CN103500855A - Sodium-sulfur cell - Google Patents
Sodium-sulfur cell Download PDFInfo
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- CN103500855A CN103500855A CN201310485385.0A CN201310485385A CN103500855A CN 103500855 A CN103500855 A CN 103500855A CN 201310485385 A CN201310485385 A CN 201310485385A CN 103500855 A CN103500855 A CN 103500855A
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- sodium
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- becket
- electrolyte ceramics
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- BNOODXBBXFZASF-UHFFFAOYSA-N [Na].[S] Chemical compound [Na].[S] BNOODXBBXFZASF-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000000919 ceramic Substances 0.000 claims abstract description 135
- 239000003792 electrolyte Substances 0.000 claims abstract description 90
- 239000011734 sodium Substances 0.000 claims abstract description 87
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 87
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 86
- 238000003860 storage Methods 0.000 claims abstract description 46
- 239000007788 liquid Substances 0.000 claims abstract description 33
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 22
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000835 fiber Substances 0.000 claims abstract description 6
- 238000009413 insulation Methods 0.000 claims description 49
- 230000009172 bursting Effects 0.000 claims description 38
- 210000002421 cell wall Anatomy 0.000 claims description 31
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 24
- 238000007789 sealing Methods 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 23
- 239000005864 Sulphur Substances 0.000 claims description 17
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 14
- 239000010410 layer Substances 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000011241 protective layer Substances 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 230000001681 protective effect Effects 0.000 claims description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 229920000914 Metallic fiber Polymers 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000000428 dust Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 3
- 230000002427 irreversible effect Effects 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 abstract description 6
- 239000011593 sulfur Substances 0.000 abstract description 6
- 238000004146 energy storage Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 208000032826 Ring chromosome 3 syndrome Diseases 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000003466 welding Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 230000006835 compression Effects 0.000 description 5
- 238000007906 compression Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910000838 Al alloy Inorganic materials 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 238000009954 braiding Methods 0.000 description 3
- 229910052571 earthenware Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 235000019628 coolness Nutrition 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- -1 sodium metals Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/39—Accumulators not provided for in groups H01M10/05-H01M10/34 working at high temperature
- H01M10/3909—Sodium-sulfur cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/138—Primary casings; Jackets or wrappings adapted for specific cells, e.g. electrochemical cells operating at high temperature
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a sodium-sulfur cell in the chemical energy storage field. The sodium-sulfur cell comprises a shell and an electrolyte ceramic tube nested inside the shell. An anode chamber radially forms between the shell and the electrolyte ceramic tube. A cathode chamber radially forms inside the electrolyte ceramic tube. The anode chamber is filled with a porous conducting fiber felt. The top of the electrolyte ceramic tube is provided with a ceramic insulating ring radially projecting out. An anode seal is disposed between the ceramic insulating ring and the shell and closes the anode chamber. A sodium storage tube and a safety tube connected to the outside of the sodium storage tube in a sleeving manner are disposed inside the cathode chamber. The top of the sodium storage tube is closed through a cathode seal cap. A cathode seal ring is disposed between the ceramic insulating ring and the cathode seal cap and closes the cathode chamber. An insulated buffer layer non-wettable to liquid sodium is disposed between the bottom of the outer wall of the safety tube and the bottom of the inner wall of the electrolyte ceramic tube. The bottom of the outer wall of the electrolyte ceramic tube is provided with an insulated bottom protection layer non-wettable to sulfur and sodium polysulfide.
Description
Technical field
The present invention relates to a kind of sodium-sulphur battery in chemical energy storage field.
Background technology
As shown in Figure 1, sodium-sulphur battery comprises shell 1 and is socketed in the electrolyte ceramics pipe 4 in shell 1.Form cathode chamber 100 between shell 1 and electrolyte ceramics pipe 4, be filled with porous, electrically conductive fibrofelt 2 in cathode chamber 100.The end face of electrolyte ceramics pipe 4 is provided with radially outward outstanding ceramic insulation ring 3, by cathode chamber 100 sealings.The inboard anode chamber 400 that forms of electrolyte ceramics pipe 4.The bursting tube 8 that is provided with storage sodium pipe 9 in anode chamber 400 and is socketed in storage sodium pipe 9 outsides.The bottom of storage sodium pipe 9 is provided with through hole 91, and the top of storage sodium pipe 9 is by 11 sealings of negative pole seal cover.Negative pole seal cover 11 is by anode chamber 400 and 9 sealings of storage sodium pipe.
The core component of sodium-sulphur battery is electrolyte ceramics pipe 4, and electrolyte ceramics pipe 4 is by β "-Al
2o
3make, it conducts sodium ion, the double barrier film of doing.Sodium-sulphur battery cycle life depends on the capability and performance of electrolyte ceramics pipe 4 to a great extent.Once electrolyte ceramics pipe 4 has micro-crack or breaks, sodium directly contacts the generation vigorous reaction with sulphur, and temperature reaches as high as 2000 ℃, and all component in the instant melting sodium-sulphur battery causes active material to leak.Existing sodium-sulphur battery safety protection structure mainly adopts socket and electrolyte ceramics pipe 4 coefficients of expansion between electrolyte ceramics pipe 4 and storage sodium pipe 9 to differ larger bursting tube 8, bursting tube 8 is made by aluminum or aluminum alloy usually, radial clearance 401 between bursting tube 8 and electrolyte ceramics pipe 4 inwalls, the width of radial clearance 401 is controlled at 100 microns, after 4 breakages of electrolyte ceramics pipe, bursting tube 8 axial expansions are close to the inwall of electrolyte ceramics pipe 4, and give the inwall of bottom of electrolyte ceramics pipe 4 with pressure, this pressure is greater than the suffered pressure of electrolyte ceramics pipe 4 bottom outer wall, radial clearance 401 between bursting tube 8 and electrolyte ceramics pipe 4 is also along with the radial expansion closure of bursting tube 8, sodium can't contact with sulphur.The perpendicularity of this means of defence to electrolyte ceramics pipe 4, and the circularity of electrolyte ceramics pipe 4 bottoms has relatively high expectations, therefore processing electrolyte ceramics pipe 4 wastes time and energy, and electrolyte ceramics pipe 4 in use very easily damages simultaneously.
Summary of the invention
The objective of the invention is in order to overcome the deficiencies in the prior art; a kind of sodium-sulphur battery is provided; its Liquid Sodium that can prevent electrolyte ceramics pipe bottom participates in reaction, in the time of protection electrolyte ceramics pipe bottom, reduces the requirement for electrolyte ceramics pipe perpendicularity and bottom circularity.
A kind of technical scheme that realizes above-mentioned purpose is: a kind of sodium-sulphur battery comprises shell and is socketed in the electrolyte ceramics pipe in described shell, described shell and described electrolyte ceramics caliber between form cathode chamber, described electrolyte ceramics caliber forms anode chamber to the inside, be filled with the porous, electrically conductive fibrofelt in described cathode chamber, the end face of described electrolyte ceramics pipe is provided with radially outward outstanding ceramic insulation ring, be provided with anodal sealing device between described ceramic insulation ring and described shell, by described cathode chamber sealing, the bursting tube that is provided with storage sodium pipe in described anode chamber and is socketed in the described storage sodium pipe outside, the top of described storage sodium pipe is by the sealing of negative pole seal cover, be provided with the negative pole sealing ring between described ceramic insulation ring and described negative pole seal cover, by described anode chamber sealing, :
Between the bottom of the bottom of described bursting tube outer wall and described electrolyte ceramics inside pipe wall, be provided with the insulation and the nonwettable resilient coating of liquid towards sodium, the bottom of described electrolyte ceramics pipe outer wall be provided with the insulation and to sulphur and the nonwettable bottom protective layer of sodium polysulfide.
Further, described resilient coating be adopt in zirconia, silicon nitride, alumina powder or carbon dust any one or multiple, described bottom protective layer adopts alumina silicate fibre to make.
Further, in the radial clearance between described bursting tube and described electrolyte ceramics pipe, be provided with the gap-fill layer, being weaved into by metallic fiber of described gap-fill layer, and the porosity of described gap-fill layer is～%.
Further, the bottom of described storage sodium pipe is provided with through hole and filter course, and described filter course is become by 304 stainless steels or 316 stainless fibrages.
Further, the bottom of described storage sodium pipe and described bursting tube is rectangular base.
Further, the end face of described bursting tube is higher than the end face of described electrolyte ceramics pipe.
Further, all be filled with protective gas in described storage sodium pipe and described cathode chamber.
Further, the upper space of described storage sodium pipe, and the protective gas in the upper space of described cathode chamber is nitrogen.
Further, the nitrogen in the upper space of described cathode chamber is decomposed to form by sodium azide is irreversible.
Further, described anodal sealing device comprises L shaped becket, flute profile becket and top metal ring;
Described L shaped becket is divided into vertical section and horizontal segment, and the bottom surface of the end face of described horizontal segment and described ceramic insulation ring is fixed, and the lateral surface of the medial surface of described vertical section and described ceramic insulation ring is fixed; The lateral surface of described vertical section separates with the medial surface of described shell, and the end face of described vertical section is higher than the end face of described ceramic insulation ring;
The bottom surface of described flute profile becket is higher than the end face of described ceramic insulation ring, described flute profile becket is provided with inner ring cell wall and outer ring cell wall, described inner ring cell wall is higher than described outer ring cell wall, the medial surface of the lateral surface of described outer ring cell wall and the vertical section of described L shaped becket is fixed, and the end face of the vertical section of the end face of described outer ring cell wall and described L shaped becket is contour;
Described top metal ring connects the lateral surface of inner ring cell wall of described flute profile becket and the medial surface of described shell, and the end face of the end face of described top metal ring and described flute profile becket inner ring cell wall and the end face of described shell are contour; The end face of described top metal ring is upper outside a cannelure.
Adopted the technical scheme of a kind of sodium-sulphur battery of the present invention; the sodium-sulphur battery that comprises the shell, electrolyte ceramics pipe, bursting tube and the storage sodium pipe that are socketed successively from outside to inside; be provided with insulation and the nonwettable resilient coating of liquid towards sodium between the bottom of the bottom of described bursting tube outer wall and described electrolyte ceramics inside pipe wall, the bottom of described electrolyte ceramics pipe outer wall is provided with insulation and to the technical scheme of sulphur and the nonwettable bottom protective layer of sodium polysulfide.Its technique effect is: its Liquid Sodium that can prevent electrolyte ceramics pipe bottom participates in reaction, in the time of protection electrolyte ceramics pipe bottom, reduces the requirement for electrolyte ceramics pipe perpendicularity and bottom circularity.
The accompanying drawing explanation
The structural representation of a kind of sodium-sulphur battery that Fig. 1 is prior art.
The structural representation that Fig. 2 is a kind of sodium-sulphur battery of the present invention.
The enlarged diagram of the A part that Fig. 3 is Fig. 2.
Embodiment
Refer to Fig. 2 and Fig. 3, the present inventor is in order to be understood technical scheme of the present invention better, below by embodiment particularly, and is described in detail by reference to the accompanying drawings:
Refer to Fig. 2 and Fig. 3, a kind of sodium-sulphur battery of the present invention, comprise shell 1, electrolyte ceramics pipe 4, the bursting tube 8 of socket from outside to inside and store up sodium pipe 9.The anode chamber 400 that the radially inner side of electrolyte ceramics pipe 4 is sodium-sulphur battery.Electrolyte ceramics pipe 4 and shell 1 are the cathode chamber 100 of sodium-sulphur battery between radially.Therefore bursting tube 8 and storage sodium pipe 9 all are positioned at anode chamber 400.The top of storage sodium pipe 9 is by the welded closure with negative pole seal cover 11.The top of storage sodium pipe 9 is Laser Welding or gas tungsten arc welding by the welding manner with negative pole seal cover 11.
Be filled with porous, electrically conductive fibrofelt 2 in cathode chamber 100, be filled with sulphur or sodium polysulfide in porous, electrically conductive fibrofelt 2.Be fixed with radially outward outstanding ceramic insulation ring 3 on the end face of electrolyte ceramics pipe 4, be provided with anodal sealing device 6 between ceramic insulation ring 3 and shell 1, by cathode chamber 100 sealings.Be provided with negative pole sealing ring 7 between the end face of negative pole seal cover 11 and ceramic insulation ring 3, by anode chamber 400 sealings.
9 effects of storage sodium pipe are storing liquid sodium metals, can adopt all good austenitic stainless steels of welding performance and rigidity, can with 11 welding of negative pole seal cover.The bottom of storage sodium pipe 9 adopts rectangular base.The bottom of storage sodium pipe 9 is provided with through hole 91.The diameter 0.3-1mm of through hole 91, flow to the flow velocity of bursting tube 8 in order to limit Liquid Sodium from storage sodium pipe 9.In order to guarantee to store up the intensity of sodium pipe 9 and the safe operation of sodium-sulphur battery, the wall thickness 0.8-1.5mm of storage sodium pipe 9.
Simultaneously, the bottom of storage sodium pipe 9 also is provided with filter course 92, and filter course 92 is mainly to be formed by the metallic fiber braiding, and particularly soft 304 or 316L stainless steel fibre braiding forms, metallic fiber diameter 8-20 micron.Filter course 92 effects are the high-melting-point contaminant particles of filtering in Liquid Sodium, such as sodium metal particulate of sodium carbonate particulate and not melting etc., prevent that through hole 91 is blocked, and prevent that these particles from entering the radial clearance 401 between bursting tube 8 and electrolyte ceramics pipe 4, and then cause this radial clearance 401 blocked, guarantee the smooth and easy inflow bursting tube 8 of Liquid Sodium, thereby prevent sodium-sulphur battery because electrolyte ceramics pipe 4 lost efficacy because can not get the supply of sufficient Liquid Sodium.
Because the bottom of bursting tube 8 is rectangular base, and the bottom of electrolyte ceramics pipe 4 is hemispheric, therefore, between the inwall of the bottom of bursting tube 8 and ceramic electrolysis tube 4 bottoms, resilient coating 5 will be set.The materials such as the adopted zirconia of resilient coating 5, silicon nitride, alumina powder, carbon dust, these materials can not with Liquid Sodium generation chemical reaction, sodium is not infiltrated, and insulation property are good.The effect of resilient coating 5 is to protect electrolyte ceramics pipe 4 bottoms; reduce bursting tube 8 and reduce the quality of the sodium of the participation reaction in anode chamber 400 for the pressure of electrolyte ceramics pipe 4 bottoms simultaneously; guarantee the fail safe of electrolyte ceramics pipe 4 bottoms, and reduce the requirement for electrolyte ceramics pipe 4 perpendicularity and bottom circularity.
Filter course 92 in storage sodium pipe 9 has loose structure, and the aperture of this loose structure is less than 10 μ m, in case the tablet footpath is greater than the impurity particle of 10 μ m, enters this radial clearance 401.
In radial clearance 401, also be filled with gap-fill layer 13, gap-fill layer 13 is by metallic fiber, and especially soft 304 or 316L stainless steel fibre braiding forms.The porosity of gap-fill layer 13 is 30-50%.13 pairs of sodium of gap-fill layer have suction-operated, simultaneously, because the sodium of participating in reaction is only the inwall of electrolyte ceramics pipe 4 and the sodium in the radial clearance 401 between bursting tube 8 outer walls, therefore the suction-operated of gap-fill layer 13 can also reduce the sodium amount that participates in reaction, control the temperature of sodium-sulphur battery, thus effectively control that electrolyte ceramics pipe 4 breaks or while generating micro-crack the temperature of sodium-sulphur battery below 600 ℃.
Simultaneously, between the bottom surface and shell 1 of electrolyte ceramics pipe 4 outer walls, the bottom of electrolyte ceramics pipe 4 outer walls is provided with bottom protective layer 10.The thickness d 3 of bottom protective layer 10 is 10～30mm.The Main Function of bottom protective layer 10 is to stop the bottom generation Liquid Sodium of electrolyte ceramics pipe 4 and the electrochemical reaction of liquid sulfur, and bottom protective layer 10 can adopt insulation property outstanding, and to sulphur or the nonwettable inorganic refractory fiber material of sodium polysulfide.The preferred material of bottom protective layer 10 is alumina silicate fibre.
By the synergy of resilient coating 5 and bottom protective layer 10, can prevent that the Liquid Sodium of electrolyte ceramics pipe 4 bottoms from participating in reaction, in the time of protection electrolyte ceramics pipe 4 bottom, reduced the requirement for electrolyte ceramics pipe 4 perpendicularity and bottom circularity.
During the work of sodium sulphur normal battery, the Liquid Sodium in storage sodium pipe 9, enter bursting tube 8 through filtering layer 92 and through hole 91, again from the top of bursting tube 8, overflow in described radial clearance 401, the sodium in described radial clearance 401 enters into the inwall of electrolyte ceramics pipe 4, and the betatopic reaction occurs, after becoming sodium ion, sodium ion sees through electrolyte ceramics pipe 4, from passing of electrolyte ceramics pipe 4 outer walls, enters cathode chamber 100, and react with the liquid sulfur in porous, electrically conductive fibrofelt 2, generate sodium polysulfide.When electrolyte ceramics pipe 4 breaks or generates micro-crack; the end face of bursting tube 8 is higher than the end face of ceramic electrolysis tube 4; the Liquid Sodium overflowed from bursting tube 8 tops also can't see through the liquid sulfur in porous, electrically conductive fibrofelt 2 electrolyte ceramics pipe 4 and cathode chamber 100 and react; the safeguard protection that has guaranteed sodium-sulphur battery is effective, controls the temperature of sodium-sulphur battery in 600 ℃.
An other improvement of sodium-sulphur battery is: the upper space of storage sodium pipe 9, in the space between the liquid level of Liquid Sodium and negative pole seal cover 11, be filled with protective gas, and this protective gas can't be dissolved in Liquid Sodium, also can't react with Liquid Sodium.This protective gas is preferably nitrogen or argon gas, the angle of large-scale production, is preferably nitrogen.Under the working temperature of sodium-sulphur battery, the air pressure P1 of storage sodium pipe 9 interior protective gas is 0.2-2 standard atmospheric pressure.The volume of the upper space of storage sodium pipe 9 is V1.
The upper space of cathode chamber 100, at the end face of porous, electrically conductive fibrofelt 2, to also being filled with between the end face of cathode chamber 100, porous, electrically conductive fibrofelt 2 can't adsorb, and the protective gas do not reacted with sulphur and sodium polysulfide.This protective gas is preferably nitrogen or argon gas, the angle of large-scale production, is preferably nitrogen.The upper space volume of cathode chamber 100 is V2.Under the working temperature of sodium-sulphur battery, the air pressure P2 in cathode chamber 100 is than the high 0.1-0.5 of the air pressure P1 standard atmospheric pressure in storage sodium pipe 9.
In the present embodiment, the nitrogen in cathode chamber 100 irreversibly decomposes generation by sodium azide, and the nitrogen in storage sodium pipe 9 is loaded in the sodium-sulphur battery assembling process.Sodium azide resolves into Liquid Sodium and nitrogen under 275 ℃.The sodium azide of 1mol can decomposite the nitrogen of 1.5mol and the sodium of 1mol.Therefore in the situation that storage sodium intraductal atmospheric pressure P1 under known 275 ℃ can pass through equation for ideal gases, i.e. P2 * V2=nRT, calculate the amount of sodium azide in cathode chamber 100.T=275 ℃ wherein, i.e. 548K, the amount that n is sodium azide.After the Liquid Sodium that sodium azide decomposites reacts with the sulphur of filling in porous, electrically conductive fibrofelt 2, the temperature of sodium-sulphur battery raises and can not surpass 5 ℃, can ignore.
After 4 breakages of electrolyte ceramics pipe, because the duplicate protection of resilient coating 5 and bottom protective layer 10 is arranged at electrolyte ceramics pipe 4 bottoms, the 4 bottom fail safes of electrolyte ceramics pipe have been guaranteed.Due to when electrolyte ceramics pipe 4 breaks or micro-crack is arranged, the air pressure P2 of the upper space of cathode chamber 100 is greater than the air pressure P1 of the upper space of storage sodium pipe 9, the Liquid Sodium of therefore participating in reaction is only the Liquid Sodium in described radial clearance 401, sulphur in the porous, electrically conductive fibrofelt 2 of cathode chamber 100 sees through electrolyte ceramics pipe 4, enter in radial clearance 401, react with Liquid Sodium.Because 2 pairs of sulphur of porous, electrically conductive fibrofelt have stronger adsorption capacity, enter sulphur in described radial clearance 401 still seldom, simultaneously, the product of Liquid Sodium and liquid sulfur reaction is adsorbed between radial clearance 401 and bursting tube 8 and storage sodium pipe 9, hinder the further reaction of Liquid Sodium and liquid sulfur, improve the security performance of battery.
Simultaneously, the present invention also improves anodal sealing device 6.Anodal sealing device 6 comprises L shaped becket 61, flute profile becket 62 and top metal ring 63.L shaped becket 61, flute profile becket 62 and top metal ring 63 are connected by the chain type connected mode, with the lateral surface by ceramic insulation ring 3, with the medial surface of shell 1, be connected, thereby by cathode chamber 100 sealings between electrolyte ceramics pipe 4 and shell 1.
L shaped becket 61 is divided into vertical section 611 and horizontal segment 612, and the bottom surface of the end face of horizontal segment 612 and ceramic insulation ring 3 is fixed.Due to the bottom surface of cotton up to dead ring 3, be provided with along the outer rim of ceramic insulation ring 3 stage structure 31 of falling from power, the bottom surface of end face that therefore also can horizontal segment 612 and the stage structure 31 of falling from power of ceramic insulation ring 3 is fixed.The lateral surface of the medial surface of vertical section 611 and ceramic insulation ring 3 is fixed; The lateral surface of vertical section 611 separates with the medial surface of shell 1, and the end face of vertical section 611 is higher than the end face of ceramic insulation ring 3.
Between ceramic insulation ring 3 and L shaped becket 61, all by thermocompression bonding, fix, because the selected scolder of thermocompression bonding is fine aluminium or aluminium alloy, therefore L shaped becket 61, flute profile becket 62 and top metal ring 63 preferred materials are fine aluminium or aluminium alloy.
The opening upwards of flute profile becket 62, and the bottom surface of grooved becket 62 is higher than the end face of ceramic insulation ring 3, and the end face of the bottom surface ceramic insulation ring 3 of grooved becket 62 separates.Flute profile becket 62 is provided with inner ring cell wall 621 and outer ring cell wall 622, and inner ring cell wall 621 is higher than outer ring cell wall 622.Wherein the medial surface of the vertical section 611 of the lateral surface of outer ring cell wall 622 and L shaped becket 61 is by being welded and fixed, and preferred welding manner is Laser Welding or inert gas tungsten electrode protection weldering, contaminated to prevent sulphur or sodium polysulfide in cathode chamber 100.And the end face of the vertical section 611 of the end face of outer ring cell wall 622 and L shaped becket 61 is contour, with the welding between the vertical section 611 of the outer ring cell wall 622 that facilitates grooved becket 62 and L shaped becket 61.
The top of inner ring cell wall 621 lateral surfaces of top metal ring 63 connection flute profile beckets 62 and the top of shell 1 medial surface.The lateral surface of the inner ring cell wall 621 of the medial surface of top metal ring 63 and flute profile becket 62 is by being welded and fixed.The top of shell 1 medial surface, be provided with limited step structure 11, and the lateral surface of top metal ring 63 and bottom surface and this limited step structure 11 be by being welded and fixed, thereby by 100 sealings of the cathode chamber of sodium-sulphur battery.Between the lateral surface of the inner ring cell wall 621 of top metal ring 63 and flute profile becket 62; and and the medial surface of shell 1 between be welded and fixed; the optimal way of welding is Laser Welding or inert gas tungsten electrode protection weldering, contaminated to prevent sulphur or sodium polysulfide in cathode chamber 100.
The end face of top metal ring 63 and the end face of flute profile becket 62 inner ring cell walls 621 and the end face of shell 1 are contour simultaneously, and the end face of top metal ring 63 is provided with a cannelure 631, so that top metal ring 63 and grooved becket 62, the welding between top metal ring 63 and shell 1.
Be connected L shaped becket 61, flute profile becket 62 and top metal ring 63 by between the medial surface of ceramic insulation ring 3 and shell 1, chain type being set, by cathode chamber 100 sealings.Such design can be in the sodium-sulphur battery temperature-fall period; the suffered compression by electrolyte ceramics pipe 4; pass to L shaped becket 61, flute profile becket 62 and top metal ring 63 by ceramic insulation ring 3; and L shaped becket 61, flute profile becket 62 and top metal ring 63 are by deformation; the compression that absorbed electrolyte earthenware 4 is suffered; thereby prevent the cracking at electrolyte ceramics pipe 4 bottoms and top or micro-crack occurs, the safe operation of protection sodium-sulphur battery.
And the bottom surface of ceramic insulation ring 3 is provided with the effect of the stage structure 31 of falling from power and is: prevent ceramic insulation ring 3 cracking when bearing the compression that electrolyte ceramics pipe 4 passes over, thereby cause sodium-sulphur battery to lose efficacy.
The effect that the top of the medial surface of shell 1 is provided with limited step structure 11 is the weld strength between reinforced top becket 63 and shell 1.
In order further to guarantee the stable operation of sodium-sulphur battery, for the size of L shaped becket 61, flute profile becket 62, also made concrete regulation:
Wherein the thickness d of L shaped becket 61 is 0.3～1mm, and the thickness d of L shaped becket 61 is lower than 0.3mm, L shaped becket 61 processing difficulties, and mechanical property is poor.Thickness is greater than 1mm, can't be by the suffered compression of the effective absorbed electrolyte earthenware 4 of deformation, the residual compressive stress that also can't make flute profile becket 62 and top metal ring 63 cause ceramic insulation ring 3 to be subject to by the suffered compression of the effective absorbed electrolyte earthenware 4 of deformation strengthens, cause ceramic insulation ring 3 crackings, sodium-sulphur battery lost efficacy.
The end face of the vertical section 611 of L shaped becket 61 is 4-10mm higher than the height h1 of the end face of ceramic insulation ring 3.If the end face of the vertical section 611 of L shaped becket 61 is less than 4mm higher than the height h1 of the end face of ceramic insulation ring 3, the easy short circuit of sodium-sulphur battery, the end face of the vertical section 611 of L shaped becket 61 is greater than 10mm higher than the height h1 of the end face of ceramic insulation ring 3, cause the waste of material in L shaped becket 61 manufacture processes for a moment, two can cause the sodium-sulphur battery height to increase, and affect sodium-sulphur battery work temperature.
The height h2 of the outer ring cell wall 622 of flute profile becket 62 is 1.5～2.5mm.The height h2 of the outer ring cell wall 622 of flute profile becket 62 is less than 1.5mm, the weld strength between the vertical section 611 of the outer ring cell wall 622 of flute profile becket 62 and L shaped becket 61 reduces, the height h2 of the outer ring cell wall 622 of flute profile becket 62 is greater than 2.5mm, distance between the end face of the bottom surface of flute profile becket 62 and ceramic insulation ring 3 reduces, the easy short circuit of sodium-sulphur battery.
After testing, after having adopted this positive pole sealing device 6, sodium-sulphur battery is after 20 coolings of experience and heating up, and the bottom of its electrolyte ceramics pipe 4 and top still remain intact and break or micro-crack without any, guarantee that can reach more than 10 years the useful life of sodium-sulphur battery.
Simultaneously, in order further to prevent ceramic insulation ring 3 crackings, on the end face of ceramic insulation ring 3, inner edge along the end face of ceramic insulation ring 3 is provided with a recessed ledge frame face 32, the bottom of negative pole sealing ring 7 is provided with a radially outward outstanding flange 71, and the bottom surface of flange 71 is fixed with this recessed ledge frame face 32.
Claims (10)
1. a sodium-sulphur battery, comprise shell (1) and be socketed in the electrolyte ceramics pipe (4) in described shell (1), described shell (1) and described electrolyte ceramics pipe (4) form cathode chamber (100) between radially, described electrolyte ceramics pipe (4) radially inner side forms anode chamber (400), be filled with porous, electrically conductive fibrofelt (2) in described cathode chamber (100), the end face of described electrolyte ceramics pipe (4) is provided with radially outward outstanding ceramic insulation ring (3), be provided with anodal sealing device (6) between described ceramic insulation ring (3) and described shell (1), described cathode chamber (100) is sealed, the bursting tube (8) that is provided with storage sodium pipe (9) in described anode chamber (400) and is socketed in described storage sodium pipe (9) outside, the top of described storage sodium pipe (9) is by negative pole seal cover (11) sealing, be provided with negative pole sealing ring (7) between described ceramic insulation ring (3) and described negative pole seal cover (11), described anode chamber (400) is sealed, it is characterized in that:
Between the bottom of the bottom of described bursting tube (8) outer wall and described electrolyte ceramics pipe (4) inwall, be provided with the insulation and the nonwettable resilient coating of liquid towards sodium (5), the bottom of described electrolyte ceramics pipe (4) outer wall be provided with the insulation and to sulphur and the nonwettable bottom protective layer of sodium polysulfide (10).
2. a kind of sodium-sulphur battery according to claim 1 is characterized in that: described resilient coating (5) be adopt in zirconia, silicon nitride, alumina powder or carbon dust any one or multiple, described bottom protective layer (10) adopts alumina silicate fibre to make.
3. a kind of sodium-sulphur battery according to claim 1, it is characterized in that: in the radial clearance (401) between described bursting tube (8) and described electrolyte ceramics pipe (4), be provided with gap-fill layer (13), being weaved into by metallic fiber of described gap-fill layer (13), and the porosity of described gap-fill layer (13) is 30～50%.
4. a kind of sodium-sulphur battery according to claim 1, it is characterized in that: the bottom of described storage sodium pipe (9) is provided with through hole (91) and filter course (92), and described filter course (92) is become by 304 stainless steels or 316 stainless fibrages.
5. according to the described a kind of sodium-sulphur battery of any one in claim 4, it is characterized in that: the bottom of described storage sodium pipe (9) and described bursting tube (8) is rectangular base.
6. according to a kind of sodium-sulphur battery described in claim 1 to 5, it is characterized in that: the end face of described bursting tube (8) is higher than the end face of described electrolyte ceramics pipe (4).
7. according to the described a kind of sodium-sulphur battery of any one in claim 1 to 5, it is characterized in that: in described storage sodium pipe (9) and described cathode chamber (100), all be filled with protective gas.
8. a kind of sodium-sulphur battery according to claim 7 is characterized in that: the protective gas in described storage sodium pipe (9) and described cathode chamber (100) is nitrogen.
9. a kind of sodium-sulphur battery according to claim 8 is characterized in that: the nitrogen in described cathode chamber (100) is decomposed to form by sodium azide is irreversible.
10. a kind of sodium-sulphur battery according to claim 1, it is characterized in that: described anodal sealing device (6) comprises L shaped becket (61), flute profile becket (62) and top metal ring (63);
Described L shaped becket (61) is divided into vertical section (611) and horizontal segment (612), the bottom surface of the end face of described horizontal segment (612) and described ceramic insulation ring (3) is fixed, and the lateral surface of the medial surface of described vertical section (611) and described ceramic insulation ring (3) is fixed; The lateral surface of described vertical section (611) separates with the medial surface of described shell (1), and the end face of described vertical section (611) is higher than the end face of described ceramic insulation ring (3);
The bottom surface of described flute profile becket (62) is higher than the end face of described ceramic insulation ring (3), described flute profile becket (62) is provided with inner ring cell wall (621) and outer ring cell wall (622), described inner ring cell wall (621) is higher than described outer ring cell wall (622), the medial surface of the vertical section (611) of the lateral surface of described outer ring cell wall (622) and described L shaped becket (61) is fixed, and the end face of the vertical section (611) of the end face of described outer ring cell wall (622) and described L shaped becket (61) is contour;
Described top metal ring (63) connects the lateral surface of inner ring cell wall (621) of described flute profile becket (62) and the medial surface of described shell (1), and the end face of the end face of described top metal ring (63) and described flute profile becket (62) inner ring cell wall (621) and the end face of described shell (1) are contour; The end face of described top metal ring (63) is upper outside a cannelure (631).
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104409732A (en) * | 2014-12-11 | 2015-03-11 | 上海宝钢磁业有限公司 | Preparation method for lithium iron phosphate material by adopting mixed iron source |
| CN104466290A (en) * | 2014-12-01 | 2015-03-25 | 上海电气钠硫储能技术有限公司 | Disassembling method of sodium-sulfur battery with faults |
| CN106784449A (en) * | 2016-12-14 | 2017-05-31 | 上海电气钠硫储能技术有限公司 | A kind of metal to ceramic sealing technique for sodium-sulphur battery production |
| CN106785106A (en) * | 2017-03-13 | 2017-05-31 | 上海电气钠硫储能技术有限公司 | A kind of controllable cathode of sodium-sulfur cell of air pressure |
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| CN104466290A (en) * | 2014-12-01 | 2015-03-25 | 上海电气钠硫储能技术有限公司 | Disassembling method of sodium-sulfur battery with faults |
| CN104466290B (en) * | 2014-12-01 | 2016-06-15 | 上海电气钠硫储能技术有限公司 | A kind of fault sodium-sulphur battery disassembling method |
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| CN106784449A (en) * | 2016-12-14 | 2017-05-31 | 上海电气钠硫储能技术有限公司 | A kind of metal to ceramic sealing technique for sodium-sulphur battery production |
| CN106784449B (en) * | 2016-12-14 | 2019-04-12 | 上海电气钠硫储能技术有限公司 | A kind of metal to ceramic sealing technique for sodium-sulphur battery production |
| CN106785106A (en) * | 2017-03-13 | 2017-05-31 | 上海电气钠硫储能技术有限公司 | A kind of controllable cathode of sodium-sulfur cell of air pressure |
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| CN103500855B (en) | 2016-01-20 |
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