High temperature battery sealing structure and high temperature battery
Technical field
The utility model belongs to energy-storage battery technical field, and in particular to a kind of high temperature battery sealing structure.
Background technology
In existing electrochemical energy storage technology, the such as energy storage such as sodium-sulphur battery, liquid metal cell of high temperature energy-storage battery
Technology has feature and long-life, the low-maintenance costs such as the collocation output of pollution-free, energy-efficient, flexible power and energy
The advantages of, it is the extraordinary energy storage technology of application prospect.
Using one or more in the alkalinous metals such as lithium, sodium, magnesium more than the electrode material of high temperature battery, battery is in middle height
Under warm environment(Between 150 DEG C ~ 700 DEG C)During work, there is melting or the possibility for vaporizing in electrode material or electrolyte.Above-mentioned
, in room temperature with regard to great activity, as temperature is raised, its activity exponentially increases for electrode material or electrolyte.This will be right
The design of cell seal proposes high requirement.In addition, sealing device needs miniaturization so as to be applied to reach during battery
The purpose of lifting battery volume energy density.
In the Seal Design about high temperature fluent metal battery, most principles using assembling realize sealing, such as " a kind of
Liquid metal cell device "(Application number 201420780918.8), " Semi-liquid metal electrode energy storage battery "(Application number
201310131587.5)Etc. in patent using the insulation of insulating ceramics ring for, by the way of installing additional or fasten, sealing cannot get
Ensure, and the battery structure of above-mentioned patent is complicated, bulky.
For another example, " a kind of liquid metal cell device and its assembly method "(Application number 201410350077.1)Etc. patent
In refer to " top of metal electric current leading-off rods and battery container being fastened using sealed insulation ceramic member " and realize sealing and exhausted
Edge, pottery are secured only toward on metal electric current leading-off rods, thus the sealing means can not to meet liquid metal cell harsh at high temperature
Seal request(Normal temperature may realize sealing when fastening, but at high temperature because material expand difference of coefficients causes ceramic securing member
Different from the expanding with heat and contract with cold of fastening matrix, so as to effectively sealing can not be reached).
Also improve in terms of the encapsulant, such as " a kind of encapsulant and preparation for high temperature energy-storage battery "
(Application number 201310702834.2)Refer to use CaAl in patent2S4As sealant, with the powder such as aluminum oxide+binding agent structure
Become a kind of encapsulant of high temperature energy-storage battery, need to use CaAl2S4As sealant, and use with the high warm of powdered substance
Manage to realize sealing, process is complicated.
Utility model content
The purpose of this utility model is to provide one kind for high temperature battery sealing structure, realizes excellent sealing
Energy.
The technical solution of the utility model is:A kind of high temperature battery sealing structure, including the gold for extracted current
Category part, metalwork be assemblied on battery assembling gap at battery on the inside of arrange one by the assembling gap at close envelope
Closed chamber, metalwork pass through the closing chamber, the closing chamber built with the fluid-tight salt deposit of a layer, two-layer, three layers or more than three layers, respectively
Salt deposit arranges fusing point by inside battery side to outside side to be reduced successively.
The fusing point of an at least salt deposit is less than temperature during battery steady operation.When fluid-tight salt deposit be two-layer and more than
When each salt deposit respectively heated melting then be cooled into.
In one specific embodiment of the utility model, the metalwork is metallic rod, and metallic rod passes through insulating ceramics
Part is assemblied on battery cover board, arranges closing chamber on the inside of the battery below insulating ceramics part, and insulating ceramics part is assemblied in battery
On assembling gap at by its closing.
In one specific embodiment of the utility model, the insulating ceramics part is earthenware, and earthenware is enclosed within metal
On bar, outside earthenware, the whole inner side end of earthenware is contacted metal exterior ring cap with closing chamber.
In one specific embodiment of the utility model, metallic rod, earthenware and metal outer shroud three are joined by interference
The mode of conjunction is assembled into single piece, and metal outer shroud and metallic rod are adopted and earthenware similar thermal expansion coefficient or basically identical gold
Category material.
In one specific embodiment of the utility model, metal outer shroud has first annular portion and second from outside to inside
Ring part, the external diameter in first annular portion are more than the second ring part, and first annular portion and the second ring part have coaxial and aperture phase
Same endoporus, sets gradually earthenware and salt deposit from outside to inside in endoporus.
In one specific embodiment of the utility model, pottery support with holes is set on metal outer shroud inner side end,
Metallic rod surrounds closing chamber jointly through the hole of pottery support, pottery support, earthenware inner side end and metal outer shroud inwall.
In one specific embodiment of the utility model, fluid-tight salt deposit has three layers, and fusing point is respectively:More than 800 DEG C,
300 DEG C ~ 800 DEG C and be less than 300 DEG C;Constitute mixed salt from two or more inorganic salts, based on mixed salt fusing point with its component
Ratio is different and change, constitute the different salt deposit of three kinds of fusing points;Or, from the different inorganic salts of three kinds of fusing points or mixed salt
Constitute three salt deposits;Or, X and Z salt is denoted as respectively from a kind of higher melt and a kind of relatively inorganic salts of low melting point or mixed salt,
Y salt is denoted as according to the mixed salt that phasor searches X and Z of the fusing point between 300 DEG C ~ 800 DEG C, thus constitutes the different salt of three kinds of fusing points
Layer.
The utility model also provides a kind of high temperature battery using the sealing structure, the battery be sodium-sulphur battery or
Liquid metal cell.
The assembly method of above-mentioned sealing structure, including:
Positioning sleeve is enclosed within metallic rod, and is welded on the specified location of metallic rod;
By ceramic care set in metallic rod, fit tightly with the upper surface of positioning sleeve under external force;
By metal exterior ring cap in metallic rod so as to be close to the upper surface of pottery support, constitute structural member A;
By structural member A in the environment of inert atmosphere, on the top of pottery support, metallic rod and the outer interannular of metal are inserted necessarily
The inorganic salts of thickness, heated make inorganic salts melting evenly laid out pottery support on, after cooling formed salt deposit;In the same way
Sequentially form each salt deposit on which;
The internal diameter earthenware that external diameter is bigger than metal bore diameter of outer ring than metallic rod is little is enclosed within by metal by the method for heat expansion and cold contraction
On bar, load metal outer shroud in the hole.
Fluid-tight medium of the present utility model inorganic fused salt of non-conductive son from diversion.On the one hand, when battery in
High temperature(150℃~700℃)During lower work, the fused salt of central filler forms liquid in the transformation that solid liquid phase occurs, and fills fused salt
Layer plays fluid-tight effect to gaseous state positive and negative pole material or electrolyte in battery, prevents above-mentioned material leakage from inside to outside, it is to avoid
Corroded by lithium, sodium, magnesium and its alloy etc. in battery, while avoiding extraneous oxygen, moisture etc. from entering in battery just affecting battery
Often run.On the other hand, under cell operating conditions, due to thermal coefficient of expansion and the thermal coefficient differences of material, general pottery
Seal is likely to form fine crack, so as to cause the seal fails;And the utility model passes through filling between structural member and melts
Salt so that be in a liquid state under cell operating conditions or the salt of semi liquid state is filled and is blocked at the gap of structural member, close so as to avoid
Envelope failure.
Further, the utility model sealing structure utilizes the different melting points of different fused salts, using at least two-layer fusing point not
Same fused salt, all kinds of inorganic salts are melted at different temperatures, and so as to form liquid airproof medium, better tightness, using temperature
Scope is wider.Preferably, the middle temperature of high-temperature molten salt of the fusing point more than 800 DEG C, fusing point between 300 DEG C ~ 800 DEG C is respectively adopted
The low-temperature molten salt of fused salt and fusing point less than 300 DEG C constitutes three layers of molten salt layer, so that fused salt is melted to some extent and is filled in bilayer
Between pottery, it is ensured that fused salt effectively assumes more excellent fluid-tight performance on the premise of filling is not lost in.The three-decker of molten salt layer sets
Meter makes the sealing of this structure more preferably, and for the fused salt packed layer of individual layer, three layers of fused salt structure can be in bigger temperature model
Enclose interior realize liquid airproof, sensitiveer to the reaction of the working environment of temperature change, using wide temperature range.
The utility model realizes first using the sandwich of " Dual-layer pottery, central filler fused salt " using fluid-tight
Resealing, in addition combined with ceramic and intermetallic interference fit(Further, select and there is in different temperatures close expansion system
Several metals and ceramic material are mated)The second resealing is realized, and fluid-tight link is increased on assembling basis, is realized
The dual-seal of battery.
The utility model realizes sealing using fused salt liquid sealant+ceramic inserts structural member, and the sealing structure has pole
Good air-tightness and Corrosion Protection, service life when having ensured that high temperature battery is worked between 150 ~ 700 DEG C, while have concurrently
Insulation characterisitic, simple structure, with low cost, with small-sized, miniature architectural feature, very big under conditions of mechanical strength is ensured
Reduce volume shared by cell sealing, save space.
Description of the drawings
Fig. 1 is the longitudinal section of one specific embodiment sealing structure of the utility model.
Fig. 2 applies the longitudinal section in liquid metal cell for the utility model sealing structure.
In accompanying drawing, fusing point salt deposit, 5- low melting point salt deposit, 6- in the ceramic support of 1- positioning sleeve, 2-, 3- high-melting-point salt deposit, 4-
Metal outer shroud, 7- earthenware, 8- metallic rod, 9- negative material, 10- electrolyte, 11- positive electrode, 12- metal cover board, 13- electricity
Pond housing.
Specific embodiment
Below in conjunction with drawings and Examples, the utility model is described in further detail.Concrete reality described herein
Example is applied only in order to explain the utility model.
In the utility model, the closing space equipped with electrolyte surrounded by battery container is battery " interior " side/portion, therewith
The relative open spaces separated by battery container are side/portion " outward "." on ", D score be the upper and lower relation that is described by figure
Understand.
Sealing structure of the present utility model is applied to high temperature energy-storage battery, for example, it is adaptable to sodium-sulphur battery, liquid metal
Battery etc..
As shown in figure 1, one specific embodiment high temperature battery sealing structure of the utility model.The structure is applied to electricity
Chi Shi, metallic rod 8 can connect positive pole or negative conductive area, and metal outer shroud 6 can connect negative pole or positive conductive area.?
As shown in Figure 2 in embodiment, metal cover board 12 is connected with anode, and metal bar 8 is connected with negative material 9.
In embodiment as shown in Figure 2, positive electrode 11, electrolyte 10, negative material 9 are in battery container 13.Adopt
Use metal polyporous material(Such as porous foam iron-nickel alloy)In electrolyte 10, and it is adsorbed with negative material 9.
Metallic rod 8 is located at the center in the hole of metal outer shroud 6 through the centre bore of earthenware 7, earthenware 7.Metallic rod 8, pottery
Porcelain tube 7 and 6 three of metal outer shroud are assembled by way of interference fit.
Specific embodiment shown in figure, metal outer shroud 6 have first annular portion from outside to inside and the second ring part, and first
The external diameter of ring part is more than the second ring part, and first annular portion and the second ring part have coaxial and aperture identical endoporus.Gold
Belong to double L-shaped of the section in specular vertically of outer shroud 6.
Pottery support 2 with holes is set on 6 inner side end of metal outer shroud, and metallic rod 8 is through the hole of pottery support 2.Using set
Positioning sleeve 1 that is outer in metallic rod 8 and being welded with which is closely attached to pottery support 2 on 6 inner side end of metal outer shroud.Pottery support 2,
7 inner side end of earthenware and 6 inner hole wall of metal outer shroud surround closing chamber jointly.The whole inner side end of earthenware 7 and closing chamber
Contact, by earthenware 7 and the sealing of 6 joining part of metal outer shroud.
Metallic rod 8 passes through the closing chamber, and the closing chamber is built with the fluid-tight salt of one layer, two-layer, three layers or more than three layers
Layer(In figure is three layers:Low melting point salt deposit 3, middle fusing point salt deposit 4 and high-melting-point salt deposit 5), each salt deposit is by inside battery side to outward
Portion side arrangement fusing point reduces successively, and the fusing point of an at least salt deposit is less than temperature during battery steady operation, each salt deposit
Then heated melting is cooled into respectively.
The concrete processing of one specific embodiment of the utility model and assembling process as follows:
First, the internal diameter of positioning sleeve 1 is machined to more than 8 external diameter 0.001-1mm of metallic rod.Will be fixed using frock clamp
Position cutting ferrule 1 is enclosed within metallic rod 8, and is welded on the specified location of metallic rod 8, it is ensured that the sealing of weld.Internal diameter is big
It is enclosed within metallic rod 8 in the pottery support 2 of the about 0.001-1mm of metallic rod 8, tight with the upper surface of positioning sleeve 1 under external force
Closely connected conjunction.
Metal outer shroud 6 is enclosed within metallic rod 8 so as to be close to the upper surface of pottery support 2, while the axle of metal outer shroud 6
Line should constitute structural member A with the dead in line of metallic rod.
Structural member A is put in glove box, in the environment of inert atmosphere, in the top of pottery support 2, metallic rod 8 and metal
Certain thickness is inserted between outer shroud 6 and high-temperature molten salt of the fusing point more than 800 DEG C, it is evenly laid out that heated melting melts inorganic salts
In 2 upper ends of pottery support, the high-melting-point salt deposit 3 of dense uniform after normal temperature cooling, is formed;Then uniform in 3 upper surface of high-melting-point salt deposit
Middle temperature molten salt of the certain thickness fusing point between 300 DEG C -800 DEG C is covered, uniform temperature is heated after melting and cooling down in high temperature
Fused salt upper surface forms middle fusing point salt deposit 4;Subsequently, same method covers certain thickness fusing point on middle fusing point salt deposit 4 and is less than
300 DEG C of low melting point salt deposit 5.
Finally, by the method for heat expansion and cold contraction, by less than metallic rod 8 for internal diameter 0.001 ~ 1mm, external diameter is bigger than metal bore diameter of outer ring
The earthenware 7 of 0.001 ~ 1mm is enclosed within metallic rod 8, loads 6 in the hole of metal outer shroud so as to which upper end is concordant with metal outer shroud upper end,
The ceramic inserts structure of interference fit is formed, and overall structure is sealed so as to constitute a high temperature battery.
When the sealing structure is applied to high temperature battery, metal outer shroud 6 and battery tank body are carried out laser welding, and structure
Become a sealing overall, it is ensured that the normal operation of battery under the conditions of high temperature.
The fused salt for using can be lithium fluoride(LiF), sodium fluoride(NaF), potassium fluoride(KF), magnesium fluoride(MgF2), chlorination
Sodium(NaCl), barium chloride(BaCl2), scandium chloride(ScCl3), lanthanum chloride(LaCl3), sodium iodide(NaI), sodium bromide(NaBr), bromine
Change lithium(LiBr), magnesium chloride(MgCl2), calcium chloride(CaCl2), zinc chloride(ZnCl2), silver chlorate(AgCl), sodium nitrate
(NaNO3), potassium nitrate(KNO3), aluminium chloride(AlCl3), mercury chloride(HgCl2), gallium chloride(GaCl3), stannic chloride(SnCl4), chlorine
Change titanium(TiCl4)Deng in simple substance salt or mixture.
Low melting point salt deposit 3, middle fusing point salt deposit 4 can be constituted for identical or different fused salt materials with high-melting-point salt deposit 5.Example
Such as, in a specific embodiment, constitute mixed salt from two or more inorganic simple substance salt, based on mixed salt fusing point with its group
It is divided into point ratio and changes, selects the mixed salt of the heterogeneity ratio of high, normal, basic three kinds of fusing points.In another embodiment, select
The simple substance salt of the different high, normal, basic three kinds of fusing points of three kinds of fusing points or mixed salt.In another embodiment, from a kind of high-melting-point and
A kind of simple substance salt of low melting point or mixed salt are denoted as X and Z salt respectively, according to phasor search X of the fusing point between 300 DEG C -800 DEG C and
Z mixed salt is denoted as Y salt, is X salt, Y salt and Z salt according to the order of high, normal, basic three kinds of fusing points.
The pottery support 2 that the utility model is used and earthenware 7 are preferably magnesia, zirconium oxide, yittrium oxide, beryllium oxide, nitrogen
Change one or more in boron, aluminium nitride or silicon nitride.The surface roughness of earthenware 7 is Ra0.2 and following.Pottery 2 Hes of support
Earthenware 7 can be identical or different ceramic material.
Preferably, used in the utility model metal outer shroud 6 and metallic rod 8 are the thermal coefficient of expansion phases with earthenware 7
Near metal material, positioning sleeve 1 are the metal material with the expansion coefficient similar of pottery support 2, preferably copper and copper alloy, aluminium
And aluminium alloy, invar alloy, 321 (1Cr18Ni9Ti), 304 (0Cr18Ni9), 304L (00Cr19Ni10), 316
(0Cr17Ni12Mo2)、316L(00Cr17Ni14Mo2)、430(1Cr17)、201(17Cr4.5Ni6)In the middle of stainless steel etc. one
Plant or multiple.The surface roughness of 6 inner surface of metal outer shroud and 8 outer surface of metallic rod is Ra0.2 and following.