CN117819821A - Sealing glass for solid electrolyte molten lithium metal battery - Google Patents
Sealing glass for solid electrolyte molten lithium metal battery Download PDFInfo
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- CN117819821A CN117819821A CN202211179332.1A CN202211179332A CN117819821A CN 117819821 A CN117819821 A CN 117819821A CN 202211179332 A CN202211179332 A CN 202211179332A CN 117819821 A CN117819821 A CN 117819821A
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- 239000005394 sealing glass Substances 0.000 title claims abstract description 66
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 46
- 239000007784 solid electrolyte Substances 0.000 title description 4
- 238000007789 sealing Methods 0.000 claims abstract description 71
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 21
- 239000011521 glass Substances 0.000 claims description 47
- 239000002994 raw material Substances 0.000 claims description 22
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 11
- 238000004321 preservation Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000005538 encapsulation Methods 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910001038 basic metal oxide Inorganic materials 0.000 claims description 4
- 229910052792 caesium Inorganic materials 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 238000010791 quenching Methods 0.000 claims description 3
- 230000000171 quenching effect Effects 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 claims description 2
- 238000000498 ball milling Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 37
- 230000007797 corrosion Effects 0.000 abstract description 36
- 150000003839 salts Chemical class 0.000 abstract description 25
- 239000002184 metal Substances 0.000 abstract description 21
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 20
- 239000000919 ceramic Substances 0.000 abstract description 20
- 229910052751 metal Inorganic materials 0.000 abstract description 19
- 229910021525 ceramic electrolyte Inorganic materials 0.000 abstract description 11
- 239000002001 electrolyte material Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 description 15
- 229910004298 SiO 2 Inorganic materials 0.000 description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 12
- 229920006395 saturated elastomer Polymers 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 229910001510 metal chloride Inorganic materials 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000005245 sintering Methods 0.000 description 7
- 239000011833 salt mixture Substances 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- -1 LLZTO Inorganic materials 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 238000007580 dry-mixing Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000009702 powder compression Methods 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 229910018068 Li 2 O Inorganic materials 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Abstract
The sealing glass formula is used for preparing a sealing glass suitable for a molten lithium metal battery, can resist corrosion of molten salt and lithium vapor, has good compatibility with lithium ion ceramic electrolyte materials, can be applied to the sealing glass in the molten lithium metal battery, realizes airtight sealing between metal and ceramic in the battery and between metal and metal, and ensures long-time stable operation of the battery.
Description
Technical Field
The application relates to the technical field of solid electrolyte molten lithium metal batteries, in particular to sealing glass for a solid electrolyte molten lithium metal battery.
Background
The sealing glass is an interlayer glass for sealing glass, ceramic, metal, composite material, etc. to each other, and when in use, it is necessary to select a sealing glass having an appropriate softening temperature and expansion coefficient.
In the existing medium-high temperature molten lithium metal battery, the active material of the negative electrode is molten lithium metal, the active material of the positive electrode is metal chloride, sulfur or selenium and the like, a lithium ion ceramic electrolyte is arranged between the positive electrode and the negative electrode, and the battery shell is made of metal materials such as stainless steel and the like. The positive electrode and the negative electrode are molten liquid and partially volatilized in the working process (the working temperature is 200-400 ℃), and meanwhile, the metal lithium negative electrode cannot contact air, so that the battery needs to be reliably sealed, and the battery relates to high-temperature resistance, corrosion resistance and insulating sealing between metals.
Glass sealing is a common high-temperature-resistant insulating sealing technology, but conventional sealing glass is difficult to resist corrosion of molten salt, lithium vapor and the like, and has poor material compatibility with lithium ion ceramic electrolyte, so that the glass cannot be applied to a molten lithium metal battery.
CN201710866105.9 discloses a sealing glass, which comprises the following components in percentage by mass: 20-40% of SiO 2 28 to 40 percent of SrO and 1.5 to 11 percent of Al 2 O 3 2 to 20 percent of B 2 O 3 17-23% of CaO.
CN202011572111.1 provides a glass material with electrolyte corrosion resistance, excellent electrochemical performance and controllable mechanical strength, which is used for sealing a lithium primary battery cover group, and the following raw materials are selected according to the following mole percentages:
SiO 2 ：40％～60％，
B 2 O 3 ：10％～30％，
Al 2 O 3 ：0％～5％，
BaO：5％～15％，
Na 2 O：5％～10％，
K 2 O：0％～5％，
MgO：0％～5％，
CaO：0％～5％，
TiO 2 ：0％～5％，
ZrO 2 ：0％～5％，
ZnO：0％～5％，
wherein each type of oxide should include each type of salt and acid-base compound thereof.
CN202010887293.5 discloses a glass, its preparation method and application, the glass comprises the following components in weight percentage: 20-50% of CaO, 10-40% of MgO and SiO 2 10％-40％、B 2 O 3 1％-30％、ZrO 2 0-5％、Al 2 O 3 0-5％、La 2 O 3 0-5％。
CN202210173208.8 discloses a lithium corrosion resistant sealing glass, a sealing cover group and a lithium battery, the sealing glass comprises SiO 2 、Al 2 O 3 、B 2 O 3 Alkali metal oxides and alkaline earth metal oxides, the alkali metal oxides including Li 2 O; the mass of the SiO is calculated as 100 percent of the sealing glass 2 The content of (C) is 10-19%, the Al 2 O 3 The content of (2) is 22-35%. The sealing glass has the defects of poor lithium vapor resistance and poor positive electrode molten salt corrosion resistance at high temperature, high sealing temperature and inapplicability to medium-high temperature molten lithium metal batteries.
The invention provides a sealing glass formula, which is used for preparing a novel sealing glass material, can resist corrosion of lithium vapor and positive molten salt including but not limited to metal chloride molten salt at high temperature, has low sealing temperature and good compatibility with lithium ion ceramic electrolyte material, can be applied to a molten lithium metal battery, realizes airtight sealing between metal and ceramic and between metal in the battery, and ensures long-time stable operation of the battery.
Disclosure of Invention
The invention aims to provide a sealing glass formula for a molten lithium metal battery, which is suitable for sealing a lithium ion electrolyte with other materials, and a preparation process thereof, wherein the sealing glass has good corrosion resistance to molten salt and lithium vapor at a high temperature of 400 ℃, and the gas tightness of a battery device after sealing is good before and after corrosion (He leakage rate is less than 2.0 multiplied by 10 -10 ) Thus, the material can be used as a sealing material in a molten lithium metal battery.
A sealing glass for molten lithium metal battery contains SiO (1-9%) 2 35% -60% of B 2 O 3 5% -25% of Al 2 O 3 5% -10% of Li 2 CO 3 Can be used for sealing the lithium ion electrolyte with other materials.
Preferably, the encapsulation glassContains 5% -50% of alkaline metal oxide; wherein the basic metal oxide comprises BaO, caO, na 2 O、K 2 O、SrO、Rb 2 O、Cs 2 O、Cr 2 O 3 And the like in any proportion.
Preferably, suitable encapsulated lithium ion ceramic electrolytes (e.g., LLZTO, LATP, etc.), and preferably, suitable metals are stainless steel (e.g., 304, 316, 446 stainless steel, etc.) and/or alloys and/or other materials.
Another object of the invention is to prepare a lithium ion electrolyte (LLZTO) seal for use in molten lithium metal batteries by sealing with the sealing glass. Other scenarios in which molten lithium metal is present include electrochemical energy storage devices and/or energy generation devices.
Another object of the present invention is to provide a lithium-corrosion-resistant lithium aluminum boron silicon-based filler (glass frit) and its use, the lithium aluminum boron silicon-based filler being free of lead; the use of the lithium aluminum boron silicon filler in the glass sealing material can reduce the use amount of aluminum oxide and can effectively resist corrosion.
The sealing glass layer comprises 1% -9% of SiO 2 35% -60% of B 2 O 3 5% -25% of Al 2 O 3 5% -10% of Li 2 CO 3 From 5% to 50% of the basic metal oxide comprises BaO, caO, na 2 O、K 2 O、SrO、Rb 2 O、Cs 2 O、Cr 2 O 3 And the like in any proportion. This combination affects in particular the coefficient of thermal expansion and at the same time controls the flow behaviour. In particular, these components can be used to give sealing glass good resistance to chemical attack.
SiO in the present invention 2 Any percentage between 1% and 9%, such as 1%,3%,6%,8%,9%, etc.; the lower content makes the sealing glass resistant to corrosion of lithium metal in high temperature environment.
B in the invention 2 O 3 Any percentage between 35% and 60%, such as 35%,45%,50%,60%, etc.; b (B) 2 O 3 The content of (2) affects the thermal expansion systemAnd simultaneously controls the flow behavior during sealing.
Al in the present invention 2 O 3 Any percentage between 5% and 25%, such as 5%,10%,15%,20%,25%, etc.; li (Li) 2 CO 3 May be any percentage between 5% and 10%, such as 5%,8%,10%, etc., due to Li 2 CO 3 The glass material has a lower melting point, provides a liquid phase sintering environment in the melting process of the glass material, promotes the formation of uniform glass, and can reduce the melting temperature of the glass material; the components lead the sealing glass to have good chemical corrosion resistance and relatively matched thermal expansion coefficients.
The sealing glass of the present invention comprises, optionally, 5% -50% of alkaline earth metal oxide MO. MO represents BaO, caO, na 2 O、K 2 O、SrO、Rb 2 O、Cs 2 O、Cr 2 O 3 And the like, which can be present in the sealing glass. Alkaline earth metal oxides can have a positive effect on the flow behavior of the glass. Since it can reduce the performance of one active component by diffusion or ion migration of lithium ions with the lithium ion ceramic electrolyte, the content thereof is reduced to the minimum according to the present invention.
In summary, when SiO is used in the present invention 2 Is 6-8%, B 2 O 3 40-50% of Al 2 O 3 Is 14-16% of Li 2 CO 3 When the content of the metal-lithium composite material is 5-10%, the compatibility of the sealing glass and the lithium ion ceramic electrolyte material is best, the sealing effect between the metal and the ceramic is the best, and the sealing glass has good corrosion resistance to molten salt and lithium vapor in a high-temperature environment at 400 ℃.
The sealing glass has the advantages of simple and easily obtained raw materials, low cost, simple and stable process, strong lithium corrosion resistance, strong molten salt corrosion resistance, high mechanical strength and strong chemical stability. The service life of the battery prepared by using the sealing glass provided by the invention is obviously prolonged.
The sealing glass of the invention has excellent product performance, and the thermal expansion coefficient alpha is not lower than 100 (10 -7 The glass powder of the sealing glass is used for sealing the lithium ion ceramic tube electrolyte at the temperature of between 700 and 800 ℃, and the leakage rate (Pa m) after sealing can be selected 3 /s.He) is less than 2.0X10 -10 Leakage rate (Pa.m) of molten salt of metal chloride after corrosion 3 /s.He) is less than 2.0X10 -10 Leakage rate (Pa.m) of lithium saturated molten salt after corrosion 3 /s.He) is less than 2.0X10 -10 Specific tests are as described in the examples.
The preparation method of the sealing glass is not particularly limited, and for example, raw materials are weighed according to weight percentage, are placed in a ball mill for uniform mixing, are placed in a crucible for heat preservation for 30-60 min at 800-900 ℃, are heated to 1000-1200 ℃ for heat preservation for 30-90 min, are poured into water for water quenching, and are dried and ball-milled to prepare the sealing glass.
For example, the raw materials are weighed according to the weight percentage, are placed in a ball mill for uniform mixing, are placed in a crucible for heat preservation for 30-60 min at 800-900 ℃, are heated to 1000-1200 ℃ for heat preservation for 30-90 min, are poured into deionized water for water quenching, and are placed in an oven for drying and ball milling to prepare the sealing glass.
The present invention also includes a seal between a first seal member and a second seal member, which uses the above-described sealing glass. The sealing member is understood to be any member connected to the sealing glass. In this case, the sealing glass forms in particular a complete bond with the individual sealing components. The complete joint is distinguished by the fact that: the mating parts, here the individual sealing parts, are held together with the sealing glass by atomic or molecular forces. This results in an inseparable joint which can only be separated by breaking the joint, here the sealing glass. It is particularly advantageous if the sealing glass is able to provide a hermetic seal between the sealing parts as a counterpart seal.
The seals between the sealing members are made of sealing glass and are present in the sealing regions of the respective sealing members joined to the sealing glass, respectively. Thus, the sealing region is a region located on the surface of each sealing member that is in contact with the sealing glass. The sealing member can be joined to the sealing glass over its entire surface area, but also over any desired area, by means of which it can be joined to other sealing members. As mentioned above, the sealing glass according to the invention is particularly suitable for sealing ceramics and/or metals. Accordingly, the seal according to the invention provides a first seal part comprising a ceramic or metal part at least in the seal area. The second sealing member also comprises a ceramic or metal at least in the sealing region. Combinations of metals or ceramics are of course equally possible and are encompassed by the present invention. In combination, this also means that the second sealing part can be a hybrid part consisting of metal and ceramic in the region of the seal. In other words and possibly simplified, the sealing glass according to the invention provides a connection between metal and metal, or ceramic and ceramic, or metal or ceramic and a hybrid component comprising metal and ceramic.
As mentioned above, the sealing glass according to the invention is particularly suitable for sealing lithium-ion ceramic electrolytes, and a seal according to the invention is thus provided, wherein the first sealing part comprises, in particular consists of, lithium-ion ceramic electrolytes at least in the sealing region. The second sealing member comprises one or a combination of metal and lithium ion ceramic electrolyte at least in the sealing region. In combination, a sealing component is obtained, in particular in the form of a hybrid component consisting of metal and lithium-ion ceramic electrolyte in the sealing region.
Very particular preference is given to using the sealing glass according to the invention for producing lithium-sulfur batteries or lithium-metal chloride batteries, in particular for hermetically sealing their housings and/or for closing and/or joining membrane parts in their electrolyte cells. It may also be joined to a suitable carrier element or the like.
The technical scheme of the invention has the following advantages:
1. the sealing glass can be used for medium-high temperature molten lithium metal batteries;
2. the sealing glass is resistant to corrosion of metal chloride fused salt and lithium saturated fused salt at 400 ℃;
3. al in the raw materials used for the sealing glass of the invention 2 O 3 And Li (lithium) 2 CO 3 Is low in cost;
4. due to Li 2 CO 3 The melting point of the raw materials of the sealing glass is low, and the melting temperature of the raw materials of the sealing glass is low;
5. the thermal expansion coefficient alpha of the sealing glass of the invention is not lower than 100 (10 -7 /℃，25～300℃)。
6. The sealing glass has low sealing temperature (700-800 ℃ or 720-750 ℃) and high thermal safety.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the present application, and the terminology used is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments based on the present application.
Some detailed embodiments of the present invention will be disclosed below, although examples of implementation are described in this disclosure, embodiments of the present invention are not limited to what has been shown. The disclosed embodiments are merely examples of what may be claimed as examples of what may be provided and other embodiments that are not shown and alternatives, modifications, equivalents, etc. may be included within the scope of the claims.
Example 1:
(1) Preparing raw materials of glass powder:
weighing SiO 2 8g，Al 2 O 3 20g，B 2 O 3 37g，Li 2 CO 3 8g，BaO 10g，CaO 10g，SrO 2g，Rb 2 O 2g，Cs 2 O 2g，Na 2 O 1g。
(2) Dry-mixing, namely putting the raw materials weighed in the step (1) into a mixer to mix for 1h;
(3) Pouring the raw materials mixed in the step (2) into a crucible, placing the crucible into a frit furnace, preserving heat for 30min at 900 ℃, then heating to 1100 ℃ and preserving heat for 2h, removing a ceramic baffle at the bottom of the crucible when glass liquid is clear and has no bubbles, and dripping the glass liquid into cold deionized water;
(4) Grinding the frit by a dry method to obtain fine glass powder;
(5) Glass sealing and sintering
And (3) placing the glass powder compression ring prepared in the step (4) at a sealing position of a battery die and the lithium ion ceramic tube electrolyte, wherein the sealing temperature is 800 ℃, and sintering in air for 1 hour.
(6) Resistance to molten salt corrosion by metal chlorides
The sealed device is placed in a fused salt mixture of KCl and NaCl at 400 ℃ for heat preservation for 200 hours. The device is taken out and cleaned, then the observation is carried out, the surface color structure of the glass sealing part is unchanged, the leakage rate of the sealing part is unchanged, the sealing performance is good, the chemical corrosion can be judged not to occur, and the chemical corrosion can be judged not to occur by observing the internal color structure unchanged after the sealing glass is damaged.
(7) Lithium-resistant saturated molten salt corrosion
Immersing the sealed device in a fused salt mixture of KCl and NaCl at 400 ℃, adding lithium metal into the upper layer of the fused salt to form lithium saturated fused salt, and preserving the temperature for 48 hours. The device is taken out and cleaned, then the observation is carried out, the surface color structure of the glass sealing part is unchanged, the leakage rate of the sealing part is unchanged, the sealing performance is good, the chemical corrosion can be judged not to occur, and the chemical corrosion can be judged not to occur by observing the internal color structure unchanged after the sealing glass is damaged.
Example 2:
(1) Preparing raw materials of glass powder:
weighing SiO 2 6g，Al 2 O 3 10g，B 2 O 3 45g，Li 2 CO 3 10g，BaO 11g，CaO 11g，SrO 2g，Rb 2 O 2g，Cs 2 O 2g，Na 2 O 1g。
(2) Dry-mixing, namely putting the raw materials weighed in the step (1) into a mixer to mix for 1h;
(3) Pouring the raw materials mixed in the step (2) into a crucible, placing the crucible into a frit furnace, preserving heat for 30min at 900 ℃, then heating to 1100 ℃ and preserving heat for 2h, removing a ceramic baffle at the bottom of the crucible when glass liquid is clear and has no bubbles, and dripping the glass liquid into cold deionized water;
(4) Grinding the frit by a dry method to obtain fine glass powder;
(5) Glass sealing and sintering
And (3) placing the glass powder compression ring prepared in the step (4) at a sealing position of a battery die and the lithium ion ceramic tube electrolyte, wherein the sealing temperature is 720 ℃, and sintering in air for 1 hour.
(6) Resistance to molten salt corrosion by metal chlorides
And placing the sealed device in a fused salt mixture of KCl and NaCl at 400 ℃ for heat preservation for 200 hours. The device is taken out and cleaned, then the observation is carried out, the surface color structure of the glass sealing part is unchanged, the leakage rate of the sealing part is unchanged, the sealing performance is good, the chemical corrosion can be judged not to occur, and the chemical corrosion can be judged not to occur by observing the internal color structure unchanged after the sealing glass is damaged.
(7) Lithium-resistant saturated molten salt corrosion
Immersing the sealed device in a fused salt mixture of KCl and NaCl at 400 ℃, adding lithium metal into the upper layer of the fused salt to form lithium saturated fused salt, and preserving the temperature for 48 hours. The device is taken out and cleaned, then the observation is carried out, the surface color structure of the glass sealing part is unchanged, the leakage rate of the sealing part is unchanged, the sealing performance is good, the chemical corrosion can be judged not to occur, and the chemical corrosion can be judged not to occur by observing the internal color structure unchanged after the sealing glass is damaged.
Example 3:
(1) Preparing raw materials of glass powder:
weighing SiO 2 5g，Al 2 O 3 15g，B 2 O 3 40g，Li 2 CO 3 5g，BaO 15g，CaO 15g，SrO 1g，Rb 2 O 1g，Cs 2 O 1g，Na 2 O 2g。
(2) Dry-mixing, namely putting the raw materials weighed in the step (1) into a mixer to mix for 1h;
(3) Pouring the raw materials mixed in the step (2) into a crucible, placing the crucible into a frit furnace, heating the crucible to 900 ℃, preserving heat for 30min at 2 ℃, heating the crucible to 1150 ℃ and preserving heat for 2h, removing a ceramic baffle at the bottom of the crucible when glass liquid is clear and has no bubbles, and dripping the glass liquid into cold deionized water;
(4) Grinding the frit by a dry method to obtain fine glass powder;
(5) Glass sealing and sintering
And (3) placing the glass powder compression ring prepared in the step (4) at a sealing position of a battery die and the lithium ion ceramic tube electrolyte, wherein the sealing temperature is 750 ℃, and sintering in air for 1 hour.
(6) Resistance to molten salt corrosion by metal chlorides
The sealed device is placed in a fused salt mixture of KCl and NaCl at 400 ℃ for heat preservation for 200 hours. The device is taken out and cleaned, then the observation is carried out, the surface color structure of the glass sealing part is unchanged, the leakage rate of the sealing part is unchanged, the sealing performance is good, the chemical corrosion can be judged not to occur, and the chemical corrosion can be judged not to occur by observing the internal color structure unchanged after the sealing glass is damaged.
(7) Lithium-resistant saturated molten salt corrosion
Immersing the sealed device in a fused salt mixture of KCl and NaCl at 400 ℃, adding lithium metal into the upper layer of the fused salt to form lithium saturated fused salt, and preserving the temperature for 48 hours. The device is taken out and cleaned, then the observation is carried out, the surface color structure of the glass sealing part is unchanged, the leakage rate of the sealing part is unchanged, the sealing performance is good, the chemical corrosion can be judged not to occur, and the chemical corrosion can be judged not to occur by observing the internal color structure unchanged after the sealing glass is damaged.
Example 4: removing SiO 2 6g，Al 2 O 3 15g，B 2 O 3 45g，Li 2 CO 3 8g，BaO 11g，CaO 11g，SrO 1g，Rb 2 O 1g，Cs 2 O 1g，Na 2 The remaining preparation process and performance test were identical to example 1 except for O1 g.
Comparative example 1: removing SiO 2 55g，Al 2 O 3 10g，B 2 O 3 22g，Li 2 CO 3 5g，BaO 2g，CaO 2g，SrO 1g，Rb 2 O 1g，Cs 2 O 1g，Na 2 The remaining preparation process and performance test were identical to example 1 except for O1 g.
Comparative example 2: removing SiO 2 16g，Al 2 O 3 31g，B 2 O 3 23g，Li 2 CO 3 5g，BaO 10g，CaO 3g，SrO 2g，Rb 2 O 3g，Cs 2 O 3g，Na 2 The remaining preparation process and performance test were identical to example 1 except for O4 g.
Comparative example 3: removing SiO 2 6g，Al 2 O 3 16g，B 2 O 3 47g，Li 2 O 3g，BaO 12g，CaO 12g，SrO 1g，Rb 2 O 1g，Cs 2 O 1g，Na 2 O1 g, and the secondary heat preservation temperature is 1300 ℃ when the raw materials are melted, and the rest preparation process and performance test are the same as those of the example 1.
Table 1 comparative tables of examples 1-4 and comparative examples 1-3
Claims (7)
1. A sealing glass for molten lithium metal battery contains SiO (1-9%) 2 35% -60% of B 2 O 3 5% -25% of Al 2 O 3 5% -10% of Li 2 CO 3 Can be used for sealing the lithium ion electrolyte with other materials.
2. A sealing glass according to claim 1, wherein the encapsulation glass contains 5% -50% of a basic metal oxide.
3. The encapsulation glass of claim 1 or 2, wherein the basic metal oxide comprises BaO, caO, na 2 O、K 2 O、SrO、Rb 2 O、Cs 2 O、Cr 2 O 3 And the like in any proportion.
4. A method of producing the encapsulation glass according to claims 1 to 3, comprising:
weighing raw materials according to weight percentage, placing the raw materials into a ball mill for uniform mixing, placing the raw materials into a crucible for heat preservation for 30-60 min at 800-900 ℃, then heating the raw materials to 1000-1200 ℃ for heat preservation for 30-90 min, pouring the raw materials into water for water quenching, drying the water quenched glass, and then performing ball milling to obtain the sealing glass.
5. Use of the encapsulation glass according to claims 1-3 for sealing lithium ion electrolytes with other materials.
6. A seal for a molten lithium metal battery, prepared by sealing the encapsulation glass of claims 1-3 or the encapsulation glass prepared by the preparation method of claim 4.
7. A lithium sulfur battery or lithium-metal chloride battery hermetically sealed with the encapsulation glass of claims 1-3 or the encapsulation glass prepared by the preparation method of claim 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211179332.1A CN117819821A (en) | 2022-09-27 | 2022-09-27 | Sealing glass for solid electrolyte molten lithium metal battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211179332.1A CN117819821A (en) | 2022-09-27 | 2022-09-27 | Sealing glass for solid electrolyte molten lithium metal battery |
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