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to the field of sealing glass and preparation thereof, and particularly relates to a preparation method and a packaging process of a sealing glass material for a lithium-manganese dioxide battery cover group. The preparation method of the sealing glass material for the lithium-manganese dioxide battery cover group comprises the following steps: 1) selecting the following raw materials in percentage by mol: SiO 22：40％～60％，B2O3：5％～25％，Al2O3：0％～5％，BaO：5％～15％，Na2O：5％～15％，K2O：0％～5％，MgO：0％～5％，CaO：0％～5％，TiO2：0％～5％，ZrO2：0％～5％，ZnO：0％～5％，Cr2O3: 0% -5%, wherein each oxide should contain each salt and acid-base compound. Book (I)The invention provides a preparation method and a sealing process of a sealing glass material for a lithium-manganese dioxide battery cover group, which improve the corrosion resistance of the lithium-manganese dioxide battery cover group glass, ensure the air tightness of a sealing piece, improve the chemical stability and high-temperature high-pressure insulativity of the sealing piece, have simple preparation process and are suitable for industrial production.
Description
Technical Field
The invention belongs to the field of sealing glass and preparation thereof, and particularly relates to a preparation method and a packaging process of a sealing glass material for a lithium-manganese dioxide battery cover group.
Background
The lithium-manganese dioxide battery is a lithium/MnO2Batteries, which are electrolytes, have a nominal voltage of up to 30V, a nominal capacity of up to 68Ah, an operating temperature of-60 ℃ to +70 ℃, are lightweight, provide a stable output voltage over most of the life cycle, are capable of providing excellent performance over a wide temperature range, have a low self-discharge rate, can be stored for more than 5 years prior to use, are structurally robust, have excellent passivation resistance characteristics even when stored for extended periods at various temperatures, and are equipped with state-of-charge indicators for battery models having exceptional performance at-20 ℃. Can be used in extremely severe environment, thus receiving wide favor in civilian use and special use in military use.
Along with the development of the internet of things and artificial intelligence, lithium-manganese dioxide batteries are more and more valued and applied by people, and are widely applied to memories and backup power supplies, memory power supplies of cameras and electronic equipment, smart electric meters, water meters, heat meters, gas meters, intelligent traffic (ETC), smart cities (well cover protection, bridge circuit sensing), smoke alarms, temperature monitors, wireless communication, night vision devices and tracking and positioning equipment. In various electronic systems, the lithium-manganese dioxide battery cover group is used for electrical connection and signal transmission among devices, assemblies and systems, and is a necessary basic element for forming a complete system. At present, in various intelligent mechanical equipment, the usage amount of the lithium-manganese dioxide battery is huge, generally the usage amount of the lithium-manganese dioxide battery can reach hundreds of millions in a year, so that the reliability and the stability of the lithium-manganese dioxide battery are more and more concerned by people, and the lithium-manganese dioxide battery is also widely applied to various intelligent manufacturing systems due to the high quality and the high reliability of a lithium-manganese dioxide battery cover group. One of the key factors in the reliability and stability of the lithium-manganese dioxide battery is the cap assembly.
The stainless steel and the iron-nickel alloy have the advantages of low cost, easy processing, good heat conductivity, good electrical conductivity and the like. In addition, in air and neutral water environment, the metal material has very good chemical stability and corrosion resistance, and is widely applied to lithium batteries.
Most of the glass used for sealing the cap group of the lithium-manganese dioxide battery commonly used at present is high silicate glass, the electrolyte corrosion resistance is poor, the mechanical vibration resistance is poor and other factors cause the easy leakage of the battery, so that the service life and the performance of the battery are severely limited, and the glass belongs to low silicate glass.
Aiming at the problems of the conventional lithium-manganese dioxide battery cover group, the invention provides the sealing glass which is corrosion-resistant and high in strength and is used for the lithium-manganese dioxide battery cover group.
Disclosure of Invention
The invention aims to provide a preparation method and a sealing process of a sealing glass material for a lithium-manganese dioxide battery cover group.
The preparation method of the sealing glass material for the lithium-manganese dioxide battery cover group comprises the following steps:
1) selecting the following raw materials in percentage by mol:
SiO2：40％～60％，
B2O3：5％～25％，
Al2O3：0％～5％，
BaO：5％～15％，
Na2O：5％～15％，
K2O：0％～5％，
MgO：0％～5％，
CaO：0％～5％，
TiO2：0％～5％，
ZrO2：0％～5％，
ZnO：0％～5％，
Cr2O3：0％～5％，
wherein, each oxide should contain various salts and acid-base compounds thereof;
2) mixing and dispersing the raw materials in an ultra-high speed dispersion machine to uniformly mix and disperse various raw materials;
3) placing the uniformly mixed materials in a crucible, placing the crucible in a silicon-molybdenum furnace, heating the crucible from room temperature to 300-plus-600 ℃ at a heating rate of 8-10 ℃/min in an air atmosphere, preserving the heat at the temperature of 300-plus-600 ℃ for 30-60min to promote the decomposition of various salts and acid-base compounds, heating the crucible to 1500-plus-1700 ℃ at the heating rate of 8-10 ℃/min, and preserving the heat at the temperature of 1500-plus-1700 ℃ for 1-2 hours; 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; pouring the glass liquid into cold distilled water, and performing water quenching to obtain glass slag;
4) placing the obtained glass broken slag in a drying oven, drying for 12 hours at the temperature of 100-150 ℃, placing the baked glass broken slag in a corundum ball milling tank, grinding for 4 hours at the rotating speed of 200-400r/min, and sieving by a 150-mesh sieve to obtain the special sealing glass powder for the lithium-manganese dioxide battery cover group;
the coefficient of thermal expansion α of the sealing glass is 80 × 10-7-150×10-7/℃；
The softening temperature Ts of the sealing glass is 580-800 ℃.
The sealing process of the lithium-manganese dioxide battery cover group comprises the following steps:
1) the metal material of the shell body for the lithium-manganese dioxide battery cover group is stainless steel series, wherein the metal material comprises 304L, 316L and the like;
2) the stainless steel in the step 1) can be 304, 304L, 316L, but is not limited to the alloy grades;
3) the core column metal material metal used for the lithium-manganese dioxide battery cover group is a series of iron-nickel alloys such as alloys 4J28, 4J50, 4J52 and the like;
4) the nickel-based alloy in the step 3) can be various alloys with the grades of 4J28, 4J50, 4J52 and the like, but is not limited to the alloys;
5) and putting the sealed metal shell, the sealed glass blank and the core column together in a graphite mold to assemble a component to be sealed, putting the component in a chain type atmosphere sealing furnace, introducing protective gas into the furnace to prevent oxidation, quickly raising the temperature in the furnace to 800-1000 ℃, and preserving the heat at 800-1000 ℃ for 15-45 min for sealing to obtain a sealing piece.
Further, the protective gas in step 5) may be nitrogen, helium, argon, and other inert gases.
The beneficial effects brought by the invention are as follows:
the invention discloses a corrosion-resistant and high-strength glass material for sealing a lithium-manganese dioxide battery cover group and a preparation method thereof, and provides a glass material which has excellent comprehensive performances such as manganese dioxide electrolyte corrosion resistance, electrochemical performance and mechanical performance and is used for sealing a lithium-manganese dioxide battery cover group, wherein the metal adopted by a shell is a stainless steel series, the metal comprises 304L, 316L and the like, and the core column adopts a series of iron-nickel alloys such as alloys 4J28, 4J50 and 4J 52. Selecting SiO2-B2O3-Na2The O-BaO glass system isThe main body is added with various metal oxides to adjust the performances of the glass such as thermal expansion coefficient, glass softening temperature, chemical stability and the like. By introducing Na2O、K2O, CaO and MgO can adjust the thermal expansion coefficient of the glass and reduce the softening temperature of the glass; meanwhile, various cations with different ionic radii can form compact accumulation and block each other, so that the strength and the electrical insulation performance of the glass can be improved; by introducing small amount of ZnO and ZrO2The glass can enter a glass network structure to play a role in connecting Si-O-Si and B-O-B, so that the chemical stability of the glass can be improved; by introducing Cr2O3The wettability and the sealing strength between the glass and the metal can be improved. The thermal expansion coefficient is 80-150 multiplied by 10 by adding various oxides-7The borosilicate glass with the glass softening temperature of 580-800 ℃ can be used for sealing the glass of the cover group of the lithium-manganese dioxide battery of various iron-based alloys, nickel-based alloys and iron-nickel-based alloys.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings.
Fig. 1 shows the thermal expansion coefficient and softening temperature of the sealing material for a lid assembly of a lithium-manganese dioxide battery of the present invention.
Fig. 2 is a schematic view of a cap assembly for a lithium-manganese dioxide battery.
Detailed Description
The invention is described in further detail below with reference to the following figures and examples:
the preparation method of the sealing glass material for the lithium-manganese dioxide battery cover group comprises the following steps:
1) selecting the following raw materials in percentage by mol:
SiO2：40％～60％，
B2O3：5％～25％，
Al2O3：0％～5％，
BaO：5％～15％，
Na2O：5％～15％，
K2O：0％～5％，
MgO：0％～5％，
CaO：0％～5％，
TiO2：0％～5％，
ZrO2：0％～5％，
ZnO：0％～5％，
Cr2O3：0％～5％，
wherein, each oxide should contain various salts and acid-base compounds thereof;
2) mixing and dispersing the raw materials in an ultra-high speed dispersion machine to uniformly mix and disperse various raw materials;
3) placing the uniformly mixed materials in a crucible, placing the crucible in a silicon-molybdenum furnace, heating the crucible from room temperature to 300-plus-600 ℃ at a heating rate of 8-10 ℃/min in an air atmosphere, preserving the heat at the temperature of 300-plus-600 ℃ for 30-60min to promote the decomposition of various salts and acid-base compounds, heating the crucible to 1500-plus-1700 ℃ at the heating rate of 8-10 ℃/min, and preserving the heat at the temperature of 1500-plus-1700 ℃ for 1-2 hours; 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; pouring the glass liquid into cold distilled water, and performing water quenching to obtain glass slag;
4) placing the obtained glass broken slag in a drying oven, drying for 12 hours at the temperature of 100-150 ℃, placing the baked glass broken slag in a corundum ball milling tank, grinding for 4 hours at the rotating speed of 200-400r/min, and sieving by a 150-mesh sieve to obtain the special sealing glass powder for the lithium-manganese dioxide battery cover group;
the coefficient of thermal expansion α of the sealing glass is 80 × 10-7-150×10-7/℃；
The softening temperature Ts of the sealing glass is 580-800 ℃.
The sealing process of the lithium-manganese dioxide battery cover group comprises the following steps:
1) the metal material of the shell body for the lithium-manganese dioxide battery cover group is stainless steel series, wherein the metal material comprises 304L, 316L and the like;
2) the stainless steel in the step 1) can be 304, 304L, 316L, but is not limited to the alloy grades;
3) the core column metal material metal used for the lithium-manganese dioxide battery cover group is a series of iron-nickel alloys such as alloys 4J28, 4J50, 4J52 and the like;
4) the nickel-based alloy in the step 3) can be various alloys with the grades of 4J28, 4J50, 4J52 and the like, but is not limited to the alloys;
5) and putting the sealed metal shell, the sealed glass blank and the core column together in a graphite mold to assemble a component to be sealed, putting the component in a chain type atmosphere sealing furnace, introducing protective gas into the furnace to prevent oxidation, quickly raising the temperature in the furnace to 800-1000 ℃, and preserving the heat at 800-1000 ℃ for 15-45 min for sealing to obtain a sealing piece.
Further, the protective gas in step 5) may be nitrogen, helium, argon, and other inert gases.
As shown in fig. 2, the schematic structural diagram of the cap assembly for a lithium-manganese dioxide battery of the present invention includes a stem 1 and a case 2, the case 2 is provided with a sealing hole 3, the stem 1 penetrates through the sealing hole 3, the stem 1 is connected with the case 2 through a sealing glass 5, and a circle of convex edge 4 is disposed at an edge of an upper surface of the case 2.
Example 1
1) The sealing glass material for the lithium-manganese dioxide battery cover group is prepared from the following raw materials in molar mass ratio: SiO 22：40％、B2O3：25％、Al2O3：3％、BaO：8％、Na2O：11％、K2O：3％、MgO：3％、CaO：3％、TiO2：1％、ZrO2：1％、ZnO：2％。
2) Mixing and dispersing the raw materials in an ultra-high speed dispersion machine to uniformly mix and disperse various raw materials;
3) placing the uniformly mixed materials in a crucible, placing the crucible in a silicon-molybdenum furnace, heating the crucible from room temperature to 300-plus-600 ℃ at a heating rate of 8-10 ℃/min in an air atmosphere, preserving the heat at the temperature of 300-plus-600 ℃ for 30-60min to promote the decomposition of various salts and acid-base compounds, heating the crucible to 1500-plus-1700 ℃ at the heating rate of 8-10 ℃/min, and preserving the heat at the temperature of 1500-plus-1700 ℃ for 1-2 hours; 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; pouring the glass liquid into cold distilled water, and performing water quenching to obtain glass slag;
4) placing the obtained glass broken slag in a drying oven, drying for 12 hours at the temperature of 100-150 ℃, placing the baked glass broken slag in a corundum ball milling tank, grinding for 4 hours at the rotating speed of 200-400r/min, and sieving by a 150-mesh sieve to obtain the special sealing glass powder for the lithium-manganese dioxide battery cover group;
coefficient of thermal expansion α of sealing glass 150 × 10-7/℃；
The softening temperature Ts of the sealing glass is 580 ℃;
the sealing glass is used for basic performance test of a lithium-manganese dioxide battery cover group by adopting the following method:
a. and (3) air tightness test: the airtightness of the sealed product is measured to be less than or equal to 1 multiplied by 10 by using a helium mass spectrometer leak detector-10Pa·m3·s-1；
b. And (3) testing the insulation resistance: the insulation property of the sealed product is measured by an ultrahigh resistance tester, the insulation resistance is 10G omega and is more than 100M omega/500V DC, and the high-temperature insulation property requirement of the product is met.
Example 2
1) The sealing glass material for the lithium-manganese dioxide battery cover group is prepared from the following raw materials in molar mass ratio: SiO 22：45％、B2O3：20％、Al2O3：3％、BaO：8％、Na2O：11％、K2O：3％、MgO：3％、CaO：3％、TiO2：1％、ZrO2：1％、ZnO：2％。
2) Mixing and dispersing the raw materials in an ultra-high speed dispersion machine to uniformly mix and disperse various raw materials;
3) placing the uniformly mixed materials in a crucible, placing the crucible in a silicon-molybdenum furnace, heating the crucible from room temperature to 300-plus-600 ℃ at a heating rate of 8-10 ℃/min in an air atmosphere, preserving the heat at the temperature of 300-plus-600 ℃ for 30-60min to promote the decomposition of various salts and acid-base compounds, heating the crucible to 1500-plus-1700 ℃ at the heating rate of 8-10 ℃/min, and preserving the heat at the temperature of 1500-plus-1700 ℃ for 1-2 hours; 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; pouring the glass liquid into cold distilled water, and performing water quenching to obtain glass slag;
4) placing the obtained glass broken slag in a drying oven, drying for 12 hours at the temperature of 100-150 ℃, placing the baked glass broken slag in a corundum ball milling tank, grinding for 4 hours at the rotating speed of 200-400r/min, and sieving by a 150-mesh sieve to obtain the special sealing glass powder for the lithium-manganese dioxide battery cover group;
the coefficient of thermal expansion α of the sealing glass is 130 × 10-7/℃；
The softening temperature Ts of the sealing glass is 640 ℃;
the sealing glass is used for basic performance test of a lithium-manganese dioxide battery cover group by adopting the following method:
a. and (3) air tightness test: the airtightness of the sealed product is measured to be less than or equal to 1 multiplied by 10 by using a helium mass spectrometer leak detector-10Pa·m3·s-1；
b. And (3) testing the insulation resistance: the insulation property of the sealed product is measured by an ultrahigh resistance tester, the insulation resistance is 10G omega and is more than 100M omega/500V DC, and the high-temperature insulation property requirement of the product is met.
Example 3
1) The sealing glass material for the lithium-manganese dioxide battery cover group is prepared from the following raw materials in molar mass ratio: SiO 22：50％、B2O3：15％、Al2O3：3％、BaO：8％、Na2O：11％、K2O：3％、MgO：3％、CaO：3％、TiO2：1％、ZrO2：1％、ZnO：2％。
2) Mixing and dispersing the raw materials in an ultra-high speed dispersion machine to uniformly mix and disperse various raw materials;
3) placing the uniformly mixed materials in a crucible, placing the crucible in a silicon-molybdenum furnace, heating the crucible from room temperature to 300-plus-600 ℃ at a heating rate of 8-10 ℃/min in an air atmosphere, preserving the heat at the temperature of 300-plus-600 ℃ for 30-60min to promote the decomposition of various salts and acid-base compounds, heating the crucible to 1500-plus-1700 ℃ at the heating rate of 8-10 ℃/min, and preserving the heat at the temperature of 1500-plus-1700 ℃ for 1-2 hours; 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; pouring the glass liquid into cold distilled water, and performing water quenching to obtain glass slag;
4) placing the obtained glass broken slag in a drying oven, drying for 12 hours at the temperature of 100-150 ℃, placing the baked glass broken slag in a corundum ball milling tank, grinding for 4 hours at the rotating speed of 200-400r/min, and sieving by a 150-mesh sieve to obtain the special sealing glass powder for the lithium-manganese dioxide battery cover group;
the coefficient of thermal expansion α of the sealing glass is 118 × 10-7/℃；
The softening temperature Ts of the sealing glass is 690 ℃;
the sealing glass is used for basic performance test of a lithium-manganese dioxide battery cover group by adopting the following method:
a. and (3) air tightness test: the airtightness of the sealed product is measured to be less than or equal to 1 multiplied by 10 by using a helium mass spectrometer leak detector-10Pa·m3·s-1；
b. And (3) testing the insulation resistance: the insulation property of the sealed product is measured by an ultrahigh resistance tester, the insulation resistance is 10G omega and is more than 100M omega/500V DC, and the high-temperature insulation property requirement of the product is met.
Example 4
1) The sealing glass material for the lithium-manganese dioxide battery cover group is prepared from the following raw materials in molar mass ratio: SiO 22：55％、B2O3：10％、Al2O3：3％、BaO：8％、Na2O：11％、K2O：3％、MgO：3％、CaO：3％、TiO2：1％、ZrO2：1％、ZnO：2％。
2) Mixing and dispersing the raw materials in an ultra-high speed dispersion machine to uniformly mix and disperse various raw materials;
3) placing the uniformly mixed materials in a crucible, placing the crucible in a silicon-molybdenum furnace, heating the crucible from room temperature to 300-plus-600 ℃ at a heating rate of 8-10 ℃/min in an air atmosphere, preserving the heat at the temperature of 300-plus-600 ℃ for 30-60min to promote the decomposition of various salts and acid-base compounds, heating the crucible to 1500-plus-1700 ℃ at the heating rate of 8-10 ℃/min, and preserving the heat at the temperature of 1500-plus-1700 ℃ for 1-2 hours; 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; pouring the glass liquid into cold distilled water, and performing water quenching to obtain glass slag;
4) placing the obtained glass broken slag in a drying oven, drying for 12 hours at the temperature of 100-150 ℃, placing the baked glass broken slag in a corundum ball milling tank, grinding for 4 hours at the rotating speed of 200-400r/min, and sieving by a 150-mesh sieve to obtain the special sealing glass powder for the lithium-manganese dioxide battery cover group;
the coefficient of thermal expansion α of the sealing glass is 99 × 10-7/℃；
The softening temperature Ts of the sealing glass is 720 ℃;
the sealing glass is used for basic performance test of a lithium-manganese dioxide battery cover group by adopting the following method:
a. and (3) air tightness test: the airtightness of the sealed product is measured to be less than or equal to 1 multiplied by 10 by using a helium mass spectrometer leak detector-10Pa·m3·s-1；
b. And (3) testing the insulation resistance: the insulation property of the sealed product is measured by an ultrahigh resistance tester, the insulation resistance is 10G omega and is more than 100M omega/500V DC, and the high-temperature insulation property requirement of the product is met.
Example 5
1) The sealing glass material for the lithium-manganese dioxide battery cover group is prepared from the following raw materials in molar mass ratio: SiO 22：60％、B2O3：5％、Al2O3：3％、BaO：8％、Na2O：11％、K2O：3％、MgO：3％、CaO：3％、TiO2：1％、ZrO2：1％、ZnO：2％。
2) Mixing and dispersing the raw materials in an ultra-high speed dispersion machine to uniformly mix and disperse various raw materials;
3) placing the uniformly mixed materials in a crucible, placing the crucible in a silicon-molybdenum furnace, heating the crucible from room temperature to 300-plus-600 ℃ at a heating rate of 8-10 ℃/min in an air atmosphere, preserving the heat at the temperature of 300-plus-600 ℃ for 30-60min to promote the decomposition of various salts and acid-base compounds, heating the crucible to 1500-plus-1700 ℃ at the heating rate of 8-10 ℃/min, and preserving the heat at the temperature of 1500-plus-1700 ℃ for 1-2 hours; 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; pouring the glass liquid into cold distilled water, and performing water quenching to obtain glass slag;
4) placing the obtained glass broken slag in a drying oven, drying for 12 hours at the temperature of 100-150 ℃, placing the baked glass broken slag in a corundum ball milling tank, grinding for 4 hours at the rotating speed of 200-400r/min, and sieving by a 150-mesh sieve to obtain the special sealing glass powder for the lithium-manganese dioxide battery cover group;
the coefficient of thermal expansion α of the sealing glass is 82 × 10-7/℃；
The softening temperature Ts of the sealing glass is 780 ℃;
the sealing glass is used for basic performance test of a lithium-manganese dioxide battery cover group by adopting the following method:
a. and (3) air tightness test: the airtightness of the sealed product is measured to be less than or equal to 1 multiplied by 10 by using a helium mass spectrometer leak detector-10Pa·m3·s-1；
b. And (3) testing the insulation resistance: the insulation property of the sealed product is measured by an ultrahigh resistance tester, the insulation resistance is 10G omega and is more than 100M omega/500V DC, and the high-temperature insulation property requirement of the product is met.
Example 6
1) The sealing glass material for the lithium-manganese dioxide battery cover group is prepared from the following raw materials in molar mass ratio: SiO 22：50％、B2O3：15％、Al2O3：3％、BaO：8％、Na2O：11％、K2O：3％、MgO：3％、CaO：3％、TiO2：1％、ZrO2：1％、ZnO：1.5％、Cr2O3：0.5％。
2) Mixing and dispersing the raw materials in an ultra-high speed dispersion machine to uniformly mix and disperse various raw materials;
3) placing the uniformly mixed materials in a crucible, placing the crucible in a silicon-molybdenum furnace, heating the crucible from room temperature to 300-plus-600 ℃ at a heating rate of 8-10 ℃/min in an air atmosphere, preserving the heat at the temperature of 300-plus-600 ℃ for 30-60min to promote the decomposition of various salts and acid-base compounds, heating the crucible to 1500-plus-1700 ℃ at the heating rate of 8-10 ℃/min, and preserving the heat at the temperature of 1500-plus-1700 ℃ for 1-2 hours; 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; pouring the glass liquid into cold distilled water, and performing water quenching to obtain glass slag;
4) placing the obtained glass broken slag in a drying oven, drying for 12 hours at the temperature of 100-150 ℃, placing the baked glass broken slag in a corundum ball milling tank, grinding for 4 hours at the rotating speed of 200-400r/min, and sieving by a 150-mesh sieve to obtain the special sealing glass powder for the lithium-manganese dioxide battery cover group;
the coefficient of thermal expansion α of the sealing glass is 120 × 10-7/℃；
The softening temperature Ts of the sealing glass is 695 ℃;
the sealing glass is used for basic performance test of a lithium-manganese dioxide battery cover group by adopting the following method:
a. and (3) air tightness test: the airtightness of the sealed product is measured to be less than or equal to 1 multiplied by 10 by using a helium mass spectrometer leak detector-10Pa·m3·s-1；
b. And (3) testing the insulation resistance: the insulation property of the sealed product is measured by an ultrahigh resistance tester, the insulation resistance is 10G omega and is more than 100M omega/500V DC, and the high-temperature insulation property requirement of the product is met.
Example 7
1) The sealing glass material for the lithium-manganese dioxide battery cover group is prepared from the following raw materials in molar mass ratio: SiO 22：50％、B2O3：15％、Al2O3：3％、BaO：10％、Na2O：11％、K2O：3％、MgO：3％、CaO：3％、TiO2：1％、ZrO2：1％、ZnO：2％。
2) Mixing and dispersing the raw materials in an ultra-high speed dispersion machine to uniformly mix and disperse various raw materials;
3) placing the uniformly mixed materials in a crucible, placing the crucible in a silicon-molybdenum furnace, heating the crucible from room temperature to 300-plus-600 ℃ at a heating rate of 8-10 ℃/min in an air atmosphere, preserving the heat at the temperature of 300-plus-600 ℃ for 30-60min to promote the decomposition of various salts and acid-base compounds, heating the crucible to 1500-plus-1700 ℃ at the heating rate of 8-10 ℃/min, and preserving the heat at the temperature of 1500-plus-1700 ℃ for 1-2 hours; 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; pouring the glass liquid into cold distilled water, and performing water quenching to obtain glass slag;
4) placing the obtained glass broken slag in a drying oven, drying for 12 hours at the temperature of 100-150 ℃, placing the baked glass broken slag in a corundum ball milling tank, grinding for 4 hours at the rotating speed of 200-400r/min, and sieving by a 150-mesh sieve to obtain the special sealing glass powder for the lithium-manganese dioxide battery cover group;
the coefficient of thermal expansion α of the sealing glass is 108 × 10-7/℃；
The softening temperature Ts of the sealing glass is 710 ℃;
the sealing glass is used for basic performance test of a lithium-manganese dioxide battery cover group by adopting the following method:
a. and (3) air tightness test: the airtightness of the sealed product is measured to be less than or equal to 1 multiplied by 10 by using a helium mass spectrometer leak detector-10Pa·m3·s-1；
b. And (3) testing the insulation resistance: the insulation property of the sealed product is measured by an ultrahigh resistance tester, the insulation resistance is 10G omega and is more than 100M omega/500V DC, and the high-temperature insulation property requirement of the product is met.
The principles and embodiments of the present invention have been explained herein using specific embodiments, which are merely used to help understand the method and its core ideas of the present invention; for those skilled in the art, the invention can be modified in the specific embodiments and applications according to the spirit of the present invention, and therefore the content of the present description should not be construed as limiting the invention.
Claims (3)
1. The preparation method of the sealing glass material for the lithium-manganese dioxide battery cover group is characterized by comprising the following steps of: the method comprises the following steps:
1) selecting the following raw materials in percentage by mol:
SiO2：40％～60％，
B2O3：5％～25％，
Al2O3：0％～5％，
BaO：5％～15％，
Na2O：5％～15％，
K2O：0％～5％，
MgO：0％～5％，
CaO：0％～5％，
TiO2：0％～5％，
ZrO2：0％～5％，
ZnO：0％～5％，
Cr2O3：0％～5％，
wherein, each oxide should contain various salts and acid-base compounds thereof;
2) mixing and dispersing the raw materials in an ultra-high speed dispersion machine to uniformly mix and disperse various raw materials;
3) placing the uniformly mixed materials in a crucible, placing the crucible in a silicon-molybdenum furnace, heating the crucible from room temperature to 300-plus-600 ℃ at a heating rate of 8-10 ℃/min in an air atmosphere, preserving the heat at the temperature of 300-plus-600 ℃ for 30-60min to promote the decomposition of various salts and acid-base compounds, heating the crucible to 1500-plus-1700 ℃ at the heating rate of 8-10 ℃/min, and preserving the heat at the temperature of 1500-plus-1700 ℃ for 1-2 hours; 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; pouring the glass liquid into cold distilled water, and performing water quenching to obtain glass slag;
4) placing the obtained glass broken slag in a drying oven, drying for 12 hours at the temperature of 100-150 ℃, placing the baked glass broken slag in a corundum ball milling tank, grinding for 4 hours at the rotating speed of 200-400r/min, and sieving by a 150-mesh sieve to obtain the special sealing glass powder for the lithium-manganese dioxide battery cover group;
the coefficient of thermal expansion α of the sealing glass is 80 × 10-7-150×10-7/℃；
The softening temperature Ts of the sealing glass is 580-800 ℃.
2. The sealing process of the lithium-manganese dioxide battery cover group is characterized by comprising the following steps of:
1) the metal material of the shell body for the lithium-manganese dioxide battery cover group is stainless steel series, wherein the metal material comprises 304L, 316L and the like;
2) the stainless steel in the step 1) can be 304, 304L, 316L, but is not limited to the alloy grades;
3) the core column metal material metal used for the lithium-manganese dioxide battery cover group is a series of iron-nickel alloys such as alloys 4J28, 4J50, 4J52 and the like;
4) the nickel-based alloy in the step 3) can be various alloys with the grades of 4J28, 4J50, 4J52 and the like, but is not limited to the alloys;
5) and putting the sealed metal shell, the sealed glass blank and the core column together in a graphite mold to assemble a component to be sealed, putting the component in a chain type atmosphere sealing furnace, introducing protective gas into the furnace to prevent oxidation, quickly raising the temperature in the furnace to 800-1000 ℃, and preserving the heat at 800-1000 ℃ for 15-45 min for sealing to obtain a sealing piece.
3. The process for sealing a glass material for sealing a cap assembly of an explosion-proof lithium primary battery according to claim 2, wherein: the protective gas in the step 5) can be nitrogen, helium, argon and other inert gases.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011572085.2A CN112645598A (en) | 2020-12-27 | 2020-12-27 | Preparation method and packaging process of sealing glass material for lithium-manganese dioxide battery cover group |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011572085.2A CN112645598A (en) | 2020-12-27 | 2020-12-27 | Preparation method and packaging process of sealing glass material for lithium-manganese dioxide battery cover group |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112645598A true CN112645598A (en) | 2021-04-13 |
Family
ID=75363105
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011572085.2A Pending CN112645598A (en) | 2020-12-27 | 2020-12-27 | Preparation method and packaging process of sealing glass material for lithium-manganese dioxide battery cover group |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112645598A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114262152A (en) * | 2021-12-02 | 2022-04-01 | 西安赛尔电子材料科技有限公司 | Preparation method and sealing process of sealing glass for displacement acceleration sensor |
| CN114873922A (en) * | 2022-06-17 | 2022-08-09 | 贵州航天电器股份有限公司 | Glass powder for glass sintering connector and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102070301A (en) * | 2010-11-26 | 2011-05-25 | 西安华泰有色金属实业有限责任公司 | Corrosion-resistant sealing glass material for primary lithium battery and preparation method thereof |
| CN102503136A (en) * | 2011-11-14 | 2012-06-20 | 中国科学院上海硅酸盐研究所 | Sealing material for medium/low-temperature solid oxide fuel battery and preparation method thereof |
| CN109250916A (en) * | 2018-09-25 | 2019-01-22 | 西安赛尔电子材料科技有限公司 | A kind of sealing glass material and preparation method thereof |
| CN109851237A (en) * | 2018-12-28 | 2019-06-07 | 西安赛尔电子材料科技有限公司 | A kind of glass sealing method of lithium ion battery cover board component aluminium pole and Stainless Steel Shell |
| WO2020091528A1 (en) * | 2018-11-02 | 2020-05-07 | 엘지전자 주식회사 | Sealing glass composition and solid oxide fuel cell using same |
-
2020
- 2020-12-27 CN CN202011572085.2A patent/CN112645598A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102070301A (en) * | 2010-11-26 | 2011-05-25 | 西安华泰有色金属实业有限责任公司 | Corrosion-resistant sealing glass material for primary lithium battery and preparation method thereof |
| CN102503136A (en) * | 2011-11-14 | 2012-06-20 | 中国科学院上海硅酸盐研究所 | Sealing material for medium/low-temperature solid oxide fuel battery and preparation method thereof |
| CN109250916A (en) * | 2018-09-25 | 2019-01-22 | 西安赛尔电子材料科技有限公司 | A kind of sealing glass material and preparation method thereof |
| WO2020091528A1 (en) * | 2018-11-02 | 2020-05-07 | 엘지전자 주식회사 | Sealing glass composition and solid oxide fuel cell using same |
| CN109851237A (en) * | 2018-12-28 | 2019-06-07 | 西安赛尔电子材料科技有限公司 | A kind of glass sealing method of lithium ion battery cover board component aluminium pole and Stainless Steel Shell |
Non-Patent Citations (3)
| Title |
|---|
| 方道腴等, 复旦大学出版社 * |
| 王伟: "《玻璃生产工艺技术》", 31 December 2013, 武汉理工大学出版社 * |
| 田英良等: "《新编玻璃工艺学》", 30 June 2009, 中国轻工业出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114262152A (en) * | 2021-12-02 | 2022-04-01 | 西安赛尔电子材料科技有限公司 | Preparation method and sealing process of sealing glass for displacement acceleration sensor |
| CN114873922A (en) * | 2022-06-17 | 2022-08-09 | 贵州航天电器股份有限公司 | Glass powder for glass sintering connector and preparation method thereof |
| CN114873922B (en) * | 2022-06-17 | 2023-12-05 | 贵州航天电器股份有限公司 | Glass powder for glass sintering connector and preparation method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109250916A (en) | A kind of sealing glass material and preparation method thereof | |
| Yao et al. | All-solid-state lithium batteries with inorganic solid electrolytes: Review of fundamental science | |
| Amatucci et al. | Failure Mechanism and Improvement of the Elevated Temperature Cycling of LiMn2 O 4 Compounds Through the Use of the LiAl x Mn2− x O 4− z F z Solid Solution | |
| KR101871017B1 (en) | Feedthrough | |
| Hori et al. | Lithium superionic conductor Li9. 42Si1. 02P2. 1S9. 96O2. 04 with Li10GeP2S12-type structure in the Li2S–P2S5–SiO2 pseudoternary system: synthesis, electrochemical properties, and structure–composition relationships | |
| CN112694257A (en) | Preparation method and sealing process of explosion-proof lithium primary battery cover group and sealing glass | |
| CN108258303B (en) | Sulfide solid electrolyte, preparation method thereof and all-solid-state lithium secondary battery | |
| CN112645598A (en) | Preparation method and packaging process of sealing glass material for lithium-manganese dioxide battery cover group | |
| CN103373813A (en) | Barium- and strontium-free vitreous or glass-ceramic jointing material and its use | |
| CN106972122B (en) | A kind of elevated-temperature seal electrode and preparation method thereof | |
| CN102509776A (en) | Method for preparing doped ferrous-lithium metasilicate anode material from micro silicon powder | |
| CN109256499B (en) | Sealing assembly for sealing electrode post glass of aluminum shell power battery and sealing method thereof | |
| CN113659193B (en) | All-solid-state sodium ion battery cell structure, preparation method and battery | |
| CN111003945A (en) | Preparation method of sealing glass material and sealing process thereof | |
| CN204632818U (en) | A kind of ceramic seal battery | |
| Ding et al. | Amorphous Materials for Lithium‐Ion and Post‐Lithium‐Ion Batteries | |
| CN111056745A (en) | Preparation method of sealing glass material for lithium thionyl chloride battery terminal | |
| CA1158302A (en) | Resistant glass in glass-metal seal and cell terminal structure for lithium electrochemical cells | |
| CN105731803A (en) | Copper sealing glass powder, preparation method and application thereof, and electrodes of battery | |
| CN113135663A (en) | Preparation method and packaging process of sealing glass material for lithium-thionyl chloride battery cover group | |
| CN109301151B (en) | Battery electrode post glass sealing structure and sealing method thereof | |
| CN112573832A (en) | Aluminum and aluminum alloy and oxygen-free copper sealing glass powder for thermal battery and preparation method and application thereof | |
| CN114213025A (en) | Preparation method and sealing process for tantalum capacitor cover group sealing glass | |
| CN111018351B (en) | Titanium and kovar alloy sealing glass material for thermal battery and preparation method and application thereof | |
| CN110176595A (en) | A kind of anode material for lithium-ion batteries LiMnO2@C and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210413 |
|
| RJ01 | Rejection of invention patent application after publication |