JPH0278162A - Sodium-sulfur battery - Google Patents
Sodium-sulfur batteryInfo
- Publication number
- JPH0278162A JPH0278162A JP63228158A JP22815888A JPH0278162A JP H0278162 A JPH0278162 A JP H0278162A JP 63228158 A JP63228158 A JP 63228158A JP 22815888 A JP22815888 A JP 22815888A JP H0278162 A JPH0278162 A JP H0278162A
- Authority
- JP
- Japan
- Prior art keywords
- electrolyte tube
- solid electrolyte
- alumina
- sodium
- powder
- 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 11
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 32
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000843 powder Substances 0.000 claims abstract description 19
- 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 10
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 10
- 239000011734 sodium Substances 0.000 claims abstract description 10
- 229910000679 solder Inorganic materials 0.000 claims abstract description 10
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 239000003792 electrolyte Substances 0.000 claims abstract 3
- 239000000835 fiber Substances 0.000 claims description 5
- 239000008187 granular material Substances 0.000 claims description 5
- 239000000565 sealant Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims 1
- 239000011261 inert gas Substances 0.000 abstract description 3
- 238000007789 sealing Methods 0.000 abstract 3
- 239000003795 chemical substances by application Substances 0.000 abstract 2
- 239000002075 main ingredient Substances 0.000 abstract 2
- 239000006104 solid solution Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 abstract 1
- 239000011593 sulfur Substances 0.000 description 9
- 229910052717 sulfur Inorganic materials 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000003466 welding Methods 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
-
- 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
- H01M50/183—Sealing members
- H01M50/186—Sealing members characterised by the disposition of the sealing members
-
- 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
- H01M50/183—Sealing members
- H01M50/184—Sealing members characterised by their shape or structure
-
- 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
- H01M50/183—Sealing members
- H01M50/19—Sealing members characterised by the material
- H01M50/191—Inorganic material
-
- 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
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明はナトリウム−硫黄電池に関するもので、さらに
詳しく言えばナトリウムイオン伝導性固体電解質管とα
−アルミナリングとの接合構造に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a sodium-sulfur battery, and more specifically, a sodium ion-conducting solid electrolyte tube and an α
- This relates to the bonding structure with the alumina ring.
従来技術とその問題点
ナシ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β′−アルミナの如
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。Conventional technology and its problems Nasilium-sulfur batteries have a completely sealed structure 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 β'-alumina. It is a high-temperature secondary battery.
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がガラス半田接合駕 され、このα−アルミ
ナリング２の上面に陰極ｌ！３が、下面に５１１極１ｉ
４がそれぞれ熱圧接合されている。前記陰極蓋３には陰
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 glass soldered to the upper end of the solid electrolyte tube 1, and a cathode 1 is placed on the upper surface of the α-alumina ring 2. 3 has 511 poles 1i on the bottom surface
4 are bonded together under heat and pressure. A cathode terminal 5 is welded to the cathode lid 3, and a cathode vibro serving as a cathode current collector is welded through the center of the cathode lid 3, 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ＩＩ繊維７が配され、約１
５０℃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ナトリウム
８が真空充填され、充填後陰極端子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１
０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蓋４と真空溶接されて
完全密閉される。Gold II fibers 7 are disposed inside this solid electrolyte tube 1, and about 1
After the inside of the solid electrolyte tube 1 is evacuated from the cathode vibro while keeping the temperature at 50° C., sodium 8 molten at the same temperature is vacuum filled, and after filling, the upper end of the cathode terminal 5 is sealed. Such a cathode chamber structure consists of a cylindrical sulfur molded body 1
0 is inserted into a battery case 9 which also serves as an anode current collector, and its upper end is vacuum welded to the anode cover 4 to be completely sealed.
上記の如き構造のナトリウム−硫黄電池では、作動温度
の３５０℃まで昇温する過程で硫黄成型体１０が熱膨張
し、固体電解質管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ａ−アルミナリング
２に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が破損するという欠
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 350° C., and the solid electrolyte tube 1 is subjected to bending stress. However, since the solid electrolyte tube 1 is firmly joined to the a-alumina ring 2 by glass solder, there is a drawback that the solid electrolyte tube 1 is damaged at the glass solder joint due to the bending stress.
発明の目的
本発明は上記欠点を解消するもので、固体電解質管の上
端とα−アルミナリングとの接合を柔軟にすることによ
り、昇温時における固体電解質管の破損の防止を目的と
する。OBJECTS OF THE INVENTION The present invention solves the above-mentioned drawbacks, and aims to prevent breakage of the solid electrolyte tube when the temperature rises by making the connection between the upper end of the solid electrolyte tube and the α-alumina ring flexible.
発明の構成
本発明のす） ＩＪウムー硫黄電池は、固体電解質管の
中央に陰極パイプを挿入し１かつ前記固体電解質管内に
金ＦＩ４１ａ維を充填するとともに、その上方の空間に
耐溶融ナトリウム性粉末または粒体にガラス半田粉末を
混合したものを充填して封口し、前記固体電解質管の上
端なα−アルミナ微粉末と珪酸ナトリウムとを主成分と
する封着剤でａ−アルミナリングに接合してなるもので
ある。Structure of the Invention The IJ Umu sulfur battery according to the present invention includes a cathode pipe inserted into the center of a solid electrolyte tube, and gold FI41a fibers are filled in the solid electrolyte tube, and a molten sodium-resistant powder is filled in the space above the cathode pipe. Alternatively, the granules are filled with a mixture of glass solder powder, sealed, and bonded to the a-alumina ring at the upper end of the solid electrolyte tube using a sealant mainly composed of α-alumina fine powder and sodium silicate. That's what happens.
実施例
以下実施例により説明する。第１図は本発明のナトリウ
ム−硫黄電池の断面図で、第２図と共通するものには同
じ符号を付している。第１図において、固体電解質管１
は外径４６ｗｍ、長す４００謔のβ′−アルミナからな
り、この固体電解質管１の中央にニッケルメッキした銅
製の陰極バイブロ（外径８鰭、内径４−）を挿入し、か
つ前記固体電解質管１内に金属繊維７としての鉄繊維（
ａ維径約１０〜２０Ｐｌを充填するとともに、その上方
の空間に耐溶融ナトリウム性粉末または粒体１１として
のａ−アルミナ粉末または粒体にガラス半田粉末１２を
混合したものを充填し、空気中または不活性ガス中、好
ましくは不活性ガス中で６００℃以上に加熱し、固体電
解質管１の上端と陰極バイブロとを接合して封口する。EXAMPLES The present invention will be explained below using examples. FIG. 1 is a cross-sectional view of the sodium-sulfur battery of the present invention, and parts common to those in FIG. 2 are given the same reference numerals. In Figure 1, solid electrolyte tube 1
is made of β'-alumina with an outer diameter of 46 wm and a length of 400 mm, and a nickel-plated copper cathode vibro (outer diameter of 8 fins, inner diameter of 4 mm) is inserted into the center of the solid electrolyte tube 1, and the solid electrolyte Iron fibers as metal fibers 7 are placed inside the tube 1 (
A-fiber diameter of about 10 to 20 Pl is filled, and the space above it is filled with a-alumina powder or granules mixed with glass solder powder 12 as molten sodium resistant powder or granules 11, and then heated in the air. Alternatively, it is heated to 600° C. or higher in an inert gas, preferably an inert gas, and the upper end of the solid electrolyte tube 1 and the cathode vibro are joined and sealed.
一方、ａ−アルミナリング２の上面に陰極蓋３を、下面
に陽極１１ｉ４を熱圧接合し、前記固体電解質管１の上
端をこのａ−アルミナリング２に内挿させ、間隙にａ−
アルミナ微粉末と珪酸ナトリウムとを主成分とする封着
剤１５の溶液を塗布し、約１００℃で１時間乾燥させた
後、約２５０℃で１〜２時間固溶化熱処理を行った。次
に、前記陰極バイブロの上端に陰Ｗ端子５を螺合させ、
該陰極端子５と陰極蓋３とを溶接した後、約１５０℃に
加熱して陰極端子５および陰極バイブロを介して固体電
解質管１内を真空排気した後、同温度で溶融させたナト
リウム８を真空充填し、充填後陰極端子５の上端を封止
して陰極室を密閉する。こうして得られた陰極室構成体
は、円筒形の硫黄成型体１０が内挿されたＳＷ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
陽極蓋４と真空溶接されて完全密閉される。On the other hand, the cathode cover 3 is bonded to the upper surface of the a-alumina ring 2, and the anode 11i4 is bonded to the lower surface of the a-alumina ring 2, the upper end of the solid electrolyte tube 1 is inserted into the a-alumina ring 2, and the a-alumina ring 2 is inserted into the gap.
A solution of a sealant 15 containing fine alumina powder and sodium silicate as main components was applied, dried at about 100°C for 1 hour, and then subjected to solution heat treatment at about 250°C for 1 to 2 hours. Next, the negative W terminal 5 is screwed onto the upper end of the negative electrode vibro,
After welding the cathode terminal 5 and the cathode cover 3, the solid electrolyte tube 1 is heated to about 150° C. and the inside of the solid electrolyte tube 1 is evacuated through the cathode terminal 5 and the cathode vibro, and then the sodium 8 melted at the same temperature is heated. Vacuum filling is performed, and after filling, the upper end of the cathode terminal 5 is sealed to seal the cathode chamber. The cathode chamber structure thus obtained is inserted into a battery case 9 which also serves as an SW current collector into which a cylindrical sulfur molded body 10 is inserted, and its upper end is vacuum welded to the anode cover 4. Completely sealed.
上記の如き構造の本発明電池と第２図の如き構造の従来
電池とをそれぞれ１〇七ルずつ製作し、ヒートサイクル
′試験（室温２５℃＃作動温度３５０℃、昇降温速度：
約２００℃／Ｈｒ、）を行ったところ、表−１のような
結果が得られた。A battery of the present invention having the structure as described above and a conventional battery having the structure as shown in FIG.
200° C./Hr), the results shown in Table 1 were obtained.
表 −１
表−１から、従来電池ではＳＯサイクルまでで全セルが
破損に至ったのに対し、本発明電池では３０サイクルま
でで破損に至ったのは２セルであったことから、本発明
電池はヒートサイクルに対する耐久性がすぐれているこ
とがわかるＯ
前記試験に供した電池を解体したところ、従来電池は全
セルが固体電解質管１とα−アルミナリンダ２とのガラ
ス半田接合部で破損していたのに対し、本発明電池は２
セルとも固体電解質管１の下部が破損していたことがわ
かり、ガラス半田接合部はヒートサイクルによって破損
しやすいことが判明した。すなわち、本発明電池はガラ
ス半田に代えてα−アルミナ微粉末と珪酸ナトリウムと
を主成分とする封着剤１６に用いたため、接合部の柔軟
性を向上させることができなことになる。ただ、そのた
めに陽極室の硫黄が接合部から陰極室側へ滲出し、硫黄
とす） ＩＪウムとが直接反応したり、電池の寿命が短
かくなることが考えられるが、固体電解質管１の上端に
耐浴融す） ＩＪウム性粉末または粒体１１とガラス半
田粉末１２とを混合したものを充填して封口しているた
め、滲出した硫黄とナトリウムとが直接反応するといっ
た事故の発生は防止でき、電池の寿命が短かくなること
もない。Table 1 From Table 1, it can be seen that in the conventional battery, all cells were damaged up to the SO cycle, whereas in the battery of the present invention, only 2 cells were damaged up to the 30th cycle. It can be seen that the battery has excellent durability against heat cycles. When the battery used in the above test was disassembled, all cells of the conventional battery were damaged at the glass soldered joint between the solid electrolyte tube 1 and the α-alumina cylinder 2. In contrast, the battery of the present invention had a
It was found that the lower part of the solid electrolyte tube 1 in both cells was damaged, and it was found that the glass solder joint was easily damaged by heat cycles. That is, in the battery of the present invention, the flexibility of the joint cannot be improved because the sealant 16 mainly consists of α-alumina fine powder and sodium silicate instead of glass solder. However, because of this, the sulfur in the anode chamber leaks from the joint to the cathode chamber side and becomes sulfur. Since the upper end is filled with IJ aluminum powder or a mixture of granules 11 and glass solder powder 12 and sealed, accidents such as direct reaction between leached sulfur and sodium are prevented. This can be prevented and the battery life will not be shortened.
発明の効果
実施例において詳述した如く、本発明のナトリウム−硫
黄電池は、固体電解質管とα−アルｔナリングとの接合
部の柔軟性を向上させたことにより、ヒートサイクルに
対する耐久性を高めることができ、電池の寿命の点にお
いてもすぐれているので、工業的価値の高いものである
。Effects of the Invention As detailed in the Examples, the sodium-sulfur battery of the present invention has improved durability against heat cycles by improving the flexibility of the joint between the solid electrolyte tube and the α-Altna ring. It is of high industrial value because it has excellent battery life.
第１図は本発明のナトリウム−硫黄電池の断面図、第２
図は従来のナトリウム−硫黄電池の断面図である。Figure 1 is a sectional view of the sodium-sulfur battery of the present invention, Figure 2 is a cross-sectional view of the sodium-sulfur battery of the present invention;
The figure is a cross-sectional view of a conventional sodium-sulfur battery.
Claims (1)
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筒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、前記固体電解質管の中央に陰極パイプ
が挿入され、かつ該管内に金属繊維が充填されるととも
に、その上方の空間に耐溶融ナトリウム性粉末または粒
体にガラス半田粉末を混合したものが充填されて封口さ
れ、かつ前記固体電解質管の上端とα−アルミナリング
とがα−アルミナ微粉末と珪酸ナトリウムとを主成分と
する封着剤で接合されてなることを特徴とするナトリウ
ム−硫黄電池。An α-alumina ring is bonded to the upper end of a sodium ion-conducting solid electrolyte tube, a cathode cover is heat-pressure bonded to the top surface of the α-alumina ring, and an anode cover is bonded to the bottom surface of the α-alumina ring, and is welded to the anode cover. In a sodium-sulfur battery that has a battery case that encloses a cylindrical 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. A cathode pipe is inserted in the center, and the pipe is filled with metal fibers, and the space above the cathode pipe is filled with a melt-resistant sodium powder or a mixture of granules and glass solder powder to seal it. A sodium-sulfur battery characterized in that the upper end of a solid electrolyte tube and an α-alumina ring are joined with a sealant whose main components are α-alumina fine powder and sodium silicate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63228158A JPH0278162A (en) | 1988-09-12 | 1988-09-12 | Sodium-sulfur battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63228158A JPH0278162A (en) | 1988-09-12 | 1988-09-12 | Sodium-sulfur battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0278162A true JPH0278162A (en) | 1990-03-19 |
Family
ID=16872139
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63228158A Pending JPH0278162A (en) | 1988-09-12 | 1988-09-12 | Sodium-sulfur battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0278162A (en) |
-
1988
- 1988-09-12 JP JP63228158A patent/JPH0278162A/en active Pending
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