JPH09180756A - Battery jar for sodium-sulfur battery - Google Patents
Battery jar for sodium-sulfur batteryInfo
- Publication number
- JPH09180756A JPH09180756A JP7341211A JP34121195A JPH09180756A JP H09180756 A JPH09180756 A JP H09180756A JP 7341211 A JP7341211 A JP 7341211A JP 34121195 A JP34121195 A JP 34121195A JP H09180756 A JPH09180756 A JP H09180756A
- Authority
- JP
- Japan
- Prior art keywords
- battery
- sodium
- base material
- sulfur
- stainless steel
- 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.)
- Granted
Links
Classifications
-
- 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
- Secondary Cells (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はナトリウム−硫黄電
池の電槽に関するもので、さらに詳しく言えば、ナトリ
ウムイオン伝導性の固体電解質管の開口部にα−アルミ
ナリングが接合され、前記α−アルミナリングの一方の
面に熱圧接合した陰極蓋によって前記固体電解質管の内
部に陰極室が形成され、前記α−アルミナリングの他方
の面に熱圧接合した陽極蓋とこの陽極蓋に溶接された電
槽とによって前記固体電解質管の外部に陽極室が形成さ
れてなるナトリウム−硫黄電池の電槽の、陽極活物質に
対する耐腐食性の向上に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a battery cell for sodium-sulfur batteries, and more specifically, an α-alumina ring is bonded to the opening of a sodium ion conductive solid electrolyte tube to form the above-mentioned α-alumina. A cathode chamber was formed inside the solid electrolyte tube by means of a cathode lid thermocompression bonded to one surface of the ring, and an anode lid thermocompression bonded to the other surface of the α-alumina ring was welded to this anode lid. The present invention relates to improvement of corrosion resistance of a sodium-sulfur battery battery case in which an anode chamber is formed outside the solid electrolyte tube by the battery case, to the anode active material.
【０００２】[0002]
【従来の技術】ナトリウム−硫黄電池の電槽は、その陽
極室に陽極活物質としての硫黄や放電によって生成する
多硫化ナトリウムが収納されるため、これらの物質に対
する耐腐食性を有したもので、しかも陽極集電体として
も作用しうる電導性を有した材料が用いられている。2. Description of the Related Art A battery cell of a sodium-sulfur battery contains sulfur as an anode active material and sodium polysulfide generated by electric discharge in its anode chamber, and therefore has a corrosion resistance against these materials. Moreover, a material having electrical conductivity that can also function as an anode current collector is used.
【０００３】上記した条件を満足する材料としては、炭
素鋼またはステンレス鋼を母材とし、その表面にクロム
を熱拡散させてクロム−鉄合金層を形成したもの、すな
わち前記炭素鋼またはステンレス鋼の表面をクロマイズ
加工したものが知られている。As a material satisfying the above-mentioned conditions, carbon steel or stainless steel is used as a base material, and chromium is thermally diffused on the surface of the base material to form a chromium-iron alloy layer, that is, the above-mentioned carbon steel or stainless steel. It is known that the surface is chromized.
【０００４】[0004]
【発明が解決しようとする課題】上記した炭素鋼または
ステンレス鋼の表面をクロマイズ加工したものは、表面
の外側に炭化クロム層が、内側にクロム−鉄合金層が形
成され、外側の炭化クロム層は多孔性のＣｒ23Ｃ6 が主
体であり、その厚みも数ミクロンであるため、剥離しや
すく、長期間にわたって硫黄や多硫化ナトリウムに対す
る耐腐食性を維持することが困難であるという問題があ
った。The surface of the above-mentioned carbon steel or stainless steel that has been chromized has a chromium carbide layer formed on the outside of the surface and a chromium-iron alloy layer formed on the inside, and the chromium carbide layer on the outside. Is mainly composed of porous Cr 23 C 6 and its thickness is also several microns, so it is easy to peel off, and it is difficult to maintain corrosion resistance to sulfur and sodium polysulfide for a long period of time. It was
【０００５】[0005]
【課題を解決するための手段】上記課題を解決するた
め、本発明は、ナトリウムイオン伝導性の固体電解質管
の開口部にα−アルミナリングが接合され、前記α−ア
ルミナリングの一方の面に陰極蓋が熱圧接合され、この
陰極蓋によって密閉される陰極室と、前記α−アルミナ
リングの他方の面に陽極蓋が熱圧接合され、この陽極蓋
によって密閉される陽極室とを有するナトリウム−硫黄
電池の電槽において、前記電槽が０．２〜０．６重量％
の炭素を含有するフェライト系ステンレス鋼を母材と
し、このフェライト系ステンレス鋼の表面にクロマイズ
加工することによってクロム−鉄合金層が形成されたも
のであることを特徴とするものである。In order to solve the above-mentioned problems, according to the present invention, an α-alumina ring is bonded to an opening of a sodium ion conductive solid electrolyte tube, and one surface of the α-alumina ring is bonded to the α-alumina ring. Sodium having a cathode chamber which is thermocompression bonded to the cathode cover and which is sealed by the cathode cover, and an anode chamber which is thermocompression bonded to the other face of the α-alumina ring and which is sealed by the anode cover. -In the battery case of the sulfur battery, the battery case is 0.2 to 0.6% by weight.
The carbon-containing ferritic stainless steel is used as a base material, and the chromium-iron alloy layer is formed by subjecting the surface of this ferritic stainless steel to chromizing.
【０００６】[0006]
【発明の実施の形態】以下、本発明をその実施の形態に
基づいて説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described based on its embodiments.
【０００７】本発明の特徴は、陽極集電体を兼ねる電槽
が０．２〜０．６重量％の炭素を含有するフェライト系
ステンレス鋼を母材とし、このフェライト系ステンレス
鋼の表面にクロマイズ加工することによってクロム−鉄
合金層が形成されるようにしたものであり、表面の外側
に形成される炭化クロム層がＣｒ23Ｃ6 より緻密なＣｒ
7 Ｃ3 を主体とするもので、しかもその厚みも十ミクロ
ン程度までになるようにしたことである。A feature of the present invention is that a battery serving as an anode current collector uses a ferritic stainless steel containing 0.2 to 0.6% by weight of carbon as a base material, and the surface of the ferritic stainless steel is chromized. A chromium-iron alloy layer is formed by processing, and the chromium carbide layer formed on the outside of the surface is a Cr denser than Cr 23 C 6.
7 C 3 is mainly used, and the thickness is set to about 10 microns.
【０００８】[0008]
【実施例１】本発明のナトリウム−硫黄電池の電槽に用
いるフェライト系ステンレス鋼母材として、炭素の含有
率が０．２４％、クロムの含有率が１８．１％、珪素の
含有率が０．１７％、マンガンの含有率が０．３２％で
ある母材Ａ、炭素の含有率が０．４２％、クロムの含有
率が１７．５％、珪素の含有率が０．２２％、マンガン
の含有率が０．２９％である母材Ｂ、炭素の含有率が
０．５４％、クロムの含有率が１７．９％、珪素の含有
率が０．２６％、マンガンの含有率が０．３８％である
母材Ｃを準備するとともに、比較のために炭素の含有率
が０．０２％、珪素の含有率が０．２２％、マンガンの
含有率が０．３８％である炭素鋼母材Ｄ、炭素の含有率
が０．０２％、クロムの含有率が１７．８％、珪素の含
有率が０．２４％、マンガンの含有率が０．２８％であ
る低炭素フェライト系ステンレス鋼母材Ｅを準備し、そ
れぞれをクロマイズ加工用合剤としての３０〜８０％の
クロム粉末、０．５〜２．０％の塩化アンモニウム粉
末、２０〜５０％のアルミナ粉末とともに鉄製の箱の中
に封入し、約１１７０℃の水素気流中で数時間加熱した
後、約１２００℃の温度下で数分間加熱し、その後急冷
することによってクロマイズ加工した。Example 1 As a ferritic stainless steel base material used in the battery case of the sodium-sulfur battery of the present invention, the carbon content is 0.24%, the chromium content is 18.1%, and the silicon content is 0.17%, base material A having a manganese content of 0.32%, carbon content of 0.42%, chromium content of 17.5%, silicon content of 0.22%, Base material B having a manganese content of 0.29%, carbon content of 0.54%, chromium content of 17.9%, silicon content of 0.26%, manganese content of A base material C having a content of 0.38% was prepared, and carbon having a carbon content of 0.02%, a silicon content of 0.22%, and a manganese content of 0.38% for comparison. Steel base material D, carbon content 0.02%, chromium content 17.8%, silicon content 0.24%, A low carbon ferritic stainless steel base material E having a gangan content of 0.28% is prepared, and each of them is 30 to 80% chromium powder as a mixture for chromizing, and 0.5 to 2.0%. It is enclosed in an iron box together with ammonium chloride powder and 20 to 50% alumina powder, heated in a hydrogen stream at about 1170 ° C for several hours, then heated at a temperature of about 1200 ° C for several minutes, and then rapidly cooled. Chromized.
【０００９】こうして得られた各母材について、光学顕
微鏡および電子線マイクロアナライザーで表面の外側に
形成される炭化クロム層の厚みおよびそのうちのＣｒ7
Ｃ3の厚みを調査し、結果を表１に示す。With respect to each of the base materials thus obtained, the thickness of the chromium carbide layer formed on the outside of the surface with an optical microscope and an electron microanalyzer, and the Cr 7
The thickness of C 3 was investigated and the results are shown in Table 1.
【００１０】[0010]
【表１】 [Table 1]
【００１１】表１から、母材中の炭素の含有率が大きい
ものほど形成される炭化クロム層の厚みが大きくなるこ
とがわかる。From Table 1, it can be seen that the larger the carbon content in the base material, the larger the thickness of the formed chromium carbide layer.
【００１２】[0012]
【実施例２】次に、前述の如くクロマイズ加工した各母
材を、ナトリウム−硫黄電池の陽極で生成する多硫化ナ
トリウムの中で最も腐食力の強いＮａ2 Ｓ3 とともにパ
イレックスガラス中に真空封入し、３５０℃の温度下で
１０００時間保存して耐腐食を調査し、結果を表２に示
す。[Embodiment 2] Next, each base material that has been chromized as described above is vacuum-encapsulated in Pyrex glass together with Na 2 S 3, which has the strongest corrosive power among sodium polysulfide generated at the anode of a sodium-sulfur battery. Then, it was stored at a temperature of 350 ° C. for 1000 hours to investigate corrosion resistance, and the results are shown in Table 2.
【００１３】[0013]
【表２】 [Table 2]
【００１４】表２から、本発明のナトリウム−硫黄電池
の電槽に用いるフェライト系ステンレス鋼母材はいずれ
も耐腐食性にすぐれていることがわかる。なお、耐腐食
性の調査は炭素鋼母材Ｄの腐食量を１００として他の母
材の腐食量を相対比較することによって行った。It can be seen from Table 2 that all the ferritic stainless steel base materials used in the battery case of the sodium-sulfur battery of the present invention have excellent corrosion resistance. The corrosion resistance was investigated by setting the corrosion amount of the carbon steel base material D to 100 and comparing the corrosion amounts of the other base materials relative to each other.
【００１５】上記した各実施例において、炭素の含有率
が０．６重量％を越えると、電槽に加工する際に割れを
生じることがあるため、０．６重量％以下にするのが好
ましい。In each of the above-mentioned examples, if the carbon content exceeds 0.6% by weight, cracks may occur during processing into a battery case. Therefore, it is preferable that the content be 0.6% by weight or less. .
【００１６】また、上記した各実施例で用いたフェライ
ト系ステンレス鋼には、本発明の目的を達成するうえで
支障のない他の成分を不純物として含有してもよいこと
は言うまでもない。It goes without saying that the ferritic stainless steel used in each of the above-mentioned examples may contain other components as impurities which do not hinder the achievement of the object of the present invention.
【００１７】[0017]
【発明の効果】上記した如く、本発明は、炭素の含有率
を０．２〜０．６重量％としたフェライト系ステンレス
鋼を母材とし、このフェライト系ステンレス鋼の表面に
クロマイズ加工することによって長期間にわたって硫黄
や多硫化ナトリウムに対する耐腐食性を維持することが
できるので、陽極集電体を兼ねる電槽の耐腐食性を向上
させることができ、ナトリウム−硫黄電池の長寿命化を
図ることができる。As described above, according to the present invention, a ferritic stainless steel having a carbon content of 0.2 to 0.6% by weight is used as a base material, and the surface of this ferritic stainless steel is subjected to chromizing. Since it is possible to maintain corrosion resistance to sulfur and sodium polysulfide over a long period of time, it is possible to improve the corrosion resistance of the battery cell that also serves as the anode current collector, and to extend the life of the sodium-sulfur battery. be able to.
Claims (1)
の開口部にα−アルミナリングが接合され、前記α−ア
ルミナリングの一方の面に陰極蓋が熱圧接合され、この
陰極蓋によって密閉される陰極室と、前記α−アルミナ
リングの他方の面に陽極蓋が熱圧接合され、この陽極蓋
によって密閉される陽極室とを有するナトリウム−硫黄
電池の電槽において、前記電槽が０．２〜０．６重量％
の炭素を含有するフェライト系ステンレス鋼を母材と
し、このフェライト系ステンレス鋼の表面にクロマイズ
加工することによってクロム−鉄合金層が形成されたも
のであることを特徴とするナトリウム−硫黄電池の電槽1. An α-alumina ring is bonded to an opening of a sodium ion conductive solid electrolyte tube, and a cathode lid is thermocompression bonded to one surface of the α-alumina ring, and the cathode lid is hermetically sealed. A sodium-sulfur battery case having a cathode chamber and an anode chamber thermocompression bonded to the other surface of the α-alumina ring, and the anode chamber being sealed by the anode chamber, wherein the battery chamber is 0.2 ~ 0.6% by weight
Of a ferritic stainless steel containing carbon as a base material, and a chrome-iron alloy layer is formed on the surface of this ferritic stainless steel by chromizing. Tank
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34121195A JP3209066B2 (en) | 1995-12-27 | 1995-12-27 | Battery case for sodium-sulfur battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34121195A JP3209066B2 (en) | 1995-12-27 | 1995-12-27 | Battery case for sodium-sulfur battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09180756A true JPH09180756A (en) | 1997-07-11 |
| JP3209066B2 JP3209066B2 (en) | 2001-09-17 |
Family
ID=18344244
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP34121195A Expired - Fee Related JP3209066B2 (en) | 1995-12-27 | 1995-12-27 | Battery case for sodium-sulfur battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3209066B2 (en) |
-
1995
- 1995-12-27 JP JP34121195A patent/JP3209066B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP3209066B2 (en) | 2001-09-17 |
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