CN103123988A - Sodium-sulfur battery - Google Patents
Sodium-sulfur battery Download PDFInfo
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- CN103123988A CN103123988A CN2012105376407A CN201210537640A CN103123988A CN 103123988 A CN103123988 A CN 103123988A CN 2012105376407 A CN2012105376407 A CN 2012105376407A CN 201210537640 A CN201210537640 A CN 201210537640A CN 103123988 A CN103123988 A CN 103123988A
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- sodium
- pipe
- ceramic electrolyte
- storage sodium
- sulphur battery
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- 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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Abstract
The invention discloses a sodium-sulfur battery in the field of energy storage. The sodium-sulfur battery comprises a ceramic electrolyte tube and a sodium storage tube which is sleeved inside the ceramic electrolyte tube, wherein the bottom surface of the sodium storage tube is provided with at least one through hole, a cathode chamber of the sodium-sulfur battery is formed between the sodium storage tube and the ceramic electrolyte tube, the bottom surface of the sodium storage tube is flat, a sodium storage tube hemispherical body is arranged right below the sodium storage tube, a gap is reserved between the sodium storage tube and the sodium storage tube hemispherical body, a fiber buffer layer is arranged between the bottom surfaces of the sodium storage tube hemispherical body and the inner wall of the ceramic electrolyte tube, and the fiber buffer layer is free from wetting liquid sodium. The sodium-sulfur battery has beneficial effects that under the situation that the through hole in the bottom surface of the sodium storage tube can be effectively sealed, the requirement on the dimensional precision of the ceramic electrolyte tube can be lowered, and the manufacturing cost of the sodium-sulfur battery can be reduced.
Description
Technical field
The present invention relates to a kind of sodium-sulphur battery in energy storage field.
Background technology
The core key part of sodium-sulphur battery is β "-Al
2O
3The ceramic electrolyte pipe of making, sodium-sulphur battery cycle life depends on the quality of ceramic electrolyte pipe to a great extent.In case the ceramic electrolyte pipe has micro-crack or breaks, Liquid Sodium will directly contact and occur vigorous reaction with liquid sulfur, and temperature reaches as high as 2000 ℃, and the metal partss such as storage sodium pipe in the instant melting sodium-sulphur battery cause the leakage of Liquid Sodium and liquid sulfur.
Existing sodium-sulphur battery is mainly by metal shell, ceramic electrolyte pipe and storage sodium pipe form, and Liquid Sodium and liquid sulfur are served as active material in addition, and metal shell is as electric current collection body and storing liquid sulphur, storage sodium pipe is the reservoir vessel of Liquid Sodium, and the flow velocity of restriction Liquid Sodium.The safeguard construction of existing sodium-sulphur battery is mainly the difference of utilizing between ceramic electrolyte pipe and storage sodium tube swelling coefficient, when sodium-sulfur battery temperature raises, the degrees of expansion of storage sodium pipe is greater than the degrees of expansion of ceramic electrolyte pipe, the lateral wall of storage sodium pipe and the gap between the ceramic electrolyte inside pipe wall are closed, Liquid Sodium in storage sodium pipe no longer flows in this gap, limited the reaction of Liquid Sodium and liquid sulfur, in case but temperature reduces, Liquid Sodium and liquid sulfur will continue reaction, and the fatigue strength of storage sodium pipe reduces.The bottom surface of existing ceramic electrolyte pipe and storage sodium pipe bottom surface, all hemispheric, all there is certain tolerance in their circularity, simultaneously, also there is certain deviation in the length of ceramic electrolyte pipe, like this, lateral wall and the gap between the ceramic electrolyte inside pipe wall of storage sodium pipe are difficult to effectively be sealed, the bottom surface of storing up simultaneously the sodium pipe also produces compression to the bottom surface of ceramic electrolyte inside pipe wall, in case the ceramic electrolyte pipe breaks, storage sodium pipe damages, and a large amount of Liquid Sodium directly flows out from the through hole of storage sodium pipe bottom, with liquid sulfur generation vigorous reaction.Therefore the dimension precision requirement of prior art ceramic electrolyte pipe size is very high, has increased the manufacturing cost of sodium-sulphur battery.
Summary of the invention
The objective of the invention is provides a kind of sodium-sulphur battery in order to overcome the deficiencies in the prior art, and it can reduce the dimension precision requirement to ceramic electrolyte pipe size in the situation that the through hole of storage sodium pipe bottom surface obtains effectively sealing, reduces the manufacturing cost of sodium-sulphur battery.
A kind of technical scheme that realizes above-mentioned purpose is: a kind of sodium-sulphur battery ceramic electrolyte pipe, comprise the ceramic electrolyte pipe and be socketed in the interior storage sodium pipe of described ceramic electrolyte pipe, the bottom surface of described storage sodium pipe is provided with at least one through hole, form the cathode chamber of sodium-sulphur battery between described storage sodium pipe and described ceramic electrolyte pipe
The bottom surface of described storage sodium pipe is flat, under described storage sodium pipe, be provided with storage sodium pipe hemisphere, leave the gap between described storage sodium pipe and described storage sodium pipe hemisphere, be provided with fiber buffer between the bottom surface of described storage sodium pipe hemisphere and described ceramic electrolyte inside pipe wall, this fiber buffer liquid towards sodium is nonwetting.
Further, in described cathode chamber, be provided with the metal fiber cloth that is close on described ceramic electrolyte pipe madial wall and the metal forming that is close to described metal fiber cloth surface, form some and the axial parallel capillary gap of described ceramic electrolyte pipe between the madial wall of described metal fiber cloth and described ceramic electrolyte pipe, described metal fiber cloth liquid towards sodium is wetting.
Further, be provided with guiding mechanism between described storage sodium pipe hemisphere and described storage sodium pipe, described guiding mechanism comprises a dividing plate that is positioned at described storage sodium pipe, and the guiding parts that connects described dividing plate and described storage sodium pipe hemisphere end face.
Further, described fiber buffer is made by carbon fiber.
Further, described metal fiber cloth is made by 304 stainless steels or 316 stainless steels, and described metal forming is made by austenitic stainless steel, and described metal fiber cloth and described metal forming are fixed together by laser spot welding.
Further, the sidewall of described storage sodium pipe is provided with bellows structure.
Adopted the technical scheme of a kind of sodium-sulphur battery of the present invention, the bottom surface that is the storage sodium pipe of sodium-sulphur battery is flat, and be provided with some through holes, be provided with storage sodium pipe hemisphere under storage sodium pipe, leave the gap between the bottom surface of storage sodium pipe and storage sodium pipe hemisphere, be provided with the technical scheme of the non-wetted fiber buffer of liquid towards sodium between the bottom surface of storage sodium pipe hemisphere and ceramic electrolyte inside pipe wall.Its technique effect is: the first, in the situation that the through hole of storage sodium pipe bottom surface can obtain effective shutoff, reduce the dimension precision requirement to ceramic electrolyte pipe size, and reduce the manufacturing cost of sodium-sulphur battery.The second, reduced storage sodium pipe to the compression of ceramic electrolyte inside pipe wall bottom surface, reduced the probability of ceramic electrolyte tracheal rupture, even ceramic electrolysis tracheal rupture also can reduce the flow velocity of Liquid Sodium, control the reaction of Liquid Sodium and liquid sulfur.
Description of drawings
Fig. 1 is the structural representation of a kind of sodium-sulphur battery of the present invention.
Fig. 2 is the enlarged diagram of A part in Fig. 1.
Embodiment
See also Fig. 1 and Fig. 2, the present inventor be in order to understand technical scheme of the present invention better, below by embodiment particularly, and is described in detail by reference to the accompanying drawings:
Present sodium-sulphur battery mainly comprises: negative lug 41, negative pole seal cover 42, upper becket 43, dead ring 44, lower becket 45, metallic cylinder 46, anodal seal cover 47, ceramic electrolyte pipe 1 and storage sodium pipe 2.Metallic cylinder 46, ceramic electrolyte pipe 1 and storage sodium pipe 2 socket successively from outside to inside, form the R2 of anode chamber of sodium-sulphur battery between metallic cylinder 46, ceramic electrolyte pipe 1 and anodal seal cover 47, form the cathode chamber R1 of sodium-sulphur battery between storage sodium pipe 2 and ceramic electrolyte pipe 1, negative pole seal cover 42 will store up the negative electrode active material in sodium pipe 2 and cathode chamber R1, be the Liquid Sodium sealing, upper becket 43 is fixed with the circumference of negative pole seal cover 42 bottom surfaces.Lower becket 45 is with the R2 of the anode chamber sealing of sodium-sulphur battery, and lower becket 45 is fixing by Laser Welding and metallic cylinder 46.The end face of dead ring 44 and underrun thermocompression bonding and upper becket 43 and lower becket 45 are fixing respectively, and dead ring 44 is fixed by lateral wall and the end face of glass sealing and ceramic electrolyte pipe 1, and ceramic electrolyte pipe 1 becomes one with metallic cylinder 46 thus.The negative lug 41 that is located at negative pole seal cover 42 end face centers is used for collected current and carries out being connected between sodium-sulphur battery and sodium-sulphur battery.Be filled with the porous fibre felt in the R2 of anode chamber, its effect storing liquid sulphur.The present invention is doing improvement to the safeguard construction between storage sodium pipe 2 and ceramic electrolyte pipe 1 on the basis of present sodium-sulphur battery.
A kind of sodium-sulphur battery of the present invention comprises ceramic electrolyte pipe 1 and is socketed in the interior storage sodium pipe 2 of ceramic electrolyte pipe 1 that form the gap of annular between storage sodium pipe 2 and ceramic electrolyte pipe 1, this gap is the cathode chamber R1 of sodium-sulphur battery.
The bottom surface of storage sodium pipe 2 is flat, the bottom surface of storage sodium pipe 2 is provided with at least one through hole 21, be provided with storage sodium pipe hemisphere 3 under storage sodium pipe 2, leave the gap between the bottom surface of storage sodium pipe hemisphere 3 and storage sodium pipe 2, the Liquid Sodium of storing up like this in sodium pipe 2 can be along through hole 21 outflows that are positioned at storage sodium pipe 2 bottom surfaces.Be provided with fiber buffer 11 between the bottom surface of storage sodium pipe hemisphere 3 and the bottom surface of ceramic electrolyte pipe 1 inwall, these fiber buffer 11 liquid towards sodium are nonwetting.When ceramic electrolyte pipe 1 lost efficacy, the temperature of sodium-sulphur battery raise, because ceramic electrolyte pipe mostly 1 is β "-aluminium oxide makes, and storing up sodium pipe mostly 2 is that stainless steel is made.Therefore store up the linear expansion coefficient of sodium pipe 2 much larger than the linear expansion coefficient of ceramic electrolyte pipe 1, the gap of therefore storing up between sodium pipe 2 and storage sodium pipe hemisphere 3 reduces gradually, until the end face of storage sodium pipe hemisphere 3 will be positioned at through hole 21 sealings of storage sodium pipe 2 bottom surfaces, Liquid Sodium no longer flows out.
Simultaneously, be provided with the non-wetted fiber buffer 11 of liquid towards sodium between bottom surface due to the bottom surface of storing up sodium pipe hemisphere 3 and ceramic electrolyte pipe 1 inwall, the bottom surface that guarantees storage sodium pipe hemisphere 3 does not contact with the bottom rigidity of ceramic electrolyte pipe 1, make the bottom of ceramic electrolyte pipe 1 not participate in reaction, what is more important, by the gap between storage sodium pipe 2 and storage sodium pipe hemisphere 3, and fiber buffer 11, when shutoff through hole 21, prevented the bottom of ceramic electrolyte pipe 1 and thoroughly broken from the pressure that stores up sodium pipe hemisphere 3 because be subject to.Guaranteed the safety of sodium-sulphur battery, even ceramic electrolysis tube 1 breaks, fiber buffer 11 also can reduce the flow velocity of Liquid Sodium, controls the reaction of Liquid Sodium and liquid sulfur.In the present embodiment, fiber buffer 11 is made by carbon fiber.
See also Fig. 1, embodiment 2 is the further improvement on embodiment 1 basis, and improvements are to be provided with the metal fiber cloth 12 that is close on ceramic electrolyte pipe 1 madial wall in cathode chamber R1, and the metal forming 13 that is close to metal fiber cloth 12 surfaces.Metal fiber cloth 12 liquid towards sodium are wetting.Metal forming 13 still has elasticity preferably under 300 ℃.Metal fiber cloth 12 has wetability preferably with Liquid Sodium under 300 ℃, simultaneously because ceramic electrolyte pipe 1 madial wall has certain roundness tolerance, and air spots, metal fiber cloth 12 can make up roundness tolerance and the air spots of ceramic electrolyte pipe 1 madial wall.The elastic reaction of complexed metal paper tinsel 13 again, form capillary gap (not shown) some and ceramic electrolyte pipe 1 axially parallel between metal fiber cloth 12 and ceramic electrolyte pipe 1 madial wall, the capillarity that relies on capillary gap, the liquid level of Liquid Sodium in cathode chamber R1 keeps constant, even like this in discharge latter stage of sodium-sulphur battery, also can guarantee the response area of ceramic electrolyte pipe 1, thereby reduce the polarization resistance of sodium-sulphur battery; On the other hand, capillary gap also can be controlled the flow velocity of Liquid Sodium, during the sidewall generation local damage of ceramic electrolyte pipe 1, can stop a large amount of Liquid Sodium and liquid sulfur moment to react; The fail safe of sodium-sulphur battery is further strengthened.
In the present embodiment, metal fiber cloth 12 is fixed together by ultrasonic spot welding technique with metal forming 13, adopts the purpose of this technique to be to facilitate metal fiber cloth 12 to be close on ceramic electrolyte pipe 1 madial wall.The preferred material of metal fiber cloth 12 is 304 stainless steels or 316 stainless steels, the metallic fiber that is used for establishment metal fiber cloth 12, its diameter is the 8-20 micron, metallic fiber is woven into metal fiber cloth 12 by the nonwoven textile technology, and the porosity of metal fiber cloth 12 is controlled at 70%-90%, and such porosity helps to improve the wetability of metal fiber cloth 12 liquid towards sodium.In the time of 350 ℃, use 304 stainless steels or 316 stainless metal fiber cloths 12, the angle of wetting of itself and Liquid Sodium is about 20 °.Metal forming 13 is by having cold drawn the forming of certain flexible austenitic stainless steel, the thickness 0.05-0.1mm of metal forming 13.Sodium-sulphur battery is under working temperature, and the edge of 13 pairs of metal fiber cloths 12 of metal forming produces pressure, and metal fiber cloth 12 is close on ceramic electrolyte pipe 1 madial wall.
Embodiment 4
Embodiment 4 is the further improvement on embodiment 1, embodiment 2 or embodiment 3, in embodiment 4, the sidewall of storage sodium pipe 2 is provided with bellows structure, store up like this sodium pipe 2 existing certain mechanical strengths, has simultaneously certain deformability, shutoff effectively can be carried out to the through hole 21 of the bottom surface of storage sodium pipe 2 in the bottom surface that guarantees storage sodium pipe hemisphere 3, reduces the requirement to electrolyte ceramics electrolytic tube 1 perpendicularity.
Those of ordinary skill in the art will be appreciated that, above embodiment illustrates the present invention, and be not to be used as limitation of the invention, as long as in connotation scope of the present invention, all will drop in claims scope of the present invention variation, the modification of the above embodiment.
Claims (6)
1. sodium-sulphur battery, comprise ceramic electrolyte pipe (1) and be socketed in the interior storage sodium pipe (2) of described ceramic electrolyte pipe (1), the bottom surface of described storage sodium pipe (2) is provided with at least one through hole (21), form the cathode chamber (R1) of sodium-sulphur battery between described storage sodium pipe (2) and described ceramic electrolyte pipe (1), it is characterized in that:
The bottom surface of described storage sodium pipe (2) is flat, under described storage sodium pipe (2), be provided with storage sodium pipe hemisphere (3), leave the gap between described storage sodium pipe (2) and described storage sodium pipe hemisphere (3), be provided with fiber buffer (11) between the bottom surface of described storage sodium pipe hemisphere (3) and described ceramic electrolyte pipe (1) inwall, this fiber buffer (11) liquid towards sodium is nonwetting.
2. a kind of sodium-sulphur battery according to claim 1, it is characterized in that: in described cathode chamber (R1), be provided with the metal forming (13) that is close to the metal fiber cloth (12) on described ceramic electrolyte pipe (1) madial wall and is close to described metal fiber cloth (12) surface, form the capillary gap of some and described ceramic electrolyte pipe (1) axially parallel between the madial wall of described metal fiber cloth (12) and described ceramic electrolyte pipe (1), described metal fiber cloth (12) liquid towards sodium is wetting.
3. a kind of sodium-sulphur battery according to claim 1 and 2, it is characterized in that: be provided with guiding mechanism (5) between described storage sodium pipe hemisphere (3) and described storage sodium pipe (2), described guiding mechanism (5) comprises a dividing plate (51) that is positioned at described storage sodium pipe (2), and the guiding parts (52) that connects described dividing plate (51) and described storage sodium pipe hemisphere (3) end face.
4. a kind of sodium-sulphur battery according to claim 1 and 2, it is characterized in that: described fiber buffer (11) is made by carbon fiber.
5. a kind of sodium-sulphur battery according to claim 2, it is characterized in that: described metal fiber cloth (12) is made by 304 stainless steels or 316 stainless steels, described metal forming (13) is made by austenitic stainless steel, and described metal fiber cloth (12) is fixed together by laser spot welding with described metal forming (13).
6. a kind of sodium-sulphur battery according to claim 1 and 2, it is characterized in that: the sidewall of described storage sodium pipe (2) is provided with bellows structure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210537640.7A CN103123988B (en) | 2012-12-12 | 2012-12-12 | Sodium-sulfur battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210537640.7A CN103123988B (en) | 2012-12-12 | 2012-12-12 | Sodium-sulfur battery |
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| CN103123988A true CN103123988A (en) | 2013-05-29 |
| CN103123988B CN103123988B (en) | 2015-01-14 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103490102A (en) * | 2013-10-17 | 2014-01-01 | 上海电气钠硫储能技术有限公司 | Positive electrode of sodium-sulfur battery |
| CN103500855A (en) * | 2013-10-17 | 2014-01-08 | 上海电气钠硫储能技术有限公司 | Sodium-sulfur cell |
| CN103531856A (en) * | 2013-10-17 | 2014-01-22 | 上海电气钠硫储能技术有限公司 | Cathode of sodium-sulfur cell |
| CN105390756A (en) * | 2015-11-23 | 2016-03-09 | 中国东方电气集团有限公司 | Safe sodium-sulfur cell |
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| CN201829577U (en) * | 2010-10-09 | 2011-05-11 | 秦磊 | Multitube sodium-sulfur battery device capable of filling sulfur into solid electrolyte tube |
| CN202423500U (en) * | 2011-12-16 | 2012-09-05 | 日本碍子株式会社 | Sodium-sulfur cell |
| CN202423404U (en) * | 2011-12-16 | 2012-09-05 | 日本碍子株式会社 | Solid electrolyte pipe for sodium-sulfur battery and sodium-sulfur battery |
| CN202996994U (en) * | 2012-12-12 | 2013-06-12 | 上海电气钠硫储能技术有限公司 | Sodium-sulfur battery |
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2012
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| GB1508803A (en) * | 1974-07-03 | 1978-04-26 | Secretary Industry Brit | Electric batteries |
| CN1037430A (en) * | 1987-12-03 | 1989-11-22 | 克劳赖德·塞兰特电力公司 | Improved alkali metal battery |
| JPH05205775A (en) * | 1991-08-29 | 1993-08-13 | Abb Patent Gmbh | Electrochemical storage battery |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103490102A (en) * | 2013-10-17 | 2014-01-01 | 上海电气钠硫储能技术有限公司 | Positive electrode of sodium-sulfur battery |
| CN103500855A (en) * | 2013-10-17 | 2014-01-08 | 上海电气钠硫储能技术有限公司 | Sodium-sulfur cell |
| CN103531856A (en) * | 2013-10-17 | 2014-01-22 | 上海电气钠硫储能技术有限公司 | Cathode of sodium-sulfur cell |
| CN103500855B (en) * | 2013-10-17 | 2016-01-20 | 上海电气钠硫储能技术有限公司 | A kind of sodium-sulphur battery |
| CN103531856B (en) * | 2013-10-17 | 2016-04-20 | 上海电气钠硫储能技术有限公司 | A kind of cathode of sodium-sulfur cell |
| CN105390756A (en) * | 2015-11-23 | 2016-03-09 | 中国东方电气集团有限公司 | Safe sodium-sulfur cell |
| CN105390756B (en) * | 2015-11-23 | 2018-01-12 | 中国东方电气集团有限公司 | A kind of safe sodium-sulphur battery |
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| CN103123988B (en) | 2015-01-14 |
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Effective date of registration: 20200907 Address after: Room 1201, no.1346 Gonghe Xin Road, Jing'an District, Shanghai 200070 Patentee after: Shanghai Electric Enterprise Development Co., Ltd Address before: 201815 Shanghai Jiading District City Jia Zhu Road No. 1997 Patentee before: SHANGHAI ELECTRIC SODIUM SULFUR ENERGY STORAGE TECHNOLOGY Co.,Ltd. |