JPH02144858A - Sodium-sulfur battery - Google Patents
Sodium-sulfur batteryInfo
- Publication number
- JPH02144858A JPH02144858A JP63299189A JP29918988A JPH02144858A JP H02144858 A JPH02144858 A JP H02144858A JP 63299189 A JP63299189 A JP 63299189A JP 29918988 A JP29918988 A JP 29918988A JP H02144858 A JPH02144858 A JP H02144858A
- Authority
- JP
- Japan
- Prior art keywords
- solid electrolyte
- covers
- anode
- battery
- electrolyte tube
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- BNOODXBBXFZASF-UHFFFAOYSA-N [Na].[S] Chemical compound [Na].[S] BNOODXBBXFZASF-UHFFFAOYSA-N 0.000 title claims description 9
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 24
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000002093 peripheral effect Effects 0.000 claims description 4
- 229910001415 sodium ion Inorganic materials 0.000 claims description 2
- 238000003466 welding Methods 0.000 abstract description 5
- 239000011149 active material Substances 0.000 abstract description 4
- 238000005452 bending Methods 0.000 abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- 229910052742 iron Inorganic materials 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- 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 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分計
本発明はナトリウム−硫黄電池に関するもので、さらに
詳しく言えばその安全性向上に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to sodium-sulfur batteries, and more particularly to improving their safety.
従来技術とその問題点
す） リウムー硫黄電池は、陰極活物質としてのナトリ
ウムと、陽極活物質としての硫黄とをｒ−アル之すの如
きナトリウムイオン伝導性の固体電解質管により分離さ
せてなる完全密閉構造の高温型二次電池である。Prior art and its problems) A lithium-sulfur battery is a complete battery in which sodium as a cathode active material and sulfur as an anode active material are separated by a sodium ion conductive solid electrolyte tube such as r-aluminum. This is a high-temperature secondary battery with a sealed structure.
このようなナトリウム−硫黄電池の従来の構造を第２図
により説明する。固体電解質管１の上端にα−アルミナ
リング２がガラス半田接合され、このα−アルミナリン
グ２の上面に陰極１１３か、下面に陽極蓋４がそれぞれ
熱圧接合されている。前記陰極蓋３１Ｃは陰極端子５が
溶接されるとともに、その中央部を貫通して陰極集電体
としての陰極バイブロが溶接され、その下方は前記固体
電解質管１内に挿入されている。The conventional structure of such a sodium-sulfur battery will be explained with reference to FIG. An α-alumina ring 2 is bonded to the upper end of the solid electrolyte tube 1 by glass soldering, and a cathode 113 is bonded to the upper surface of the α-alumina ring 2, and an anode cover 4 is bonded to the lower surface of the α-alumina ring 2 by heat pressure. The cathode terminal 5 is welded to the cathode lid 31C, and a cathode vibro serving as a cathode current collector is welded through the center of the cathode lid 31C, and the lower part thereof is inserted into the solid electrolyte tube 1.
この固体電解質管１内には金属繊維７が配され、約１５
０℃の保温下において前記陰極バイブロより固体電解質
管１内を排気した後、同温度で溶融させたす） ＩＪウ
ム８が真空充填され、充填後論極端子５の上端は封止さ
れる。このような陰極室構成体は、円筒形の硫黄成型体
１０が内挿された陽極集電体を兼ねる電槽９内に挿入さ
れるとともに、その上端は前記陽極１ｆ４と真空溶接さ
れて完全密閉される。Metal fibers 7 are disposed inside this solid electrolyte tube 1, and approximately 15
After evacuating the inside of the solid electrolyte tube 1 from the cathode vibrotube while keeping the temperature at 0° C., IJum 8 is vacuum filled and the upper end of the logic terminal 5 is sealed. Such a cathode chamber structure is inserted into a battery case 9 which also serves as an anode current collector into which a cylindrical sulfur molded body 10 is inserted, and its upper end is vacuum welded to the anode 1f4 to completely seal it. be done.
上記の如ぎ構造のナトリウム−硫黄電池では、作動温度
の５５０℃まで昇温する過程で硫黄成型体１０が熱膨張
し、固体電解束管１が曲げ応力を受ける。ところが、固
体電解質管１はガラス半田によってα−アル之ナリング
２１ｃ強固に接合されているため、前記曲げ応力を受け
てガラス半田接合部で固体電解質管１が破損することが
あった。このように固体電解質管が破損すると、硫黄と
す） リウムとが直接反応し、内圧が上昇して陰１ｉ１
ｆ３がα−アｐｉナリング２の上面から剥離し、活物質
などが飛散して正常な電池も破損させて大規模な事故に
なるという問題点があった。In the sodium-sulfur battery having the above structure, the sulfur molded body 10 thermally expands during the process of increasing the temperature to the operating temperature of 550° C., and the solid electrolytic flux tube 1 is subjected to bending stress. However, since the solid electrolyte tube 1 is firmly joined to the α-aluminum ring 21c by glass solder, the solid electrolyte tube 1 may be damaged at the glass solder joint due to the bending stress. When the solid electrolyte tube is damaged in this way, it reacts directly with sulfur and lithium, increasing the internal pressure and producing negative
There was a problem in that f3 peeled off from the upper surface of the α-api ring 2, and the active material etc. were scattered, damaging even normal batteries and causing a large-scale accident.
発明の目的
本発明は上記欠点を解消するもので、＠極補助蓋と電槽
とを柔軟性をもたせて溶接するとともに、陰極蓋の上方
で前記陽極補助蓋に溶接された陽極蓋を溶接することに
より、破損時の活物質の飛散を防止するものである◇
発明の構成
本発明のナトリウム−硫黄電池は、α−アルミナリング
の上面に熱圧接合された陰極蓋の上方に、α−アルミナ
リングの外周面に沿って上方へ延長させた陽極蓋を位置
させるとともに、この陽極蓋を陽極補助蓋を介して電槽
に溶接したものである。OBJECTS OF THE INVENTION The present invention solves the above-mentioned drawbacks by welding the auxiliary electrode cover and the battery case with flexibility, and by welding the anode cover welded to the auxiliary anode cover above the cathode cover. ◇ Structure of the Invention The sodium-sulfur battery of the present invention has an α-alumina ring placed above the cathode lid that is thermo-pressure bonded to the top surface of the α-alumina ring. An anode cover extending upward is positioned along the outer peripheral surface of the ring, and this anode cover is welded to the battery case via an anode auxiliary cover.
実施例
以下実施例により説明する。第１図は本発明のす） Ｉ
Ｊウムー硫黄電池の断面図で、第２図と共通する部分に
は同じ符号を付している。第１図において、固体電解質
管１は、その上部が開放された外径４６ｍ、内径４０１
ｍ、長さ４００ｍ１１１のβ′−アルミナからなり、そ
の上部開放端に外径５６鰭、内径４０ｆｉ、厚さ１５ｆ
ｉのα−アルミナリング２がガラス半田接合される。こ
のα−ア／ｋｌナリング２の上面には、厚さ０．５簡の
アルミニウム被覆鉄からなる第１の陰極蓋３−１が熱圧
接合され、その先端を一旦固体電解質管１内に垂下させ
てから、厚さ０．５鰭のり田ム拡散鉄からなる第２の陰
極蓋３−２により上方に延長される。このように固体電
解質管１内に垂下させることにより、固体電解質管１に
柔軟性をもたせることができ、ナトリウム８が上昇して
熱圧接合部の腐食防止の効果を有する。−方、前記α−
アルミナリング２の下面には、厚さ０．５調のアルミニ
ウム被覆鉄からなる第１の陽極蓋４−１が熱圧接合され
、この第１の陽極蓋４−１からα−アルミナリング２の
外周面に沿って上方に厚さＱ、５ｍ、内径６６誌のクロ
ム拡散鉄からなる第２の＠極蓋・４−２を延長させ、さ
らに前記第１の陰極蓋３−１の上方をおおうように厚さ
０．５簡のアルミニウム拡散鉄からなる第３の陽極蓋４
−３を溶接する。このような構成体の固体電解質管１内
に金属繊維７として、繊維径約１０〜２０μｍの鉄繊維
を気孔率９４．５％された陰極端子５が溶接され、その
先端から固体電解質管１内に溶融させたす） ＩＪウム
８を真空充填する。さらに、前記第５の＠極蓋４−５を
、厚さが０．５簡のクロム拡散鉄からなり、−部にベロ
ーズ部が設けられた第１の陽極補助蓋４Ａ−１と厚さ０
．５簡のアルミニウム拡散鉄からなる第２の陽極補助蓋
４Ａ−２とを介して電槽９に溶接し、前記電ＷＩ９内に
底部から円筒状の硫黄成形体１０を挿入して底蓋１１を
嵌合させて完成電池とする。なお、第１の陰極ＭＳ−１
、第２の陰極蓋３−２および第１の陽極ｌ！４−１、第
２の陽極蓋４−２、第５の陽極蓋４−３の外表面には珪
酸ナトリウムとアルミナとを主成分とする電気絶縁材を
焼結、被覆している。EXAMPLES The present invention will be explained below using examples. Figure 1 shows the present invention) I
This is a cross-sectional view of a Jumu sulfur battery, and parts common to those in FIG. 2 are given the same reference numerals. In FIG. 1, the solid electrolyte tube 1 has an open upper part with an outer diameter of 46 m and an inner diameter of 401 m.
It is made of β'-alumina with a length of 400 m and a length of 111 mm, and an outer diameter of 56 fins, an inner diameter of 40 fi, and a thickness of 15 f at its upper open end.
The α-alumina ring 2 of i is joined by glass solder. A first cathode lid 3-1 made of aluminum-coated iron with a thickness of 0.5 strips is heat-pressure bonded to the upper surface of this α-A/kl nut ring 2, and its tip is temporarily suspended inside the solid electrolyte tube 1. Then, it is extended upward by a second cathode cover 3-2 made of diffusion iron with a thickness of 0.5 fins. By hanging the solid electrolyte tube 1 in this manner, the solid electrolyte tube 1 can be made flexible, and the sodium 8 will rise, thereby having the effect of preventing corrosion of the thermopressure joint. -, the above α-
A first anode cover 4-1 made of aluminum-coated iron with a thickness of 0.5 is thermo-pressure bonded to the lower surface of the alumina ring 2. A second cathode lid 4-2 made of chromium-diffused iron with a thickness Q of 5 m and an inner diameter of 66 mm is extended upward along the outer peripheral surface, and further covers the upper part of the first cathode lid 3-1. The third anode cover 4 is made of aluminum diffused iron with a thickness of 0.5 mm.
-Weld 3. A cathode terminal 5 made of iron fibers with a fiber diameter of about 10 to 20 μm and a porosity of 94.5% is welded into the solid electrolyte tube 1 of such a structure as the metal fiber 7, and the cathode terminal 5 is welded as the metal fiber 7 into the solid electrolyte tube 1 from its tip. Vacuum-filled with IJum 8. Further, the fifth @electrode lid 4-5 is connected to a first anode auxiliary lid 4A-1, which is made of chromium-diffused iron and has a thickness of 0.5 mm and has a bellows portion at the negative part.
．． It is welded to the battery case 9 via the second anode auxiliary lid 4A-2 made of 5 pieces of aluminum diffused iron, and the cylindrical sulfur molded body 10 is inserted from the bottom into the battery case WI9, and the bottom lid 11 is closed. They are mated together to form a completed battery. Note that the first cathode MS-1
, second cathode lid 3-2 and first anode l! 4-1, the outer surfaces of the second anode lid 4-2 and the fifth anode lid 4-3 are sintered and coated with an electrical insulating material whose main components are sodium silicate and alumina.
このような本発明電池と第２図のような従来電池とをそ
れぞれ１〇七ルずつ製作し、３５０℃で電池電圧が急降
下するまで過充電する電池破壊試験と室温＝３５０℃の
ヒートサイクル試験とを行った。なお、１０サイクルの
ヒートサイクル試験で破損しなかった電池については、
破損するまで電池破壊試験を行い、結果を表−１に示す
。表−１において、分子は陰極蓋が剥離、脱落した電池
数、分母は破損電池数を示す。A battery of the present invention and a conventional battery as shown in Figure 2 were manufactured in 107 cells each, and were subjected to a battery destruction test in which the batteries were overcharged at 350°C until the battery voltage suddenly dropped, and a heat cycle test at room temperature = 350°C. I did this. For batteries that were not damaged in the 10-cycle heat cycle test,
A battery destructive test was conducted until the battery broke, and the results are shown in Table 1. In Table 1, the numerator indicates the number of batteries whose cathode lids were peeled off or fell off, and the denominator indicates the number of damaged batteries.
表 −
表−１から本発明電池は、第１の陽極補助蓋４ム−１の
一部に設けたベローズ部により、また第１の陰極蓋３−
１と第２の陰極蓋５−２との溶接部を固体電解質管１内
に画工させたことにより、固体電解質管１の曲゛げ応力
が緩和でき、と−トサイクル試験に十分耐えうろことが
わかる。また、陰極蓋の剥馬、脱落も防止できるので、
活物質の飛散も防止することができる。Table - Table 1 shows that the battery of the present invention has a bellows section provided in a part of the first anode auxiliary cover 4-1, and a first cathode cover 3-1.
By welding the welded portion between the first and second cathode lids 5-2 into the solid electrolyte tube 1, the bending stress of the solid electrolyte tube 1 can be alleviated, and the solid electrolyte tube 1 can withstand a full cycle test. I understand. It also prevents the cathode lid from peeling off or falling off.
It is also possible to prevent the active material from scattering.
発明の効果
実施例において詳述した如く、本発明電池は破損時の安
全性を向上させることができ、ヒートサイクル試験にも
十分耐えうるものである。Effects of the Invention As detailed in the Examples, the battery of the present invention can improve safety in the event of breakage and can sufficiently withstand heat cycle tests.
第１図は本発明電池の断面図、第２図は従来電池の断面
図である。FIG. 1 is a sectional view of the battery of the present invention, and FIG. 2 is a sectional view of a conventional battery.
Claims (3)
α−アルミナリングが接合され、このα−アルミナリン
グの上面に陰極蓋が、下面に陽極蓋が熱圧接合され、か
つこの陽極蓋に溶接されて前記固体電解質管を下方から
被包する電槽を有し、前記固体電解質管内を陰極室、固
体電解質管と前記電槽との間隙を陽極室とするナトリウ
ム−硫黄電池において、前記陽極蓋をα−アルミナリン
グの外周面に沿って上方へ延長させ、かつこの陽極蓋の
外周面に沿って一端が電槽に溶接された陽極補助蓋を上
方へ延長させ、前記陽極蓋と陽極補助蓋の他端とを陰極
蓋の上方で溶接したことを特徴とするナトリウム−硫黄
電池。(1) An α-alumina ring is bonded to the upper end of a solid electrolyte tube that conducts sodium ions, and a cathode cover is heat-pressure bonded to the top surface of this α-alumina ring, and an anode cover is bonded to the bottom surface of the α-alumina ring, and welded to this anode cover. In the sodium-sulfur battery, the battery has a battery case that covers the solid electrolyte tube from below, the inside of the solid electrolyte tube is a cathode chamber, and the gap between the solid electrolyte tube and the battery case is an anode chamber, is extended upward along the outer peripheral surface of the α-alumina ring, and an anode auxiliary lid, one end of which is welded to the battery case, is extended upward along the outer peripheral surface of the anode lid, and the anode lid and the anode auxiliary lid are A sodium-sulfur battery characterized in that the other end is welded above the cathode cover.
蓋の一部にベローズ部が設けられていることを特徴とす
る請求項第１項記載のナトリウム−硫黄電池。(2) The sodium-sulfur battery according to claim 1, wherein a bellows portion is provided on the top of the battery case or a part of the anode auxiliary lid welded to the battery case.
蓋の一部が固体電解質管内に垂下されていることを特徴
とする請求項第１項記載のナトリウム−硫黄電池。(3) The sodium-sulfur battery according to claim 1, characterized in that a part of the cathode cover bonded by thermo-pressure to the upper surface of the α-alumina ring is suspended within the solid electrolyte tube.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63299189A JPH02144858A (en) | 1988-11-25 | 1988-11-25 | Sodium-sulfur battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63299189A JPH02144858A (en) | 1988-11-25 | 1988-11-25 | Sodium-sulfur battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02144858A true JPH02144858A (en) | 1990-06-04 |
Family
ID=17869295
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63299189A Pending JPH02144858A (en) | 1988-11-25 | 1988-11-25 | Sodium-sulfur battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02144858A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5962160A (en) * | 1995-07-17 | 1999-10-05 | Hitachi, Ltd. | Sodium-sulfur battery, and a battery system using same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57180084A (en) * | 1981-04-09 | 1982-11-05 | Bbc Brown Boveri & Cie | Chargeable battery cell |
| JPS6248665B2 (en) * | 1979-11-30 | 1987-10-15 | Toyo Soda Mfg Co Ltd | |
| JPH0675408A (en) * | 1992-08-26 | 1994-03-18 | Fuji Xerox Co Ltd | Electrophotographic sensitive body |
-
1988
- 1988-11-25 JP JP63299189A patent/JPH02144858A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6248665B2 (en) * | 1979-11-30 | 1987-10-15 | Toyo Soda Mfg Co Ltd | |
| JPS57180084A (en) * | 1981-04-09 | 1982-11-05 | Bbc Brown Boveri & Cie | Chargeable battery cell |
| JPH0675408A (en) * | 1992-08-26 | 1994-03-18 | Fuji Xerox Co Ltd | Electrophotographic sensitive body |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5962160A (en) * | 1995-07-17 | 1999-10-05 | Hitachi, Ltd. | Sodium-sulfur battery, and a battery system using same |
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