CN101462828A - Sealing material for sodium-sulfur cell and preparation thereof - Google Patents
Sealing material for sodium-sulfur cell and preparation thereof Download PDFInfo
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- CN101462828A CN101462828A CNA2009100448939A CN200910044893A CN101462828A CN 101462828 A CN101462828 A CN 101462828A CN A2009100448939 A CNA2009100448939 A CN A2009100448939A CN 200910044893 A CN200910044893 A CN 200910044893A CN 101462828 A CN101462828 A CN 101462828A
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Abstract
The invention relates to a sealing material for a sodium-sulfur cell and a preparation method thereof, in particular to a beta-Al2O3 ceramic and alpha-Al2O3 ceramic sealing material and a preparation method thereof. The invention belongs to the field of energy source material. The sealing material for the sodium-sulfur cell is characterized in that the sealing material is glass powder which comprises the following components: 20 to 90 weight percent of SiO2, 5 to 40 weight percent of B2O3, 0 to 10 weight percent of Al2O3 and the balance being R2O; R2O can be one or more of Na2O, K2O and Li2O; the sealing material also comprises the following components counted by the weight of all the oxides: 0.5 to 6 weight percent of TiO2 and 0 to 6 weight percent of Y2O3 or CeO2 or La2O3; all raw materials are smelted for 30 to 360 minutes at the high temperature of 1,400 to 1,600 DEG C; and the glass powder is obtained after water quenching and crushing. The sealing material solves the problem of the imperfect heat matching between the borosilicate sealing glass for the sodium-sulfur cell and the beta-Al2O3 ceramics and alpha-Al2O3 ceramics. The sealing body has good resistance to thermal shocks; and after 50 thermal shocks, the sealing body can still not be broken off by hands and can not be fractured and have no micro-cracks when the sealing body is freely dropped onto the cement floor from a 2-meter high position.
Description
Technical field
The present invention relates to a kind of sealing material for sodium-sulfur cell and preparation method thereof, be specifically related to beta-Al
2O
3Pottery and alpha-Al
2O
3Seal, sealing materials of pottery and preparation method thereof belongs to field of energy source materials.
Technical background
Sodium-sulfur cell is a kind of with sodium ion conductor beta-Al
2O
3For solid electrolyte, sodium and sulphur are respectively negative pole and anodal novel high-energy store battery, be U.S. Ford in 1967 Invention Announce at first.In in the past nearly 40 years, sodium-sulfur cell is subjected to great attention in the world as a kind of advanced person's high-energy density secondary battery, and development work has obtained very significant progress.Just stride forward at present towards practicability, commercialization direction.
Cell sealing is a very important sport technique segment in the sodium-sulfur cell manufacturing processed.An important feature of sodium-sulfur cell design is to adopt all-sealed structure, to guarantee battery plus-negative plate active substance and isolate from outer air.Packing technique is to make one of necessary gordian technique of sodium-sulfur cell, and the quality of sealing property will directly influence the performance and the life-span of battery.Three kinds of complete dissimilar seal form are arranged on the sodium-sulfur cell structure: (1) pottery (is connected beta-Al with the sealing of pottery
2O
3Pottery and alpha-Al
2O
3Pottery).(2) sealing of pottery and metal, this type of sealing initial stage is adopted the mechanical seal of flange fastening-type, because the structure heaviness is huge, and difficulty reaches seal request, so can not be satisfactory.Compagnie Genrale d ' Electricite studies successful hot-press sealing, is about to metal and ceramic seal part and is heated to the after-applied certain pressure of a certain temperature to reach sealing purpose.Can reach good sealing property and bond strength with aluminium as the hot-press sealing of intermediary material, this type of sealing is considered to a kind of optimal selection of pottery and metal sealing in the battery.(3) sealing of metal and metal equally at the development initial stage, also is to adopt the mechanical seal of flange fastening-type, and its outward appearance and sealing effectiveness are all not ideal.Use generally now that the heat affected zone is little instead, advanced welding technique such as the electron beam of high-energy-density melting welding or Laser Welding, successfully solve battery metal container sealing problem after loaded low melting point active substances such as sodium and sulphur respectively itself, reached hermetic matching requirements.
Beta-Al in the sodium-sulfur cell
2O
3Pottery and alpha-Al
2O
3The sealing-in of pottery is particularly important, beta-Al
2O
3The ionogen both sides are respectively sodium and sulphur, if sealing-in is bad, then can cause the leakage of sodium and sulphur, and the internal resistance of cell is increased, and reduce the energy density of battery, even cause short circuit.Simultaneously, beta-Al
2O
3Pottery and alpha-Al
2O
3The sealing-in of pottery is also very difficult, and seal, sealing materials will satisfy a lot of exacting terms.Primary is exactly to satisfy hot matching principle, beta-Al
2O
3Pottery is about 7.5 * 10 at the thermal expansivity of room temperature-650 ℃
- 6K
-1, alpha-Al
2O
3Pottery (95% purity) is about 6.7 * 10 at the thermal expansivity of room temperature-400 ℃
-6K
-1If seal, sealing materials and do not matched by the thermal expansivity between the seal, sealing materials so just is easy to crack.Past is adopted glass sealing always, and forefathers have also dropped into big quantity research for this reason.Though obtained significant progress, the coefficient of expansion of glass is difficult to and the pottery coupling.And, the shortcoming that exists glass itself to be difficult to overcome all the time, for example, the thermal shock resistance of seal glass is very poor; In the preparation process of battery, can produce thermal stresses in the seal glass, even crackle; Under battery operated temperature, densification can take place in seal glass, produces harmful stress.Adopt the glass-ceramic sealing-in then can effectively overcome these problems, still, the glass-ceramic sealing-in but rarely has employing.
Summary of the invention
The objective of the invention is to preparation and optimize a kind of sodium-sulfur cell glass-ceramic seal, sealing materials, when making it overcome glass sealing the coefficient of expansion do not match, defective such as thermal shock resistance difference.
The present invention is a parent glass with traditional borosilicate glass, and basic components is 20～90wt.%SiO
2(using raw material can be silica sand, silica powder etc., preferred analytical pure), 5～40wt.%B
2O
3(using raw material can be borax, boric acid etc., preferred analytical pure), 0～10wt.%Al
2O
3(use raw material can be as feldspar etc., preferred analytical pure) and surplus be R
2O, R
2O is Na
2O, K
2O, Li
2Among the O one or more (using raw material can be saltcake, soda ash etc., preferred analytical pure).Na
2O, K
2O, Li
2Proportioning or the replacement mutually arbitrarily of the proportionlity of O.
By optimizing component, the base of optimum selection component is 40～80wt.%SiO
2, 10～30wt.%B
2O
3, 0～5wt.%Al
2O
3, 0～15wt.%R
2O.
Add 0.5～6wt.%TiO on the basis of the above in addition
2Powder (preferred analytical pure) as the nucleus agent, promotes this devitrification of glass, and 0～6wt.%Y mixes
2O
3Powder (preferred analytical pure) or CeO
2Powder (preferred analytical pure) or La
2O
3Powder long radius, high field intensity ionic oxide formation things such as (preferred analytical pure) are regulated thermal expansivity.
Whole raw material melting 30～360min under 1400～1600 ℃ of high temperature, shrend obtains the glass slag, and ball milling obtains glass powder.Preferred diameter of particle is 5～300 μ m.
Described glass powder consist of 20～90wt.%SiO
2, 5～40wt.%B
2O
3, 0～10wt.%Al
2O
3R with surplus
2O, R
2O is Na
2O, K
2O, Li
2Among the O one or more, Na
2O, K
2O, Li
2Proportioning or the replacement mutually arbitrarily of the proportionlity of O.Contain in addition and account for above-mentioned whole oxide compound (basic components) 0.5～6wt.%TiO
2With account for whole oxide compounds (basic components) 0～6wt.%Y
2O
3Or CeO
2Or La
2O
3
Behind the granulation compressing tablet, by strictness control temperature increasing schedule, select suitable sealing temperature and time, the temperature and time of control nucleation and crystallization finally obtains glass-ceramic of the present invention and sealing-in body.Wherein, sealing temperature is 1000-1200 ℃ of scopes, and the sealing-in time, nucleation temperature was 550-700 ℃ of scopes in 7-15min scope, and nucleation time is in 30-480min scope, and recrystallization temperature is 800-900 ℃ of scopes, and the crystallization time is in 30-480min scope.
Glass-ceramic thermal expansivity and beta-Al that invention obtains
2O
3Pottery and alpha-Al
2O
3The pottery good match, it is smaller with the borosilicate seal glass coefficient of expansion to have solved sodium-sulfur cell, with beta-Al
2O
3Pottery and alpha-Al
2O
3The bad problem of pottery heat coupling.Simultaneously, utilize beta-Al in glass-ceramic that the present invention obtains and the method for sealing sealing-in sodium-sulfur cell among the present invention
2O
3Pottery and alpha-Al
2O
3Pottery, the sealing-in body has good thermal shock resistance, and after the thermal shock 50 times, the sealing-in body still can't be broken into two with one's hands with hand, freely falls on the concrete floor from 2 meters high-altitudes and also can not rupture, and do not have tiny crack to exist.
Method for sealing among the present invention is very easy, promptly utilizes tabletting machine that glass powder is pressed into the small column of φ 5 * 5mm, directly glass cylinder is placed on beta-Al
2O
3Ceramic plate and alpha-Al
2O
3Between the ceramic plate, according to the sealing-in system sealing-in of strictness.
The present invention is not limited to the sealing-in of sodium-sulfur cell, and it can be applicable to the sealing-in of the ceramic component that any thermal expansion is complementary.
Description of drawings
Fig. 1 is the sealing-in system of glass-ceramic, is divided into to be densification sealing-in, nucleation, crystallization four-stage.For guaranteeing to obtain good sealing-in body, need strict control sealing-in system.Sealing temperature is 1000-1200 ℃ of scopes, and the sealing-in time, nucleation temperature was 550-700 ℃ of scopes in 7-15min scope, and nucleation time is in 30-480min scope, and recrystallization temperature is 800-900 ℃ of scopes, and the crystallization time is in 30-480min scope.
Fig. 2 is the XRD figure spectrum of G1 glass behind 850 ℃ of crystallization 300min.As can be seen, glass has been separated out the cristobalite crystalline phase from the XRD figure spectrum, and glassy phase still occupies bigger ratio in the glass-ceramic.
Fig. 3 be G2 glass at 700 ℃ of nucleation 120min, the XRD figure spectrum behind 850 ℃ of crystallization 360min.
Fig. 4 be G3 glass at 700 ℃ of nucleation 120min, the XRD figure spectrum behind 850 ℃ of crystallization 360min.As can be seen, glass has been separated out cristobalite, quartz, YBO from the XRD figure spectrum
3Crystalline phase, glassy phase still occupies bigger ratio in the glass-ceramic.
Embodiment
Be further to set forth technique effect of the present invention, below be illustrated, but the present invention is not limited to following embodiment by comparative example and embodiment.
Comparative example 1
With SiO
2, Al
2O
3, H
3BO
3, Na
2CO
3, K
2CO
3, TiO
2, Y
2O
3According to the proportion design batching of G3 in the table 1, all the components is analytical pure, ball mill mixing 4h in the alcohol medium, and oven dry, 800 ℃ of insulation 0.5h found 2h for 1400 ℃, pour shrend in the frozen water into, obtain the glass slag, obtain glass powder behind the ball milling.Cross 200 mesh sieves, add 2% PVB, utilize tabletting machine to be pressed into rectangular of 6 * 6 * 27mm as binding agent.Take off binding agent at 600 ℃ of insulation 2h, be raised to 580 ℃ with 4 ℃/min, be raised to 730 ℃ with 0.5 ℃/min, insulation 15min is raised to 1000 ℃ of sealing temperatures with 4 ℃/min, and stove is as cold as room temperature, obtains glass block.Measure thermal expansivity with thermal dilatometer, heat-up rate is 5 ℃/min.Thermal expansivity in room temperature to 300 ℃ and room temperature to 400 ℃ is respectively 4.97 * 10
-6K
-1With 5.16 * 10
-6K
-1
Embodiment 1
With SiO
2, Al
2O
3, H
3BO
3, Na
2CO
3, K
2CO
3, TiO
2, Y
2O
3According to the proportion design batching of G1 in the table 1, all the components is analytical pure, ball mill mixing 4h in the alcohol medium, and oven dry, 800 ℃ of insulation 0.5h found 2h for 1400 ℃, pour shrend in the frozen water into, obtain the glass slag, obtain glass powder behind the ball milling.Cross 200 mesh sieves, add 2% PVB, utilize tabletting machine to be pressed into rectangular of 6 * 6 * 27mm as binding agent.Take off binding agent at 600 ℃ of insulation 2h, the sealing-in system sealing-in according to Fig. 3 is raised to 1000 ℃ of sealing temperatures with 4 ℃/min, and insulation 15min drops to 600 ℃ of nucleation temperatures, and insulation 240min is raised to 850 ℃ of recrystallization temperatures, insulation 240min.Obtain final seal glass pottery.Measure thermal expansivity with thermal dilatometer, heat-up rate is 5 ℃/min.Thermal expansivity in room temperature-300 ℃ and room temperature-400 ℃ is respectively 6.99 * 10
-6K
-1With 6.78 * 10
-6K
-1
Embodiment 2
With SiO
2, Al
2O
3, H
3BO
3, Na
2CO
3, K
2CO
3, TiO
2, Y
2O
3According to the proportion design batching of G2 in the table 1, all the components is analytical pure, ball mill mixing 4h in the alcohol medium, and oven dry, 800 ℃ of insulation 0.5h found 2h for 1400 ℃, pour shrend in the frozen water into, obtain the glass slag, obtain glass powder behind the ball milling.Cross 40 mesh sieves, add 2% PVB, utilize tabletting machine to be pressed into rectangular of 6 * 6 * 27mm as binding agent.Take off binding agent at 600 ℃ of insulation 2h, according to the sealing-in system sealing-in of Fig. 3, sealing temperature is 1000 ℃, and the sealing-in time is 15min, at 700 ℃ of nucleation 240min, is raised to 800 ℃ of recrystallization temperatures, insulation 400min.Obtain final seal glass pottery.Measure thermal expansivity with thermal dilatometer, heat-up rate is 5 ℃/min.Thermal expansivity in room temperature-300 ℃ and room temperature-400 ℃ is respectively 6.72 * 10
-6K
-1With 6.51 * 10
-6K
-1
Embodiment 3
With SiO
2, Al
2O
3, H
3BO
3, Na
2CO
3, K
2CO
3, TiO
2, Y
2O
3According to the proportion design batching of G3 in the table 1, all the components is analytical pure, ball mill mixing 4h in the alcohol medium, and oven dry, 800 ℃ of insulation 0.5h found 2h for 1400 ℃, pour shrend in the frozen water into, obtain the glass slag, obtain glass powder behind the ball milling.Cross 60 mesh sieves, add 2% PVB, utilize tabletting machine to be pressed into rectangular of 6 * 6 * 27mm as binding agent.Take off binding agent at 600 ℃ of insulation 2h, according to the sealing-in system sealing-in of Fig. 3, sealing temperature is 1000 ℃, and the sealing-in time is 15min, at 700 ℃ of nucleation 240min, is raised to 800 ℃ of recrystallization temperatures, insulation 400min.Obtain final seal glass pottery.Measure thermal expansivity with thermal dilatometer, heat-up rate is 5 ℃/min.Thermal expansivity in room temperature-300 ℃ and room temperature-400 ℃ is respectively 7.66 * 10
-6K
-1With 7.27 * 10
-6K
-1
Embodiment 4
With SiO
2, Al
2O
3, H
3BO
3, Na
2CO
3, K
2CO
3, TiO
2, Y
2O
3According to the proportion design batching of G4 in the table 1, all the components is analytical pure, ball mill mixing 4h in the alcohol medium, and oven dry, 800 ℃ of insulation 0.5h found 2h for 1400 ℃, pour shrend in the frozen water into, obtain the glass slag, obtain glass powder behind the ball milling.Cross 200 mesh sieves, add 2% PVB, utilize tabletting machine to be pressed into rectangular of 6 * 6 * 27mm as binding agent, according to the sealing-in system sealing-in of Fig. 3, sealing temperature is 1000 ℃, and the sealing-in time is 15min, at 700 ℃ of nucleation 120min, be raised to 850 ℃ of recrystallization temperatures, insulation 60min.Obtain final seal glass pottery.Measure thermal expansivity with thermal dilatometer, heat-up rate is 5 ℃/min.Thermal expansivity in room temperature-300 ℃ and room temperature-400 ℃ is respectively 8.59 * 10
-6K
-1With 8.10 * 10
-6K
-1
Embodiment 5
With SiO
2, Al
2O
3, H
3BO
3, Na
2CO
3, K
2CO
3, TiO
2, Y
2O
3According to the proportion design batching of G5 in the table 1, all the components is analytical pure, ball mill mixing 4h in the alcohol medium, and oven dry, 800 ℃ of insulation 0.5h found 2h for 1400 ℃, pour shrend in the frozen water into, obtain the glass slag, obtain glass powder behind the ball milling.Cross 100 mesh sieves, add 2% PVB, utilize tabletting machine to be pressed into rectangular of 6 * 6 * 27mm as binding agent.Take off binding agent at 600 ℃ of insulation 2h, according to the sealing-in system sealing-in of Fig. 3, sealing temperature is 1200 ℃, and the sealing-in time is 15min, at 600 ℃ of nucleation 360min, is raised to 900 ℃ of recrystallization temperatures, insulation 60min.Obtain final seal glass pottery.Measure thermal expansivity with thermal dilatometer, heat-up rate is 5 ℃/min.Thermal expansivity in room temperature-300 ℃ and room temperature-400 ℃ is respectively 4.69 * 10
-6K
-1With 5.07 * 10
-6K
-1
Embodiment 6
According to above-mentioned sealing-in system, adopt glass material of the present invention to carry out sealing-in, the sealing-in body that obtains carries out the thermal shock performance test.Earlier stove is warmed up to 350 ℃, the sealing-in body is put into is incubated 1h in the stove, take the room temperature cooling, and then be put in 350 ℃ the stove and be incubated 1h, so circulate 50 times.Glass-ceramic sealing-in body and function both hands of the present invention can't be broken off with the fingers and thumb disconnected, freely fall also not fracture on the concrete floor from 2 meters high-altitudes.And there is not tiny crack to produce.This seal glass pottery and beta-Al is described
2O
3Pottery and alpha-Al
2O
3The sealing-in body thermal shock resistance of pottery is good.
By above embodiment as seen, beta-Al in seal glass pottery of the present invention and the sodium-sulfur cell
2O
3Pottery and alpha-Al
2O
3The heat coupling of pottery is good, is alternative sodium-sulfur cell seal, sealing materials.Seal glass pottery of the present invention is not limited to the sealing-in of sodium-sulfur cell, as long as the coefficient of expansion is complementary, it can be applicable to the sealing-in between any ceramic component.
Table 1 is the proportioning of glass-ceramic, with TiO
2Be the nucleus agent, add Y
2O
3Regulate thermal expansivity.
Table 2 is the proportioning of glass-ceramic, with TiO
2Be the nucleus agent, add CeO
2Regulate thermal expansivity.
Table 3 is the proportioning of glass-ceramic, with TiO
2Be the nucleus agent, add La
2O
3Regulate thermal expansivity.
The glass-ceramic that table 4 obtains for different systems is at the thermal expansivity of room temperature-300 ℃ and room temperature-400 ℃.As can be seen with sodium-sulfur cell in beta-Al
2O
3Pottery and alpha-Al
2O
3The coefficient of thermal expansion coupling of pottery is good.
Claims (6)
1, sealing material for sodium-sulfur cell is characterized in that, is glass powder, and it consists of 20～90wt.%SiO
2, 5～40wt.%B
2O
3, 0～10wt.%Al
2O
3R with surplus
2O, described R
2O is Na
2O, K
2O, Li
2Among the O one or more also contain and account for above-mentioned whole oxide compound 0.5～6wt.%TiO
2With 0～6wt.%Y
2O
3Or CeO
2Or La
2O
3
2, by the described sealing material for sodium-sulfur cell of claim 1, it is characterized in that SiO
2Component is 40～80wt.%, B
2O
3Component is 10～30wt.%, Al
2O
3Component is 0～5wt.%, R
2The O component is 0～15wt.%.
3, by the described sealing material for sodium-sulfur cell of claim 1, it is characterized in that described Na
2O, K
2O, Li
2Proportioning or the replacement mutually arbitrarily of the proportionlity of O.
4, the preparation method of sealing material for sodium-sulfur cell comprises the steps:
(1) by 20～90wt.%SiO
2, 5～40wt.%B
2O
3, 0～10wt.%Al
2O
3With surplus R
2O, R
2O is Na
2O, K
2O, Li
2One or more proportioning raw materials among the O,
Add 0.5～6wt.%TiO on the basis of the above
2Powder adds 0～6wt.%Y
2O
3Powder or CeO
2Powder or La
2O
3Powder;
(2) whole raw material melting 30～360min under 1400～1600 ℃ of high temperature pulverize after the shrend and obtain glass powder.
5, by the described preparation method of claim 4, it is characterized in that described SiO
2Raw material comprise silica sand, silica powder; B
2O
3Raw material comprise borax, boric acid; Al
2O
3Raw material comprise feldspar; Na
2O, K
2O, Li
2The raw material of O comprises saltcake, soda ash.
By claim 4 or 5 described preparation methods, it is characterized in that 6, pulverizing and obtaining the glass powder particle diameter is 5～300 μ m.
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|---|---|---|---|
| CNA2009100448939A CN101462828A (en) | 2009-01-05 | 2009-01-05 | Sealing material for sodium-sulfur cell and preparation thereof |
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|---|---|---|---|
| CNA2009100448939A CN101462828A (en) | 2009-01-05 | 2009-01-05 | Sealing material for sodium-sulfur cell and preparation thereof |
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|---|---|
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Family
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| CN103123984B (en) * | 2012-12-12 | 2014-12-10 | 上海电气钠硫储能技术有限公司 | Glass sealing process of sodium-sulfur battery |
| CN103198982A (en) * | 2013-03-07 | 2013-07-10 | 上海电气钠硫储能技术有限公司 | Inorganic gelling agent for fuse for sodium-sulfur cell module and preparation technology thereof |
| CN103435264A (en) * | 2013-08-01 | 2013-12-11 | 广东格斯泰气密元件有限公司 | Seal glass material for improving performances of wiring terminal of refrigeration compressor |
| CN103435264B (en) * | 2013-08-01 | 2015-06-17 | 广东格斯泰气密元件有限公司 | Seal glass material for improving performances of wiring terminal of refrigeration compressor |
| CN104671663A (en) * | 2013-11-26 | 2015-06-03 | 肖特股份有限公司 | Sodium-resistant joining glass and the use 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 |
| CN109250916B (en) * | 2018-09-25 | 2022-04-05 | 西安赛尔电子材料科技有限公司 | Sealing glass material and preparation method thereof |
| CN113937262A (en) * | 2021-09-22 | 2022-01-14 | 浙江钠创新能源有限公司 | Metal oxide modified positive electrode material for sodium ion battery and preparation method and application thereof |
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