CN102875179A - Method for sealing heterogeneous ceramic materials for batteries - Google Patents
Method for sealing heterogeneous ceramic materials for batteries Download PDFInfo
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- CN102875179A CN102875179A CN2012104052858A CN201210405285A CN102875179A CN 102875179 A CN102875179 A CN 102875179A CN 2012104052858 A CN2012104052858 A CN 2012104052858A CN 201210405285 A CN201210405285 A CN 201210405285A CN 102875179 A CN102875179 A CN 102875179A
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Abstract
A method for sealing heterogeneous ceramic materials for batteries includes raw material preparation: preparing a heterogeneous ceramic base sealed material 1 and power or pulp of a sealed material 2; preparing powder or pulp of N kinds of sealing materials containing the sealed material 1 and the sealed material 2; fabric forming: respectively preforming the sealed material 1 and the sealed material 2 to obtain a blank layer 1 and a blank layer 2; stacking the N kinds of sealing materials on the blank layer 1 so as to form a sealing material layer, subjecting the sealing material layer to forming a biscuit with the blank layer 2 or staking the N kinds of sealing materials on the blank layer 2 to form a sealing material layer which can form a biscuit with the blank layer 1; sintering: sintering the biscuit at a certain high temperature, and accordingly, preparing the heterogeneous base sealed material 1 and the sealed material 2, and sealing the materiel 1 and the material 2, wherein the sealed material 1 and the sealed material 2 contained in the N kinds of sealing materials are respectively increased and decreased progressively, and the N is larger than or equal to 2.
Description
Technical field
The invention belongs to field of energy source materials, be specifically related to a kind of battery with the sealing technology of heterogeneous stupalith.
Background technology
Sode cell is that a class is take sodium Metal 99.5 as electrode, with Na-beta-Al
2O
3Be the high-performance secondary cell of barrier film Deng the sodium ion conducting solid electrolyte.Take the Na/S battery as example, it be with sodium and sulphur content not as electrode negative pole and anodal active substance, use Na-beta-Al
2O
3Be ionogen and positive and negative electrode barrier film.Sodium-sulfur cell is the heavy-duty battery that is specially adapted to energy storage, and its advantage has high specific energy and specific power, and working temperature is stable, and abundant raw materials is cheap is conducive to large-scale production.As far back as the nineteen sixty-five U.S. Ford this battery that begins one's study, China, Britain, France, Germany and Japan are studied in succession subsequently.Twentieth century the mid-80, Tokyo Electric Power (TEPCO) and NGK company begin to preside over the research and development plan of Japanese Na/S battery, NGK company begins Na/S battery industry production (A.Okuno in March, 2003, T.Maruyama, H.Rachi, et.al Electrochemical Society of Japan, 69
ThConference Lecture Abstract Collection, 11,2002, Taku Oshima and Masaharu Kajita, Int.J.Ceram.Technol.1[3] 269-276 (2004)).TEPCO and NGK company utilize sodium-sulfur cell to obtain a large amount of application at aspects such as balancing power network load, emergency source of electric power, quality of power supply improvement and the stable outputs of renewable energy source.Shanghai Silicate Inst., Chinese Academy of Sciences to development, the exploitation of sodium-sulfur cell, should be used as a large amount of research work (Zhaoyin Wen, et al.Solid State Ionics 179 (2008) 1697-1701; Zhaoyin Wen, et al.Journal of Power Sources, 184 (2008) 641-645).At present sodium-sulfur cell has been successfully used to the stable output of the renewable energy sources such as peak load shifting, emergency source of electric power, wind-power electricity generation and has improved the aspect such as power quality.In order to keep electrode to be in the state of melting, the working temperature of sodium-sulfur cell is about 300-350 ℃, Na-beta-Al in the sodium-sulfur cell
2O
3Pottery is not only as ionogen, simultaneously also as the barrier film of separating the positive and negative electrode material.Because sodium and the direct reaction of sulphur under molten state are very violent even can blast.So the strict isolation in sodium-sulfur cell between the positive and negative electrode working spaces is very important.Have a plurality ofly with parts that battery plus-negative plate contacts simultaneously, be in the same place by various materials and technical combinations between these parts.Usually the material of these parts of combination must meet the requirements such as matched coefficients of thermal expansion, chemically stable, thermal shock resistance are good, air tight.In various parts and combination thereof, insulating ceramic α-Al
2O
3And Na-beta-Al
2O
3Between sealing-in particularly important, α-Al on the one hand
2O
3And Na-beta-Al
2O
3Be the pottery of certain fragility, usually adopt the larger glass of fragility to carry out the sealing-in combination between two parts simultaneously.
Present stage is in the Na/S battery, at Na-beta-Al
2O
3And α-Al
2O
3Between adopt conventional glass sealing or adopt glass-ceramic to carry out sealing-in, people (Shufeng Song, et al.Journal of Solid State Electrochem, 14 (2010) 1735-1740 such as Shufeng Song; Shufeng Song et al.Ceramics International, 35 (2009) 3037-3042) to done a large amount of research work take glass as binding agent.Patent US2010086846-A1, US2010119847-A1 etc. have carried out particular design to the component of glass sealing material, have proposed the seal glass of different systems, have improved the stability of seal glass, the mechanical property of kinds of anti-sulfur corrosion ability and seal glass.Yet because glass two layers of material structure is different, performance difference is large, particularly thermal expansion coefficient difference is larger, and the fragility of glass own is large, and battery discharges and recharges at high temperature, in the Thermal Cycling, and seal glass easily ftractures.Simultaneously, composition is volatile in poor, the work of the resistance to corrosion of glass own, sealing strength is low etc.Another kind of sode cell sodium/chloride battery (also claiming the ZEBRA battery) is then similar with sodium-sulfur cell, Na-beta-Al
2O
3And α-Al
2O
3Sealing-in also be crucial operation and technology, its sealing property directly affects the safety and stability of battery.
Seeking a kind of new method instead of glass sealing-in is very important to the development of sode cell.The present invention connects inconsistent bi-material (beta-Al with the ceramic base gradient composites as interfacial layer
2O
3And α-Al
2O
3), can greatly improve sealing strength.Solve the problem on the caused many safety of glass sealing, improved the safety and stability of sode cell.
Summary of the invention
The present invention proposes a kind of battery with heterogeneous stupalith sealing technology, main purpose be for seal, sealing materials in the battery from by sealing-in two layers of material structure, thermal expansivity is different and the fragility of material itself, battery high-temperature discharges and recharges, the factor such as element evaporation in the Thermal Cycling material, the problem that causes the performance of sealing-in to reduce has to a great extent proposed a kind of battery with heterogeneous stupalith gradient sealing technology.
At this, the invention provides a kind of battery with the method for sealing of heterogeneous stupalith, comprising: A) raw material preparation section: prepare heterogeneous ceramic base by powder or the slurry of seal, sealing materials 1 and material 2; Preparation comprises by powder or the slurry of the N kind seal, sealing materials of seal, sealing materials 1 and material 2, and the included amount by seal, sealing materials 1 and material 2 of wherein said N kind seal, sealing materials is respectively the graded that increases progressively and successively decrease, and described N 〉=2; B) cloth molding procedure: premolding is got green layer 1 and green layer 2 by seal, sealing materials 1 and material 2 respectively; Stacked described N kind seal, sealing materials is to form the seal, sealing materials layer on described green layer 1, make the biscuit body with described green layer 2 moulding again, perhaps stacked described N kind seal, sealing materials is made the biscuit body with described green layer 1 moulding again to form the seal, sealing materials layer on described green layer 2; C) sintering circuit: thus with described biscuit body at a certain temperature high temperature burn till and make described heterogeneous ceramic base and be integral by seal, sealing materials 1 and material 2 and with its sealing-in.
The present invention with by 2 by seal, sealing materials by the ceramic base gradient composites of graded composition of proportions as the seal, sealing materials layer connect inconsistent two kinds by seal, sealing materials, can greatly improve sealing strength.Solved seal, sealing materials and both sides by the problem of seal, sealing materials on material, structure, the different caused many safety of thermal expansivity, improved the safety and stability of battery.
In the method for the invention, described graded is preferably the included amount by seal, sealing materials 1 and material 2 of described N kind seal, sealing materials and is respectively that equivalent increases progressively or equivalent is successively decreased.Preferably, the amount that described equivalent increases progressively and the graded of successively decreasing refers to material 1 that described N kind seal, sealing materials is included and material 2 is respectively to increase progressively and successively decrease less than or equal to 35% variable quantity equivalent more than or equal to 5%.
In addition, in described cloth molding procedure, be that the powder of maximum seal, sealing materials or slurry cloth are on green layer 1 with comprising in the described N kind seal, sealing materials by the amount of seal, sealing materials 1 at first preferably, then according to by the amount of seal, sealing materials 1 be the graded of successively decreasing successively with the powder of other seal, sealing materials or slurry layering cloth on green layer 1, put at last green layer 2, moulding makes the biscuit body.Perhaps preferably, in described cloth molding procedure, be that the powder of maximum seal, sealing materials or slurry cloth are on green layer 2 with comprising in the described N seal, sealing materials by the amount of seal, sealing materials 2 at first, then according to by the amount of seal, sealing materials 2 be the graded of successively decreasing successively with the powder of other seal, sealing materials or slurry layering cloth on green layer 2, put at last green layer 1, moulding makes the biscuit body.
When cloth, will comprise by the maximum seal, sealing materials of the amount of seal, sealing materials 1 with directly contacted by seal, sealing materials 1, to comprise by the maximum seal, sealing materials of the amount of seal, sealing materials 2 with directly contacted by seal, sealing materials, all the other seal, sealing materials then successively decrease successively by graded, can make so adjacent material realize engaging better, thereby overcome because of the problem on material, structure, the different caused many safety of thermal expansivity.
On by the seal, sealing materials green layer during stacked seal, sealing materials, preferably by casting method or the stacked described N kind seal, sealing materials of dry pressing.
Battery of the present invention preferably is applicable to insulating ceramic alpha-Al in sode cell sodium/chloride battery (also claiming the ZEBRA battery) and the sodium-sulfur cell with the method for sealing of heterogeneous stupalith
2O
3With electrolyte ceramics Na-beta-Al
2O
3Sealing-in.More preferably be applicable to insulating ceramic alpha-Al in the sode cell
2O
3With the electrolyte ceramics Na-beta-Al that makees stablizer with Li, Mg or other elements
2O
3Sealing-in.
In the sode cell glass for sealing material with by sealing-in two layers of material (α-Al
2O
3And Na-beta-Al
2O
3) structure, thermal expansivity difference and the fragility of glass own, the factors such as battery high-temperature discharges and recharges, the volatilization of Thermal Cycling glass element, the problem that causes glass-sealed performance to reduce to a great extent.The present invention connects inconsistent bi-material (Na-beta-Al with the ceramic base gradient composites as interfacial layer
2O
3And α-Al
2O
3), can greatly improve sealing strength.Solve the problem on the caused many safety of glass sealing, improved the safety and stability of sode cell.
The thickness of seal, sealing materials layer is preferably 3～6mm described in the biscuit body of moulding.That is, seal, sealing materials layer thickness of the present invention controlled, and regulate as required and select.
Preferably, described sintering process firing temperature is 1400～1700 ℃ of insulations 0.5～5 hour.
Method of the present invention adopt a plurality of have the seal, sealing materials that gradient forms stacked, with by seal, sealing materials green article stage be moulding be integrated, with seal, sealing materials with realized burning altogether means by seal, sealing materials, can prepare the gradient material with premium properties and replace glass and realize the gradient sealing-in.
The present invention by powder (perhaps casting films) stacked-burn altogether the method for sealing-in, realize the gradient sealing-in, the gradient transition seal, sealing materials has high density, good chemical stability, good thermal shock, seal, sealing materials and is sealed body (such as α-Al
2O
3And Na-beta-Al
2O
3) without sharp interface, excellent bonding performance.Gradient seal, sealing materials thickness is controlled, but gradient matrix material transition layer optimization design.Can reach the purpose that improves sealing property by the gradient sealing-in.
Description of drawings
Fig. 1 is that embodiment 1 adopts the gradient material of 20wt.% variation, 3mm thickness to α-Al
2O
3, Na-beta-Al
2O
3The biscuit body carries out the design diagram of common burning sealing-in gradient layer;
Fig. 2 is that embodiment 3 adopts the gradient material of 10wt.% variation, 3mm thickness to α-Al
2O
3, Na-beta-Al
2O
3The biscuit body carries out the design diagram of common burning sealing-in gradient layer;
Fig. 3 is that embodiment 5 adopts the gradient material of 5wt.% variation, 3mm thickness to α-Al
2O
3, Na-beta-Al
2O
3The biscuit body carries out the design diagram of common burning sealing-in gradient layer.
Embodiment
Further specify the present invention below in conjunction with accompanying drawing and following embodiment, should be understood that following embodiment and/or accompanying drawing only are used for explanation the present invention, and unrestricted the present invention.
In the present invention, proposed a kind of new method for sealing, the present invention connects inconsistent bi-material (Na-beta-Al with the ceramic base gradient composites as interfacial layer
2O
3And α-Al
2O
3), can greatly improve sealing strength.Solve the problem on the caused many safety of glass sealing, improved the safety and stability of sode cell.
Method of the present invention comprises:
A) raw material preparation section: prepare heterogeneous ceramic base by powder or the slurry of seal, sealing materials 1 and material 2; Preparation comprises by powder or the slurry of the N kind seal, sealing materials of seal, sealing materials 1 and material 2, and the included amount by seal, sealing materials 1 and material 2 of wherein said N kind seal, sealing materials is respectively the graded that increases progressively and successively decrease, and described N 〉=2;
B) cloth molding procedure: premolding is got green layer 1 and green layer 2 by seal, sealing materials 1 and material 2 respectively; Stacked described N kind seal, sealing materials is to form the seal, sealing materials layer on described green layer 1, make the biscuit body with described green layer 2 moulding again, perhaps stacked described N kind seal, sealing materials is made the biscuit body with described green layer 1 moulding again to form the seal, sealing materials layer on described green layer 2;
C) sintering circuit: thus with described biscuit body at a certain temperature high temperature burn till and make described heterogeneous ceramic base and be integral by seal, sealing materials 1 and material 2 and with its sealing-in.
At above-mentioned operation A) in, seal, sealing materials can also comprise other additives except comprising by seal, sealing materials 1 and material 2, should understanding.For example by the stacked seal, sealing materials of casting method the time, to be prepared powders with material 2 by different gradient design by seal, sealing materials 1, through adding certain solvent (ethanol+butanone), dispersion agent (triglyceride), binding agent (PVB), ball milling 5-10h behind the fluidizer (PEG-200), the slurry for preparing by curtain coating, is controlled the thickness of every layer of cast layer, obtain curtain coating gradient complexin embryo ceramic body by behind stacked-pre-molding-wait static pressure at last.
At above-mentioned operation A) in, described graded refers to that the included amount by seal, sealing materials 1 and material 2 of described N kind seal, sealing materials is respectively that equivalent increases progressively or equivalent is successively decreased.The amount that described equivalent increases progressively and the graded of successively decreasing refers to material 1 that described N kind seal, sealing materials is included and material 2 is respectively to increase progressively and successively decrease less than or equal to 35% variable quantity equivalent more than or equal to 5%.For example, in the situation of not calculating additive possible in the seal, sealing materials, when described N equals 3, it is 25% and when being 75% by the amount of seal, sealing materials 2 that the 1st seal, sealing materials contains by the amount of seal, sealing materials 1, then to contain by the amount of seal, sealing materials 1 be 50% to described the 2nd seal, sealing materials and be 50% by the amount of seal, sealing materials 2, and described the 3rd seal, sealing materials contains by the amount of seal, sealing materials 1 to be 25% and to be 75% by the amount of seal, sealing materials 2.And for example, when described N equals 4, do not calculating equally in the situation of additive possible in the seal, sealing materials, be 20% and when being 80% by the amount of seal, sealing materials 2 when the 1st seal, sealing materials contains by the amount of seal, sealing materials 1, then to contain by the amount of seal, sealing materials 1 be 40% to described the 2nd seal, sealing materials and be 60% by the amount of seal, sealing materials 2, described the 3rd seal, sealing materials contains by the amount of seal, sealing materials 1 to be 60% and to be 40% by the amount of seal, sealing materials 2, and described the 4th seal, sealing materials contains by the amount of seal, sealing materials 1 to be 80% and to be 20% by the amount of seal, sealing materials 2.Need to prove here respectively with variable quantity 25% and 20% as example, but it should be understood that and to increase progressively with 5%, 10%, 15%, 20%, 25%, 30% or 35% variable quantity equivalent and to successively decrease.In addition, the thickness of gradient layer can be controlled as required, for example can be 3～6mm.
At above-mentioned steps B) in, example ground can pass through casting method or the stacked described N kind seal, sealing materials of dry pressing.Be preferably and make that to comprise by the amount of seal, sealing materials 1 or 2 be that the powder of maximum seal, sealing materials or slurry next-door neighbour are by on seal, sealing materials 1 or 2, for example quote the example that top N equals 4, then will by the amount of seal, sealing materials 1 be 80% seal, sealing materials next-door neighbour by seal, sealing materials 1, be followed successively by that to contain by the amount of seal, sealing materials 1 be 60%, 40% and 20% seal, sealing materials.
More specifically, take by seal, sealing materials as insulating ceramic alpha-Al
2O
3With electrolyte ceramics Na-beta-Al
2O
3As example method of the present invention is described further.It can comprise the steps:
(a) can adopt Na-zeta(NaAl
5O
8) and Li-zeta(LiAl
5O
8) precursor that mixes also can be the Na-beta-Al of other stablizers
2O
3Precursor, or the synthetic Na-beta-Al of other chemical processes (sol-gel method, co-precipitation, hydrothermal method etc.)
2O
3Powder;
(b) join in the ball grinder according to certain stoichiometric (Na-zeta/Li-zeta=5/1-6/1) as an example of Na-zeta and Li-zeta example, about ball milling 5-10h, specifically decide the Na-beta-Al that obtains mixing on ball milling condition and physical property
2O
3Precursor;
(c) according to the gradient design requirement, add the α-Al of different mass ratio
2O
3Powder, further ball milling is 5-10h approximately, and preparation is by α-Al
2O
3Na-beta-Al in opposite directions
2O
3The composite powder material that phase gradient changes;
(d) according to the gradient design requirement, with different α-Al
2O
3Content (perhaps Na-beta-Al
2O
3Content) presoma composite granule (comprising by seal, sealing materials and seal, sealing materials) obtains the biscuit body through behind stacked-pre-molding-wait static pressure; Perhaps the material powder process of different gradient design is added a certain amount of solvent (ethanol+butanone), dispersion agent (triglyceride), binding agent (PVB), ball milling certain hour behind the fluidizer (PEG-200), the slurry for preparing is passed through curtain coating, control the thickness of every layer of cast layer, obtain gradient biscuit ceramic body by behind stacked-pre-molding-wait static pressure at last;
(e) the biscuit body that obtains is carried out at a certain temperature common burning and the insulation certain hour is finished the gradient sealing-in, form α-Al
2O
3/ (α-Al
2O
3/ Na-beta-Al
2O
3) gradient composites/Na-beta-Al
2O
3Assembly.
The sealed knot material of different gradient design can be by forming the preparation of osmose process (pickling process) or gas-phase permeation reaction method.
In addition, in above-mentioned steps (b), described uniform mixing method adopts the general milling technology, speed range is minute rev/min of 250-350rpm(revolutions per), can adopt two kinds of approach of wet method and dry method to carry out, adoptable ball-milling medium comprises organic solvent such as raw spirit or the acetone etc. of non-aqueous media, also can adopt water medium.In above-mentioned steps (e), the described heat-treat condition of burning altogether is 1400-1700 ℃, 0.5-5h.And described heat treatment process can adopt under air, vacuum or the protective atmosphere carries out, and shielding gas can be argon gas, nitrogen or argon hydrogen, nitrogen and hydrogen mixture, and burning altogether heat-treat condition is 1400-1700 ℃, 0.5-5h.
The below further exemplifies embodiment to describe the present invention in detail.Should understand equally; following examples only are used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.The quality that following example is concrete, reaction times and temperature, processing parameter etc. also only are examples in the OK range, namely, those skilled in the art can do in the suitable scope by the explanation of this paper and select, and not really want to be defined in the hereinafter concrete numerical value of example.The experimental technique of unreceipted actual conditions in the following example usually according to normal condition, or carries out according to the condition that manufacturer advises.Unless otherwise defined or explanation, same meanings of being familiar with of all specialties used herein and scientific words and those skilled in the art.Any method similar or impartial to described content and material all can be applicable in the inventive method in addition
In addition, in implementation of the present invention, described precursor is by desirable Na-beta-Al
2O
3Chemical equation: Na
1.67Al
10.67Li
0.33O
17Proportioning, namely Na-zeta and Li-zeta mol ratio are 1.67:0.33; Or with Mg
2+Be the Na-beta-Al of stablizer
2O
3, chemical formula is: Na
1.67Al
10.67Mg
0.67O
17Also can be by sol-gel or the synthetic Na-beta-Al of other chemical processes
2O
3
Comparative Examples 1
Adopt glass to α-Al
2O
3With Na-beta-Al
2O
3Ceramic plate carries out sealing-in.Concrete steps are as follows: density is respectively α-Al of 99%
2O
3With Na-beta-Al
2O
3Ceramic plate cleans up in ultrasonic, puts into 80 ℃ baking oven until drying; The cutting thickness of glass is 3mm, and length and width is respectively 40mm and 5mm, after glass cleaning is clean with same method, the oven dry, with glass clamp at α-Al
2O
3With Na-beta-Al
2O
3In the middle of the ceramic plate, put into retort furnace at 1500 ℃ of heat sealing 2-5 hours.Test sealing-in folding strength, thermal shock resistance (putting into immediately cold water after being heated to 300 ℃) find that vitreum crackle occurs after through 20 anti-thermal shocks.Concrete test result sees Table 1.
Embodiment 1
Adopt the gradient material sealing-in α-Al of 20wt.% variation, 3mm thickness
2O
3And Na-beta-Al
2O
3Concrete steps are as follows: take by weighing certain mass Na-beta-Al
2O
3Precursor powder Na-zeta and Li-zeta be take alcohol as medium, and be behind the ball milling 5-10h, dry, sieve to such an extent that granularity is 200 order mixed powder powder.With same method to α-Al
2O
3Carry out ball milling, drying, sieve.Then, prepare α-Al with same ball milling, drying, the method for sieving
2O
3Massfraction is respectively α-Al of 20wt.%, 40wt.%, 60wt.%, 80wt.%
2O
3/ Na-beta-Al
2O
3Composite granule.The first precompressed thickness α-Al that is 1mm respectively in mould
2O
3With Na-beta-Al
2O
3Biscuit is then at α-Al
2O
3Stack gradually α-Al on the biscuit
2O
3Massfraction is respectively the composite granule of 80wt.%, 60wt.%, 40wt.%, 20wt.%, and the thickness of control gradient material is 3mm, puts at last Na-beta-Al
2O
3The further precompressed of biscuit, wait static pressure after, 1500 ℃ are burnt 2h altogether in retort furnace.Test sealing-in folding strength, thermal shock resistance (putting into immediately cold water after being heated to 300 ℃) find that the sealing-in combiner crackle do not occur after through 100 times.Concrete test result sees Table 1, and its graded design as shown in Figure 1.
Adopt the gradient material sealing-in α-Al of 20wt.% variation, 6mm thickness
2O
3And Na-beta-Al
2O
3Concrete steps are as follows: take by weighing certain mass Na-beta-Al
2O
3Precursor powder Na-zeta and Li-zeta be take alcohol as medium, and be behind the ball milling 5-10h, dry, sieve to such an extent that granularity is 200 order mixed powder powder.With same method to α-Al
2O
3Carry out ball milling, drying, sieve.Then, same ball milling, drying, the method for sieving prepare α-Al
2O
3Massfraction is respectively α-Al of 20wt.%, 40wt.%, 60wt.%, 80wt.%
2O
3/ Na-beta-Al
2O
3Composite granule.The first precompressed thickness α-Al that is 1mm respectively in mould
2O
3With Na-beta-Al
2O
3Biscuit is then at α-Al
2O
3Stack gradually α-Al on the biscuit
2O
3Massfraction is respectively the composite granule of 80wt.%, 60wt.%, 40wt.%, 20wt.%, and the thickness of control gradient material is 6mm, puts at last Na-beta-Al
2O
3The further precompressed of biscuit, wait static pressure after, 1500 ℃ are burnt 2h altogether in retort furnace.Test sealing-in folding strength, thermal shock resistance (putting into immediately cold water after being heated to 300 ℃) find that the sealing-in combiner crackle do not occur after through 100 times.Concrete test result sees Table 1.
Adopt the gradient material sealing-in α-Al of 10wt.% variation, 3mm thickness
2O
3And Na-beta-Al
2O
3Concrete steps are as follows: take by weighing certain mass Na-beta-Al
2O
3Precursor powder Na-zeta and Li-zeta be take alcohol as medium, and be behind the ball milling 5-10h, dry, sieve to such an extent that granularity is 200 order mixed powder powder.With same method to α-Al
2O
3Carry out ball milling, drying, sieve.Then, same ball milling, drying, the method for sieving prepare α-Al
2O
3Massfraction is respectively α-Al of 10wt.%, 20wt.%, 30wt.%, 40wt.%, 50wt.%, 60wt.%, 70wt.%, 80wt.%, 90wt.%
2O
3/ Na-beta-Al
2O
3Composite granule.The first precompressed thickness α-Al that is 1mm respectively in mould
2O
3With Na-beta-Al
2O
3Biscuit is then at α-Al
2O
3Stack gradually α-Al on the biscuit
2O
3Massfraction is respectively the composite granule of 90wt.%, 80wt.%, 70wt.%, 60wt.%, 50wt.%, 40wt.%, 30wt.%, 20wt.%, 10wt.%, and the thickness of control gradient material is 3mm, puts at last Na-beta-Al
2O
3The further precompressed of biscuit, wait static pressure after, 1500 ℃ are burnt 2h altogether in retort furnace.Test sealing-in folding strength, thermal shock resistance (putting into immediately cold water after being heated to 300 ℃) find that the sealing-in combiner crackle do not occur after through 200 times.Concrete test result sees Table 1, and its graded design as shown in Figure 2.
Embodiment 4
Adopt the gradient material sealing-in α-Al of 10wt.% variation, 6mm thickness
2O
3And Na-beta-Al
2O
3Concrete steps are as follows: take by weighing certain mass Na-beta-Al
2O
3Precursor powder Na-zeta and Li-zeta be take alcohol as medium, and be behind the ball milling 5-10h, dry, sieve to such an extent that granularity is 200 order mixed powder powder.With same method to α-Al
2O
3Carry out ball milling, drying, sieve.Then, same ball milling, drying, the method for sieving prepare α-Al
2O
3Massfraction is respectively α-Al of 10wt.%, 20wt.%, 30wt.%, 40wt.%, 50wt.%, 60wt.%, 70wt.%, 80wt.%, 90wt.%
2O
3/ Na-beta-Al
2O
3Composite granule.The first precompressed thickness α-Al that is 1mm respectively in mould
2O
3With Na-beta-Al
2O
3Biscuit is then at α-Al
2O
3Stack gradually α-Al on the biscuit
2O
3Massfraction is respectively the composite granule of 90wt.%, 80wt.%, 70wt.%, 60wt.%, 50wt.%, 40wt.%, 30wt.%, 20wt.%, 10wt.%, and the thickness of control gradient material is 6mm, puts at last Na-beta-Al
2O
3The further precompressed of biscuit, wait static pressure after, 1500 ℃ are burnt 2h altogether in retort furnace.Test sealing-in folding strength, thermal shock resistance (putting into immediately cold water after being heated to 300 ℃) find that the sealing-in combiner crackle do not occur after through 200 times.Concrete test result sees Table 1.
Adopt the gradient material sealing-in α-Al of 5wt.% variation, 3mm thickness
2O
3And Na-beta-Al
2O
3Concrete steps are as follows: take by weighing certain mass Na-beta-Al
2O
3Precursor powder Na-zeta and Li-zeta be take alcohol as medium, and be behind the ball milling 5-10h, dry, sieve to such an extent that granularity is 200 order mixed powder powder.With same method to α-Al
2O
3Carry out ball milling, drying, sieve.Then, same ball milling, drying, the method for sieving prepare α-Al
2O
3Massfraction is respectively α-Al of 5wt.%, 10wt.%, 15wt.%, 20wt.%, 25wt.%, 30wt.%, 35wt.%, 40wt.%, 45wt.%, 50wt.%, 55wt.%, 60wt.%, 65wt.%, 70wt.%, 75wt.%, 80wt.%, 85wt.%, 90wt.%, 95wt.%
2O
3/ Na-beta-Al
2O
3Composite granule.The first precompressed thickness α-Al that is 1mm respectively in mould
2O
3With Na-beta-Al
2O
3Biscuit is then at α-Al
2O
3Stack gradually α-Al on the biscuit
2O
3Massfraction is respectively the composite granule of 95wt.%, 90wt.%, 85wt.%, 80wt.%, 75wt.%, 70wt.%, 65wt.%, 60wt.%, 55wt.%, 50wt.%, 45wt.%, 40wt.%, 35wt.%, 30wt.%, 25wt.%, 20wt.%, 15wt.%, 10wt.%, 5wt.%, the thickness of control gradient material is 3mm, puts at last Na-beta-Al
2O
3The further precompressed of biscuit, wait static pressure after, 1500 ℃ are burnt 2h altogether in retort furnace.Test sealing-in folding strength, thermal shock resistance (putting into immediately cold water after being heated to 300 ℃) find that the sealing-in combiner crackle do not occur after through 500 times.Concrete test result sees Table 1, and its graded design as shown in Figure 3.
Embodiment 6
Adopt the gradient material sealing-in α-Al of 5wt.% variation, 6mm thickness
2O
3And Na-beta-Al
2O
3Concrete steps are as follows: take by weighing certain mass Na-beta-Al
2O
3Precursor powder Na-zeta and Li-zeta be take alcohol as medium, and be behind the ball milling 5-10h, dry, sieve to such an extent that granularity is 200 order mixed powder powder.With same method to α-Al
2O
3Carry out ball milling, drying, sieve.Then, same ball milling, drying, the method for sieving prepare α-Al
2O
3Massfraction is respectively α-Al of 5wt.%, 10wt.%, 15wt.%, 20wt.%, 25wt.%, 30wt.%, 35wt.%, 40wt.%, 45wt.%, 50wt.%, 55wt.%, 60wt.%, 65wt.%, 70wt.%, 75wt.%, 80wt.%, 85wt.%, 90wt.%, 95wt.%
2O
3/ Na-beta-Al
2O
3Composite granule.The first precompressed thickness α-Al that is 1mm respectively in mould
2O
3With Na-beta-Al
2O
3Biscuit is then at α-Al
2O
3Stack gradually α-Al on the biscuit
2O
3Massfraction is respectively the composite granule of 95wt.%, 90wt.%, 85wt.%, 80wt.%, 75wt.%, 70wt.%, 65wt.%, 60wt.%, 55wt.%, 50wt.%, 45wt.%, 40wt.%, 35wt.%, 30wt.%, 25wt.%, 20wt.%, 15wt.%, 10wt.%, 5wt.%, the thickness of control gradient material is 6mm, puts at last Na-beta-Al
2O
3The further precompressed of biscuit, wait static pressure after, 1500 ℃ are burnt 2h altogether in retort furnace.Test sealing-in folding strength, thermal shock resistance (putting into immediately cold water after being heated to 300 ℃) find that the sealing-in combiner crackle do not occur after through 500 times.Concrete test result sees Table 1.
Embodiment 7
Adopt the Mg of 5wt.% variation, 6mm thickness
2+Stablize Na-beta-Al
2O
3Gradient material sealing-in α-Al
2O
3And Na-beta-Al
2O
3Method is: take by weighing certain mass Mg
2+Stable Na-beta-Al
2O
3Powder take alcohol behind medium ball milling 5-10h, dry, sieve to such an extent that granularity is 200 order mixed powder powder.With same method to α-Al
2O
3Carry out ball milling, drying, sieve.Then, same ball milling, drying, the method for sieving prepare α-Al
2O
3Massfraction is respectively α-Al of 5wt.%, 10wt.%, 15wt.%, 20wt.%, 25wt.%, 30wt.%, 35wt.%, 40wt.%, 45wt.%, 50wt.%, 55wt.%, 60wt.%, 65wt.%, 70wt.%, 75wt.%, 80wt.%, 85wt.%, 90wt.%, 95wt.%
2O
3/ Na-beta-Al
2O
3Composite granule.The first precompressed thickness α-Al that is 1mm respectively in mould
2O
3With Na-beta-Al
2O
3Biscuit is then at α-Al
2O
3Stack gradually α-Al on the biscuit
2O
3Massfraction is respectively the composite granule of 95wt.%, 90wt.%, 85wt.%, 80wt.%, 75wt.%, 70wt.%, 65wt.%, 60wt.%, 55wt.%, 50wt.%, 45wt.%, 40wt.%, 35wt.%, 30wt.%, 25wt.%, 20wt.%, 15wt.%, 10wt.%, 5wt.%, the thickness of control gradient material is 6mm, puts at last Na-beta-Al
2O
3The further precompressed of biscuit, wait static pressure after, 1500 ℃ are burnt 2h altogether in retort furnace.The thermal shock resistance (putting into immediately cold water after being heated to 300 ℃) of test sealing-in finds that the sealing-in combiner crackle do not occur after through 500 times.Concrete test result sees Table 1.
Embodiment 8
The Li by the preparation of sol-gel method with 5wt.% variation, 6mm thickness
+Stable Na-beta-Al
2O
3Gradient material sealing-in α-Al
2O
3And Na-beta-Al
2O
3, concrete grammar is identical with embodiment 7 with the sealing-in process, by the thermal shock resistance (putting into immediately cold water after being heated to 300 ℃) of test sealing-in parts, finds that the sealing-in combiner crackle do not occur yet after through 500 times.Concrete test result sees Table 1.
Embodiment 9
Adopt the curtain coating gradient composites of 5wt.% variation, 1mm thickness to α-Al
2O
3And Na-beta-Al
2O
3Carry out sealing-in.Method is: with the powder (α-Al of different gradient design
2O
3Massfraction is respectively 5wt.%, 10wt.%, 15wt.%, 20wt.%, 25wt.%, 30wt.%, 35wt.%, 40wt.%, 45wt.%, 50wt.%, 55wt.%, 60wt.%, 65wt.%, 70wt.%, 75wt.%, 80wt.%, 85wt.%, 90wt.%, the composite granule of 95wt.%) through adding certain solvent (ethanol+butanone), dispersion agent (triglyceride), binding agent (PVB), ball milling 5-10h behind the fluidizer (PEG-200), the slurry for preparing is passed through curtain coating, control the thickness of every layer of cast layer, obtain curtain coating gradient complexin embryo ceramic body by behind stacked-pre-molding-wait static pressure at last.The first precompressed thickness α-Al that is 1mm respectively in mould
2O
3With Na-beta-Al
2O
3Biscuit is then at α-Al
2O
3Folded upper curtain coating gradient composite ceramic biscuit is put Na-beta-Al at last on the biscuit
2O
3The further precompressed of biscuit, wait static pressure after, behind 500 ℃ of binder removal 2h, 1500 ℃ are burnt 2h altogether in retort furnace.The thermal shock resistance (putting into immediately cold water after being heated to 300 ℃) of test sealing-in finds that the sealing-in combiner crackle do not occur after through 300 times.Concrete test result sees Table 1.
Table 1:
Data listed from table 1 can be found out, adopt by α-Al
2O
3Na-beta-Al in opposite directions
2O
3The instead of glass of the gradient material that phase gradient changes is carried out sealing-in to sode cell, can greatly improve the sealing-in folding strength, has greatly improved the quality of sealing-in parts, has improved sealing property.
The above only is preferred embodiment of the present invention, be not to limit essence technology contents scope of the present invention, essence technology contents of the present invention is broadly to be defined in the claim scope of application, any technology entity or method that other people finish, if defined identical with the claim scope of application, also or a kind of change of equivalence, all will be regarded as being covered by among this claim scope.
All quote in this application as a reference at all documents that the present invention mentions, just as each piece document is quoted separately as a reference.Should be understood that in addition after having read foregoing of the present invention, those skilled in the art can make various changes or modifications the present invention, these equivalent form of values fall within the application's appended claims limited range equally.
Claims (10)
1. a battery is characterized in that comprising with the method for sealing of heterogeneous stupalith:
Raw material preparation: prepare heterogeneous ceramic base by powder or the slurry of seal, sealing materials 1 and material 2; Preparation comprises by powder or the slurry of the N kind seal, sealing materials of seal, sealing materials 1 and material 2, and the included amount by seal, sealing materials 1 and material 2 of wherein said N kind seal, sealing materials is respectively the graded that increases progressively and successively decrease, and described N 〉=2;
The cloth moulding: premolding is got green layer 1 and green layer 2 by seal, sealing materials 1 and material 2 respectively; Stacked described N kind seal, sealing materials is to form the seal, sealing materials layer on described green layer 1, make the biscuit body with described green layer 2 moulding again, perhaps stacked described N kind seal, sealing materials is made the biscuit body with described green layer 1 moulding again to form the seal, sealing materials layer on described green layer 2;
Sintering: thus with described biscuit body at a certain temperature high temperature burn till and make described heterogeneous ceramic base and be integral by seal, sealing materials 1 and material 2 and with its sealing-in.
2. method for sealing according to claim 1 is characterized in that described graded refers to that the included amount by seal, sealing materials 1 and material 2 of described N kind seal, sealing materials is respectively that equivalent increases progressively or equivalent is successively decreased.
3. method for sealing according to claim 2, it is characterized in that described equivalent increases progressively and the graded of successively decreasing refer to described N kind seal, sealing materials included by the amount of seal, sealing materials 1 and material 2 respectively to increase progressively and successively decrease less than or equal to 35% variable quantity equivalent more than or equal to 5%.
4. each described method for sealing in 3 according to claim 1 is characterized in that in described cloth molding procedure,
Be that the powder of maximum seal, sealing materials or slurry cloth are on green layer 1 with comprising in the described N kind seal, sealing materials by the amount of seal, sealing materials 1 at first, then according to by the amount of seal, sealing materials 1 be the graded of successively decreasing successively with the powder of other seal, sealing materials or slurry layering cloth on green layer 1, put at last green layer 2, moulding makes the biscuit body; Perhaps
Be that the powder of maximum seal, sealing materials or slurry cloth are on green layer 2 with comprising in the described N seal, sealing materials by the amount of seal, sealing materials 2 at first, then according to by the amount of seal, sealing materials 2 be the graded of successively decreasing successively with the powder of other seal, sealing materials or slurry layering cloth on green layer 2, put at last green layer 1, moulding makes the biscuit body.
5. each described method for sealing in 4 according to claim 1 is characterized in that by casting method or the stacked described N kind seal, sealing materials of dry pressing.
6. each described method for sealing in 5 according to claim 1 is characterized in that, described heterogeneous pottery is respectively insulating ceramic alpha-Al by seal, sealing materials 1 and material 2
2O
3With electrolyte ceramics Na-beta-Al
2O
3
7. method for sealing according to claim 6 is characterized in that described electrolyte ceramics is the Na-beta-Al that Li or Mg element are made stablizer
2O
3
8. according to claim 6 or 7 described method for sealing, the thickness that it is characterized in that seal, sealing materials layer described in the described biscuit body is 3～6mm.
9. each described method for sealing in 8 according to claim 6 is characterized in that described seal, sealing materials is by forming the preparation of osmose process or gas-phase permeation reaction method.
10. each described method for sealing in 9 according to claim 6 is characterized in that described sintering process firing temperature is 1400～1700 ℃ of insulations 0.5～5 hour.
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