JP3325238B2 - Anode and cathode fittings for sodium-sulfur battery and method of joining these to insulating ring - Google Patents
Anode and cathode fittings for sodium-sulfur battery and method of joining these to insulating ringInfo
- Publication number
- JP3325238B2 JP3325238B2 JP03193799A JP3193799A JP3325238B2 JP 3325238 B2 JP3325238 B2 JP 3325238B2 JP 03193799 A JP03193799 A JP 03193799A JP 3193799 A JP3193799 A JP 3193799A JP 3325238 B2 JP3325238 B2 JP 3325238B2
- Authority
- JP
- Japan
- Prior art keywords
- fitting
- anode
- cathode
- insulating ring
- metal
- 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.)
- Expired - Lifetime
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)
Description
【０００１】[0001]
【発明の属する技術分野】 本発明は、ナトリウム−硫
黄電池の陽極金具及び陰極金具並びにこれらと絶縁リン
グとの接合方法に関する。[0001] The present invention relates to an anode and a cathode of a sodium-sulfur battery and a method of joining these to an insulating ring.
【０００２】[0002]
【従来の技術】 ナトリウム−硫黄電池は、一方に陰極
活物質である溶融金属ナトリウム、他方には陽極活物質
である溶融硫黄を配し、両者をナトリウムイオンに対し
て選択的な透過性を有するβ−アルミナ固体電解質で隔
離し、３００〜３５０℃で作動させる高温二次電池であ
る。2. Description of the Related Art A sodium-sulfur battery has molten metal sodium as a cathode active material on one side and molten sulfur as an anode active material on the other side, and both have selective permeability to sodium ions. This is a high-temperature secondary battery operated at 300 to 350 ° C. isolated by a β-alumina solid electrolyte.
【０００３】 このようなナトリウム−硫黄電池は、例
えば図８に示すように、カーボンフェルト等に含浸され
た溶融硫黄Ｓを収容する円筒状の陽極容器７と、陽極容
器７内部にあって、溶融金属ナトリウムＮａを収容し、
ナトリウムイオンＮａ+を選択的に透過させる機能を有
する有底円筒状の固体電解質管９とを有する。Such a sodium-sulfur battery includes, as shown in FIG. 8, for example, a cylindrical anode container 7 containing molten sulfur S impregnated in carbon felt or the like, and a molten metal inside the anode container 7. Containing metallic sodium Na,
A bottomed cylindrical solid electrolyte tube 9 having a function of selectively transmitting sodium ions Na + .
【０００４】 固体電解質管９はα−アルミナ製の絶縁
リング５及び陽極金具１を介して陽極容器７と結合され
ている。陽極金具１は、円筒部と円筒部下端に設けられ
たフランジ部とを有する。絶縁リング５は、この陽極金
具１の円筒部内に挿入され、その絶縁リング５の下端面
に対して陽極金具１のフランジ部の上面が熱圧接合され
ている。また、絶縁リング５の上端面には陰極金具３が
熱圧接合され、この陰極金具３に陰極蓋１１が溶接固定
されている。陽極容器７の外周上部と陰極蓋１１の上面
には、それぞれ陽極側端子１３と陰極側端子１５が設け
られている。The solid electrolyte tube 9 is connected to the anode container 7 via an insulating ring 5 made of α-alumina and the anode fitting 1. The anode fitting 1 has a cylindrical portion and a flange provided at the lower end of the cylindrical portion. The insulating ring 5 is inserted into the cylindrical part of the anode fitting 1, and the upper surface of the flange of the anode fitting 1 is hot-press bonded to the lower end surface of the insulating ring 5. A cathode metal fitting 3 is joined to the upper end surface of the insulating ring 5 by heat and pressure, and a cathode lid 11 is fixed to the cathode metal fitting 3 by welding. An anode terminal 13 and a cathode terminal 15 are provided on the outer peripheral upper portion of the anode container 7 and the upper surface of the cathode lid 11, respectively.
【０００５】 このような構造を有するナトリウム−硫
黄電池において、放電時にはナトリウムＮａが、固体電
解質管９をナトリウムイオンとなって透過して、陽極容
器７内の硫黄Ｓ及び外部回路を通ってきた電子と反応し
多硫化ナトリウムを生成する。充電時には放電とは逆に
ナトリウム及び硫黄の生成反応が起こる。[0005] In the sodium-sulfur battery having such a structure, at the time of discharge, sodium Na permeates through the solid electrolyte tube 9 as sodium ions, and sulfur S in the anode container 7 and electrons that have passed through the external circuit. Reacts with to form sodium polysulfide. At the time of charging, a reaction of forming sodium and sulfur occurs in reverse to discharging.
【０００６】 図９は陽極金具及び陰極金具と絶縁リン
グとの接合状態を示す要部拡大図である。陽極金具１
は、円筒部１ａと円筒部１ａの下端から内部方向に張り
出したフランジ部１ｂとを有し、フランジ部１ｂの上面
が絶縁リング５の下端面に熱圧接合されている。また、
陰極金具３は、円筒部３ａと円筒部３ａの外周から外部
方向に張り出したフランジ部３ｂとを有し、フランジ部
３ｂの下面が絶縁リング５の上端面に熱圧接合されてい
る。従来、これらの陽極金具１及び陰極金具３は、何れ
もアルミニウム又はアルミニウム合金のインゴットを、
目的とする金具形状に切削加工することによって得られ
ていた。FIG. 9 is an enlarged view of a main part showing a bonding state between an anode fitting, a cathode fitting, and an insulating ring. Anode fitting 1
Has a cylindrical portion 1a and a flange portion 1b projecting inward from the lower end of the cylindrical portion 1a. The upper surface of the flange portion 1b is hot-pressed to the lower end surface of the insulating ring 5. Also,
The cathode metal fitting 3 has a cylindrical portion 3a and a flange portion 3b projecting outward from the outer periphery of the cylindrical portion 3a, and the lower surface of the flange portion 3b is hot-press bonded to the upper end surface of the insulating ring 5. Conventionally, each of the anode fitting 1 and the cathode fitting 3 is made of an ingot of aluminum or aluminum alloy,
It was obtained by cutting into the desired metal fitting shape.
【０００７】[0007]
【発明が解決しようとする課題】 しかしながら、上記
のようにインゴットから直接切削加工によって作製され
た陽極金具や陰極金具は、その金属組織中に、鋳造時に
インゴット中に形成された粗大結晶がそのまま残存して
いるため、ナトリウム−硫黄電池のように作動時と停止
時の温度差が大きく、かつ腐食性の活物質にさらされる
環境下では、腐食による損傷を受けやすく、このことが
電池寿命を短命化する一因となっていた。However, as described above, in the anode fitting and the cathode fitting made by direct cutting from the ingot, the coarse crystals formed in the ingot at the time of casting remain in the metal structure as they are. Therefore, in an environment such as a sodium-sulfur battery where the temperature difference between operation and shutdown is large, and where the battery is exposed to corrosive active materials, it is easily damaged by corrosion, which shortens the battery life. Was one of the causes.
【０００８】 例えば、陽極金具１では、電池放電時に
生成された多硫化ナトリウムにより円筒部１ａが腐食さ
れ、更にこの腐食部分に陽極容器の熱膨張や熱収縮によ
る繰り返し応力が加わって、短期間のうちに亀裂が生じ
ることがあった。また、陰極金具３では、陰極活物質で
あるナトリウムにより、絶縁リング５との接合部におい
てフランジ部３ｂが浸食され、接合部の気密性が維持で
きなくなったり、接合強度が低下して接合部が剥離した
りすることがあった。For example, in the anode fitting 1, the cylindrical portion 1 a is corroded by sodium polysulfide generated at the time of battery discharge, and the corroded portion is subjected to repeated stress due to thermal expansion and thermal shrinkage of the anode container, so that the corroded portion is short-lived. A crack was sometimes formed. Further, in the cathode fitting 3, the flange 3b is eroded at the joint with the insulating ring 5 by sodium as the cathode active material, and the airtightness of the joint cannot be maintained, or the joint strength is reduced and the joint is reduced. Peeling sometimes occurred.
【０００９】 本発明は、このような従来の事情に鑑み
てなされたものであり、その目的とするところは、多硫
化ナトリウムやナトリウムの存在する腐食環境下おい
て、優れた耐腐食性と疲労耐久性を示し、容易に腐食よ
る損傷を受けないような陽極金具と陰極金具を提供する
ことにある。また、このような陽極金具と陰極金具を絶
縁リングに接合する方法であって、接合部が浸食されに
くく、長期にわたって良好な接合状態が得られるような
接合方法を提供することにある。The present invention has been made in view of such conventional circumstances, and has as its object to provide excellent corrosion resistance and fatigue in a corrosive environment in which sodium polysulfide or sodium is present. An object of the present invention is to provide an anode fitting and a cathode fitting that are durable and are not easily damaged by corrosion. Another object of the present invention is to provide a method for joining such an anode fitting and a cathode fitting to an insulating ring, wherein the joining portion is hardly eroded and a good joining state can be obtained for a long period of time.
【００１０】[0010]
【課題を解決するための手段】 本発明によれば、円筒
部と当該円筒部の下端から内部方向に張り出したフラン
ジ部とを有し、当該フランジ部の上面を絶縁リングの下
端面に熱圧接合して使用されるナトリウム−硫黄電池の
陽極金具であって、当該陽極金具は、金属素材を冷間鍛
造により金具の概略形状に成形した後、これを所定の金
具形状にまで加工することによって得られたものであ
り、少なくとも絶縁リングに熱圧接合するフランジ部の
上面についての前記加工が切削加工にて行われているこ
とを特徴とするナトリウム−硫黄電池の陽極金具、が提
供される。According to the present invention, there is provided a cylindrical portion and a flange portion projecting inward from a lower end of the cylindrical portion, and an upper surface of the flange portion is heat-pressed to a lower end surface of the insulating ring. An anode fitting of a sodium-sulfur battery used by joining, the anode fitting being formed by cold forging a metal material into a rough shape of a metal fitting, and then processing this into a predetermined metal fitting shape. An anode fitting for a sodium-sulfur battery, wherein the anode fitting is obtained, wherein at least the upper surface of the flange portion to be hot-pressure bonded to the insulating ring is subjected to cutting.
【００１１】 また、本発明によれば、円筒部と当該円
筒部の外周から外部方向に張り出したフランジ部とを有
し、当該フランジ部の下面を絶縁リングの上端面に熱圧
接合して使用されるナトリウム−硫黄電池の陰極金具で
あって、当該陰極金具は、金属素材を冷間鍛造により金
具の概略形状に成形した後、これを所定の金具形状にま
で加工することによって得られたものであり、少なくと
も絶縁リングに熱圧接合するフランジ部の下面について
の前記加工が切削加工にて行われていることを特徴とす
るナトリウム−硫黄電池の陰極金具、が提供される。Further, according to the present invention, it has a cylindrical portion and a flange portion projecting outward from an outer periphery of the cylindrical portion, and a lower surface of the flange portion is hot-pressed to an upper end surface of the insulating ring for use. The cathode metal fitting of a sodium-sulfur battery to be obtained, which is obtained by forming a metal material into an approximate shape of a metal fitting by cold forging, and then processing the metal material into a predetermined metal fitting shape. A cathode metal fitting for a sodium-sulfur battery, characterized in that at least the lower surface of the flange portion to be thermally and pressure-bonded to the insulating ring is cut by cutting.
【００１２】 更に、本発明によれば、前記陽極金具の
フランジ部の上面を絶縁リングの下端面に、また、前記
陰極金具のフランジ部の下面を絶縁リングの上端面に同
時に熱圧接合する方法であって、熱圧接合後の陽極金具
のフランジ部及び陰極金具のフランジ部の金属組織中の
結晶粒の粒長が３ｍｍ以下となるように熱圧接合を行う
ことを特徴とするナトリウム−硫黄電池の陽極金具及び
陰極金具と絶縁リングとの接合方法、が提供される。Further, according to the present invention, a method of simultaneously hot-press bonding the upper surface of the flange portion of the anode fitting to the lower end surface of the insulating ring and the lower surface of the flange portion of the cathode fitting to the upper end surface of the insulating ring. Wherein sodium-sulfur is subjected to hot-pressure bonding so that the grain length of crystal grains in the metal structure of the flange portion of the anode fitting and the flange portion of the cathode fitting after the hot-pressure joining is 3 mm or less. A method for joining an anode metal and a cathode metal of a battery to an insulating ring is provided.
【００１３】[0013]
【発明の実施の形態】 本発明の陽極金具は、まず最初
に、金属素材を冷間鍛造によって金具の概略形状に成形
し、その後、これを所定の金具形状にまで加工すること
によって得られたものである。陽極金具の金属素材に
は、従来どおりアルミニウムやアルミニウム合金が用い
られる。この金属素材は、最初の冷間鍛造により、陽極
金具の概略形状が付与されると同時に素材が強加工さ
れ、後の絶縁リングとの熱圧接合時に金属組織が微細化
されて、ナトリウムや多硫化ナトリウムに対する耐腐食
性や疲労耐久性が向上したものとなる。BEST MODE FOR CARRYING OUT THE INVENTION The anode fitting of the present invention is obtained by first forming a metal material into a rough shape of a fitting by cold forging, and then processing it into a predetermined fitting shape. Things. Aluminum or an aluminum alloy is used as a metal material of the anode fitting as before. In this metal material, the initial cold forging gives the general shape of the anode fitting and at the same time, the material is strongly worked, and the metal structure is refined at the time of hot-pressure bonding with the insulating ring, so that the sodium metal and the Corrosion resistance to sodium sulfide and fatigue durability are improved.
【００１４】 図１のように、陽極金具１は、円筒部１
ａと円筒部１ａの下端から内部方向に張り出したフラン
ジ部１ｂとを有しており、このフランジ部１ｂの上面が
絶縁リングの下端面に熱圧接合された状態でナトリウム
−硫黄電池に使用される。なお、図１の例では、円筒部
１ａの上端から外部方向に張り出したフランジ部１ｃが
形成されているが、これは陽極容器との接合（溶接）を
容易にするためのものであり、本発明の陽極金具に必須
のものではない。前記のとおり、本発明の陽極金具は、
金属素材を冷間鍛造にて概略形状に成形した後、これを
図１のような目的とする所定の金具形状にまで加工して
得られるが、少なくとも絶縁リングに熱圧接合するフラ
ンジ部１ｂの上面についての加工は切削加工にて行われ
る。As shown in FIG. 1, the anode fitting 1 includes a cylindrical portion 1
a and a flange portion 1b projecting inward from a lower end of the cylindrical portion 1a. The upper surface of the flange portion 1b is used for a sodium-sulfur battery in a state where the upper surface is hot-pressed to the lower end surface of the insulating ring. You. In the example shown in FIG. 1, a flange portion 1c is formed to protrude outward from the upper end of the cylindrical portion 1a. This is for facilitating joining (welding) with the anode container. It is not essential to the anode fitting of the invention. As described above, the anode fitting of the present invention includes:
After the metal material is formed into a general shape by cold forging, it is processed to a desired metal fitting shape as shown in FIG. 1, and at least the flange portion 1b which is hot-press bonded to the insulating ring is obtained. Processing on the upper surface is performed by cutting.
【００１５】 本発明の陽極金具を作製するための最初
の工程である冷間鍛造による成形は、鍛造型を用いた型
鍛造にて行われるが、この際、鍛造後の離型を容易にす
るために離型材が金属素材若しくは鍛造型に塗布処理さ
れる。したがって、鍛造後の成形体の表面には、離型材
が付着した状態となっているが、この離型材が完全に除
去されず、フランジ部１ｂの上面に残存した状態で絶縁
リングとの熱圧接合が実施されると、良好な接合状態が
得られず、実用に耐えることができない。そこで、少な
くともフランジ部１ｂの上面については、切削加工によ
り加工し、所定形状を付与すると同時に、付着していた
離型材を完全に除去するようにした。The cold forging, which is the first step for manufacturing the anode fitting of the present invention, is performed by die forging using a forging die. In this case, the mold release after forging is facilitated. For this purpose, a release material is applied to a metal material or a forging die. Therefore, although the mold release material is adhered to the surface of the molded body after forging, the mold release material is not completely removed and remains in the upper surface of the flange portion 1b. When the joining is performed, a good joining state cannot be obtained, and the joint cannot be put to practical use. Therefore, at least the upper surface of the flange portion 1b is machined by a cutting process to give a predetermined shape and, at the same time, completely remove the adhered release material.
【００１６】 なお、フランジ部１ｂの上面以外の部分
を、目的とする所定の金具形状にまで加工する方法は特
に限定されず、フランジ部１ｂの上面と同様に切削加工
であってもよいし、他の加工方法により加工されていて
もよい。また、当該部分については、最初の冷間鍛造工
程で目的とする所定の形状まで成形してしまってもよ
い。The method of processing a portion other than the upper surface of the flange portion 1b to a desired predetermined metal fitting shape is not particularly limited, and may be a cutting process like the upper surface of the flange portion 1b. It may be processed by another processing method. In addition, the portion may be formed to a desired predetermined shape in the first cold forging step.
【００１７】 このようにして作製された本発明の陽極
金具１は、冷間鍛造によって金属組織に高ひずみが与え
られ、熱圧接合時の加熱によって金属組織が微細化され
ることにより、従来の切削加工で作製したものに比し
て、多硫化ナトリウムにさらされても腐食されにくく、
疲労耐久性にも優れたものとなるので、陽極容器の熱膨
張や熱収縮に伴う繰り返し応力を受けても、円筒部１ａ
に亀裂等の損傷が生じにくい。また、後述の接合方法に
て説明するように、この陽極金具１を絶縁リングに熱圧
接合したものは、その接合部である陽極金具１のフラン
ジ部１ｂ上面と絶縁リング下端面との接合部において、
フランジ部１ｂが多硫化ナトリウムにより容易に浸食さ
れることはなく、良好な接合状態が長期にわたって維持
される。In the anode fitting 1 of the present invention thus manufactured, a high strain is given to the metal structure by cold forging, and the metal structure is refined by heating at the time of hot-press bonding, so that the conventional metal structure is refined. Compared to those made by cutting, it is less corrosive even when exposed to sodium polysulfide,
Since it also has excellent fatigue durability, the cylindrical portion 1a can be subjected to repeated stress due to thermal expansion and thermal contraction of the anode container.
Hardly cause damage such as cracks. Further, as will be described in a joining method described later, the anode metal fitting 1 which is hot-pressed to the insulating ring is a joint between the upper surface of the flange 1b of the anode metal fitting 1 and the lower end face of the insulating ring. At
The flange portion 1b is not easily eroded by sodium polysulfide, and a good joining state is maintained for a long time.
【００１８】 本発明の陽極金具１は、絶縁リングとの
熱圧接合後において、円筒部１ａの金属組織中の結晶粒
の粒径が３００μｍ以下にまで微細化されることが好ま
しく、２００μｍ以下にまで微細化されることがより好
ましく、１００μｍ以下にまで微細化さることがより一
層好ましい。このように微細化されることにより、円筒
部１ａは耐腐食性と疲労耐久性が向上する。結晶粒の粒
径の制御は、冷間鍛造の際に加工率を制御する（１０％
程度が好ましい）ことによって行うことができる。In the anode fitting 1 of the present invention, the grain size of the crystal grains in the metal structure of the cylindrical portion 1a is preferably reduced to 300 μm or less, preferably 200 μm or less, after the heat and pressure bonding with the insulating ring. It is more preferable that the fineness is reduced to 100 μm or less. By being miniaturized in this manner, the cylindrical portion 1a has improved corrosion resistance and fatigue durability. The control of the grain size of the crystal grains controls the working ratio during cold forging (10%
(Preferably the degree).
【００１９】 また、本発明の陽極金具は、図２に示す
ように、その円筒部１ａが、上方部分と下方部分とで肉
厚が異なる段付き形状を有し、上方部分の肉厚ｔ1に対
して下方部分の肉厚ｔ2が薄肉となるように形成したも
のであってもよい。As shown in FIG. 2, in the anode fitting of the present invention, the cylindrical portion 1a has a stepped shape in which an upper portion and a lower portion have different thicknesses, and the upper portion has a thickness t1. On the other hand, it may be formed such that the thickness t2 of the lower portion becomes thinner.
【００２０】 ナトリウム−硫黄電池は、電池作動時と
停止時の間に温度差があり、停止時の低温状態では、多
硫化ナトリウム又は硫黄が固化し、図８に示す構造のナ
トリウム−硫黄電池において、固体電解質管９と陽極容
器７とが相互に拘束することになる。そして、電池降温
時には、固体電解質管９及び陽極容器７はともに熱収縮
するが、金属である陽極容器７の熱収縮は大きく、この
陽極容器７の収縮が熱収縮の小さい固体電解質管９に抑
制されるため、固体電解質管９と陽極容器７とを結合さ
せている絶縁リング５と陽極金具１との接合部に荷重が
働き、この接合部が損傷することがある。In the sodium-sulfur battery, there is a temperature difference between when the battery is operating and when the battery is stopped. In a low temperature state when the battery is stopped, sodium polysulfide or sulfur solidifies, and in the sodium-sulfur battery having the structure shown in FIG. The electrolyte tube 9 and the anode container 7 are mutually restrained. When the temperature of the battery is lowered, both the solid electrolyte tube 9 and the anode container 7 are thermally contracted. However, the heat contraction of the metal anode container 7 is large, and the contraction of the anode container 7 is suppressed by the solid electrolyte tube 9 having a small heat contraction. Therefore, a load acts on the joint between the insulating ring 5 connecting the solid electrolyte tube 9 and the anode container 7 and the anode fitting 1, and the joint may be damaged.
【００２１】 図２のように、陽極金具１の円筒部１ａ
を段付き形状とすると、熱圧接合による絶縁リング５と
陽極金具１との接合部の強度信頼性が向上し、前記のよ
うに電池降温時の固体電解質管９と陽極容器７の熱収縮
差により接合部に荷重が生じても接合部が損傷しにくく
なる。この理由は定かではないが、薄肉部分を設けるこ
とにより、熱圧接合時の接合治具横からの保持力が向上
し、フランジ部１ｂへのせん断力が減少するためと考え
られる。As shown in FIG. 2, the cylindrical portion 1 a of the anode fitting 1
Has a stepped shape, the strength reliability of the joint between the insulating ring 5 and the anode fitting 1 by the heat and pressure bonding is improved, and the difference in heat shrinkage between the solid electrolyte tube 9 and the anode container 7 when the temperature of the battery is lowered as described above. Therefore, even if a load is applied to the joint, the joint is less likely to be damaged. The reason for this is not clear, but it is considered that the provision of the thin portion improves the holding force from the side of the joining jig during the hot-pressure joining and reduces the shearing force to the flange portion 1b.
【００２２】 なお、従来のようにインゴットから直接
切削加工で作製された陽極金具では、円筒部をこのよう
な段付き形状とした場合、絶縁リングとの接合強度は向
上するものの、電池使用時に応力が集中しやすい、薄肉
部分から厚肉部分へと移行する段差部において、腐食に
よる亀裂が生じやすいため、時として問題となった。こ
れに対して、本発明の陽極金具は、前記のように冷間鍛
造と熱圧接合時の加熱とによる金属組織中の結晶粒の微
細化によって耐腐食性や疲労耐久性を高めてられている
ので、円筒部を段付き形状にしても段差部に容易に亀裂
が生じることはなく、長期の実用にも耐え得る。[0022] In the case of a conventional anode fitting made by direct cutting from an ingot, when the cylindrical portion has such a stepped shape, the joint strength with the insulating ring is improved, but the stress during use of the battery is increased. This is sometimes a problem because cracks due to corrosion are likely to occur at the step portion where the transition from the thin portion to the thick portion is likely to occur. On the other hand, the anode fitting of the present invention has improved corrosion resistance and fatigue durability by refining crystal grains in the metal structure by cold forging and heating during hot-pressure bonding as described above. Therefore, even if the cylindrical portion has a stepped shape, a crack is not easily generated in the step portion, and it can withstand long-term practical use.
【００２３】 次に、本発明の陰極金具について説明す
る。本発明の陰極金具も上記陽極金具と同様に、まず冷
間鍛造により金具の概略形状に成形し、その後、これを
所定の金具形状にまで加工することによって得られたも
のである。この陰極金具の素材には、従来どおりアルミ
ニウムやアルミニウム合金が用いられる。この金属素材
は、最初の冷間鍛造により、陰極金具の概略形状が付与
されると同時に素材が強加工され、後の絶縁リングとの
熱圧接合時に金属組織が微細化されて、ナトリウムや多
硫化ナトリウム対する耐腐食性や疲労耐久性が向上した
ものとなる。Next, the cathode fitting of the present invention will be described. Similarly to the above-mentioned anode metal fitting, the cathode metal fitting of the present invention is obtained by first forming the metal fitting into a rough shape by cold forging, and then processing it into a predetermined metal fitting shape. Aluminum or an aluminum alloy is used as a material of the cathode metal fitting as before. The initial cold forging gives the rough shape of the cathode metal at the same time as the cold forging, and at the same time, the material is strongly worked. Corrosion resistance and fatigue durability against sodium sulfide are improved.
【００２４】 図３のように、陰極金具３は、円筒部３
ａと円筒部３ａの外周から外部方向に張り出したフラン
ジ部３ｂとを有しており、このフランジ部３ｂの下面が
絶縁リングの上端面に熱圧接合された状態でナトリウム
−硫黄電池に使用される。前記のとおり、本発明の陰極
金具は、金属素材を冷間鍛造にて概略形状に成形した
後、これを図３のような目的とする所定の金具形状にま
で加工して得られるが、少なくとも絶縁リングに熱圧接
合するフランジ部３ｂの下面についての当該加工は、研
削加工によりなされたものとなっている。As shown in FIG. 3, the cathode fitting 3 includes a cylindrical portion 3
a and a flange portion 3b projecting outward from the outer periphery of the cylindrical portion 3a, and is used in a sodium-sulfur battery in a state where the lower surface of the flange portion 3b is hot-pressed to the upper end surface of the insulating ring. You. As described above, the cathode metal fitting of the present invention is obtained by forming a metal material into a rough shape by cold forging, and then processing the metal material into a desired metal fitting shape as shown in FIG. The processing on the lower surface of the flange portion 3b to be thermally and pressure-bonded to the insulating ring is performed by grinding.
【００２５】 前記陽極金具と同様に、本発明の陰極金
具の作製においても、冷間鍛造による成形は、鍛造後の
離型を容易にするために離型材が金属素材若しくは鍛造
型に塗布処理されて行われるので、少なくとも絶縁リン
グに熱圧接合するフランジ部３ｂの下面については、切
削加工により加工し、目的とする所定の金具形状を付与
すると同時に、冷間鍛造時に付着した離型材を完全に除
去して、絶縁リングとの良好な接合性が得られるように
している。Similarly to the above-mentioned anode metal fitting, in the production of the cathode metal fitting of the present invention, the forming by cold forging is performed by applying a release material to a metal material or a forging die in order to facilitate the release after forging. Therefore, at least the lower surface of the flange portion 3b to be hot-pressed to the insulating ring is machined by cutting to give a desired predetermined metal fitting shape, and at the same time, completely remove the release material adhered during cold forging. It is removed so that good bonding with the insulating ring can be obtained.
【００２６】 なお、フランジ部３ｂの下面以外の部分
を、目的とする所定の金具形状にまで加工する方法は特
に限定されず、フランジ部３ｂ下面と同様に切削加工で
あってもよいし、他の加工方法により加工されていても
よい。また、当該部分については、最初の冷間鍛造工程
で目的とする所定の形状まで成形してしまってもよい。It should be noted that a method of processing a portion other than the lower surface of the flange portion 3b to a desired predetermined metal fitting shape is not particularly limited, and may be a cutting process like the lower surface of the flange portion 3b. May be processed by the above processing method. In addition, the portion may be formed to a desired predetermined shape in the first cold forging step.
【００２７】 このようにして作製された本発明の陰極
金具３は、冷間鍛造によって金属組織に高ひずみが与え
られ、その後の絶縁リングとの熱圧接合工程における加
熱により金属組織中の結晶粒の粒径が微細化されること
により、従来の切削加工で作製したものに比して、ナト
リウムにさらされても腐食されにくく、疲労耐久性にも
優れたものとなるので、円筒部３ａに腐食による損傷が
生じにくい。また、後述の接合方法にて説明するよう
に、この陰極金具３を絶縁リングに熱圧接合したもの
は、その接合部である陰極金具３のフランジ部３ｂ下面
と絶縁リング上端面との接合部において、フランジ部３
ｂがナトリウムにより容易に浸食されることはなく、良
好な接合状態が長期にわたって維持される。In the thus produced cathode metal fitting 3 of the present invention, a high strain is given to the metal structure by cold forging, and the crystal grains in the metal structure are heated by the subsequent heating and pressure bonding process with the insulating ring. Since the particle size of is smaller than that produced by conventional cutting, it is less susceptible to corrosion even when exposed to sodium and has excellent fatigue durability. Less likely to be damaged by corrosion. Further, as will be described in a joining method to be described later, the cathode metal member 3 which is thermally and pressure-bonded to the insulating ring is a joint between the lower surface of the flange portion 3b of the cathode metal member 3 and the upper end surface of the insulating ring. At the flange 3
b is not easily eroded by sodium, and a good bonding state is maintained for a long time.
【００２８】 本発明の陰極金具３は、絶縁リングとの
熱圧接合後において、円筒部３ａの金属組織中の結晶粒
の粒径が３００μｍ以下にまで微細化されることが好ま
しく、２００μｍ以下にまで微細化されることがより好
ましく、１００μｍ以下にまで微細化されることがより
一層好ましい。このように微細化されることにより、円
筒部３ａは耐腐食性と疲労耐久性が向上する。結晶粒の
粒径の制御は、冷間鍛造の際に加工率を制御する（１０
％程度が好ましい）ことによって行うことができる。In the cathode metal fitting 3 of the present invention, the grain size of the crystal grains in the metal structure of the cylindrical portion 3a is preferably reduced to 300 μm or less, preferably 200 μm or less, after the hot-pressure bonding with the insulating ring. It is more preferable that the size is reduced to 100 μm or less. By being miniaturized in this manner, the cylindrical portion 3a has improved corrosion resistance and fatigue durability. The control of the grain size of the crystal grains controls the working ratio during cold forging (10
% Is preferable).
【００２９】 次に、本発明の接合方法について説明す
る。本発明の接合方法では、前記本発明の陽極金具と陰
極金具とを用い、これらをナトリウム−硫黄電池の絶縁
リングに同時に接合する。絶縁リングに対する陽極金具
と陰極金具との接合には、熱圧接合を用いる。すなわ
ち、図４(ａ)のように、下側接合治具１９上にセットさ
れた陽極金具１の円筒部１ａにα−アルミナからなる絶
縁リング５を挿入してフランジ部１ｂ上に載置し、更に
絶縁リング５の上面に陰極金具３を載置する。なお、陽
極金具１のフランジ部１ｂ上面と絶縁リング５下端面と
の間、及び陰極金具３のフランジ部３ｂ下面と絶縁リン
グ５上端面との間には、金属ロウ材が介在されている。Next, the joining method of the present invention will be described. In the joining method according to the present invention, the anode metal fitting and the cathode metal fitting according to the present invention are used, and these are simultaneously bonded to an insulating ring of a sodium-sulfur battery. Hot pressure bonding is used for joining the anode and cathode fittings to the insulating ring. That is, as shown in FIG. 4A, the insulating ring 5 made of α-alumina is inserted into the cylindrical portion 1a of the anode fitting 1 set on the lower joining jig 19 and placed on the flange portion 1b. Then, the cathode fitting 3 is placed on the upper surface of the insulating ring 5. A metal brazing material is interposed between the upper surface of the flange portion 1b of the anode fitting 1 and the lower end surface of the insulating ring 5, and between the lower surface of the flange portion 3b of the cathode fitting 3 and the upper end surface of the insulating ring 5.
【００３０】 このような状態で、５００〜５６０℃程
度に加熱し、上側接合治具１７にて加圧を行うと、図４
(ｂ)に示すように、陽極金具１のフランジ部１ｂは、そ
の厚さが減じて内部方向（矢印Ａ方向）に延びるととも
に、その上面が絶縁リング５の下端面に接合され、ま
た、陰極金具３のフランジ部３ｂは、その厚さが減じて
外部方向（矢印Ｂ方向）に延びるとともに、その下面が
絶縁リング５の上端面に接合される。In this state, when heating is performed to about 500 to 560 ° C. and pressure is applied by the upper joining jig 17, FIG.
As shown in (b), the flange portion 1b of the anode fitting 1 is reduced in thickness and extends inward (in the direction of arrow A), the upper surface thereof is joined to the lower end surface of the insulating ring 5, and The flange portion 3 b of the metal fitting 3 is reduced in thickness and extends outward (in the direction of arrow B), and has a lower surface joined to the upper end surface of the insulating ring 5.
【００３１】 本発明の接合方法において、この熱圧接
合は、熱圧接合後の陽極金具１のフランジ部１ｂ及び陰
極金具３のフランジ部３ｂの金属組織中の結晶粒の粒長
が３ｍｍ以下となるように行う。熱圧接合の際の加熱と
圧力によって、フランジ部１ｂ、３ｂの金属組織中の結
晶粒は、その粒長が水平方向へ延びるが、熱圧接合後の
粒長が３ｍｍ以下（好ましくは２ｍｍ以下、より好まし
くは１ｍｍ以下）である場合には、ナトリウム−硫黄電
池内の活物質であるナトリウムや放電時に生成される多
硫化ナトリウムにさらされても、フランジ部１ｂ、３ｂ
と絶縁リング５との接合部においてフランジ部１ｂ、３
ｂが浸食されにくく、良好な接合状態が長期にわたって
維持される。この熱圧接合における結晶粒の粒長の制御
は、熱圧接合の際に温度と加圧力を所定範囲に制御する
ことによって行うことができる。In the joining method of the present invention, the hot-pressure joining is performed so that the grain length of the crystal grains in the metal structure of the flange 1b of the anode fitting 1 and the flange 3b of the cathode fitting 3 after the hot-press joining is 3 mm or less. Do so. Due to the heating and pressure at the time of the heat and pressure bonding, the crystal grains in the metal structure of the flange portions 1b and 3b have a grain length extending in the horizontal direction, but the grain length after the heat and pressure bonding is 3 mm or less (preferably 2 mm or less). (More preferably 1 mm or less), the flange portions 1b and 3b are exposed to sodium as an active material in the sodium-sulfur battery or sodium polysulfide generated at the time of discharge.
Flange portions 1b, 3
b is not easily eroded, and a good bonding state is maintained for a long time. The control of the grain length of the crystal grains in the thermo-compression bonding can be performed by controlling the temperature and the pressure in a predetermined range during the thermo-compression bonding.
【００３２】 陰極金具と陽極金具には、それぞれの円
筒部の金属組織中の結晶粒の粒径が、絶縁リングとの熱
圧接合後において３００μｍ以下にまで微細化されるよ
うなもの使用することが好ましく、このような金具を用
いて得られた接合体は、接合部における高い耐浸食性が
得られるとともに、絶縁リングに接合されている各金具
自体の耐腐食性や疲労耐久性も非常に優れたものとな
る。The cathode metal fittings and the anode metal fittings used should be such that the grain size of the crystal grains in the metal structure of each cylindrical portion is reduced to 300 μm or less after hot-pressure bonding with the insulating ring. It is preferable that the joined body obtained by using such a fitting has high erosion resistance at the joint, and also has extremely high corrosion resistance and fatigue durability of each fitting itself joined to the insulating ring. It will be excellent.
【００３３】[0033]
【実施例】 以下、本発明を実施例に基づいて更に詳細
に説明するが、本発明はこれらの実施例に限定されるも
のではない。EXAMPLES Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.
【００３４】（実施例１）金属素材としてアルミニウム
を用い、これを冷間鍛造により概略形状に成形した後、
切削加工により図１に示すような所定の金具形状にまで
加工して陽極金具を得た。同様に、金属素材としてアル
ミニウムを用い、これを冷間鍛造により概略形状に成形
した後、切削加工により図３に示すような所定の金具形
状に加工して陰極金具を得た。これら陽極金具の円筒部
と陰極金具の円筒部とは、冷間鍛造の際に加工率を制御
することにより、何れも熱圧接合後の金属組織中の結晶
粒子の粒径が３００μｍ以下となるようにした。(Example 1) Aluminum was used as a metal material, and after being formed into a rough shape by cold forging,
The anode metal fitting was obtained by processing to a predetermined metal fitting shape as shown in FIG. 1 by cutting. Similarly, aluminum was used as a metal material, formed into a rough shape by cold forging, and then processed into a predetermined metal shape as shown in FIG. 3 by cutting to obtain a cathode metal. By controlling the working ratio during cold forging, the cylindrical part of the anode fitting and the cylindrical part of the cathode fitting have a crystal grain size of 300 μm or less in the metallographic structure after hot-press bonding. I did it.
【００３５】 次いで、図４(ａ)のように、前記の陽極
金具１を下側接合治具１９上にセットして、α−アルミ
ナ製の絶縁リング５をその円筒部１ａに挿入し、フラン
ジ部１ｂ上に載置した。また、前記の陰極金具３を、絶
縁リング５の上端面に載置した。陽極金具１のフランジ
部１ｂ上面と絶縁リング５下端面との間、及び陰極金具
３のフランジ部３ｂ下面と絶縁リング５上端面との間に
は、金属ロウ材を介在させた。このような状態で５６０
℃に加熱してから、上側接合治具１７にて加圧を行い、
図４(ｂ)のように、陽極金具１と陰極金具３とが絶縁リ
ング５に熱圧接合された本発明の実施例に係る試験片Ａ
を得た。なお、この熱圧接合の際に温度と加圧力を所定
範囲に制御することによって、熱圧接合後の陽極金具１
のフランジ部１ｂと陰極金具３のフランジ部３ｂの金属
組織中の結晶粒子の粒長が３ｍｍ以下となるようにし
た。Next, as shown in FIG. 4 (a), the anode fitting 1 is set on the lower joining jig 19, and the insulating ring 5 made of α-alumina is inserted into the cylindrical portion 1a. Placed on the part 1b. Further, the above-mentioned cathode metal fitting 3 was placed on the upper end surface of the insulating ring 5. A metal brazing material was interposed between the upper surface of the flange portion 1b of the anode fitting 1 and the lower end surface of the insulating ring 5, and between the lower surface of the flange portion 3b of the cathode fitting 3 and the upper end surface of the insulating ring 5. 560 in such a state
° C, pressurize with the upper joint jig 17,
As shown in FIG. 4B, a test piece A according to an embodiment of the present invention in which the anode fitting 1 and the cathode fitting 3 are hot-press bonded to the insulating ring 5.
I got In addition, by controlling the temperature and the pressing force within a predetermined range at the time of the thermo-compression bonding, the anode fitting 1 after the thermo-compression bonding is formed.
The grain length of the crystal grains in the metal structure of the flange portion 1b and the flange portion 3b of the cathode fitting 3 was set to 3 mm or less.
【００３６】 また、冷間鍛造を行うことなく、アルミ
ニウムのインゴットから切削加工のみで陽極金具と陰極
金具を作製し、これを前記と同様に絶縁リングに熱圧接
合して従来例に係る試験片Ｂを得た。Also, without performing cold forging, an anode fitting and a cathode fitting were prepared only by cutting from an aluminum ingot, and were hot-press bonded to an insulating ring in the same manner as described above to obtain a test piece according to a conventional example. B was obtained.
【００３７】 このようにして得られた試験片Ａと試験
片Ｂとについて、高温下での陰極金具と絶縁リングとの
接合部における陰極金具の耐腐食性を調べる試験を実施
した。この試験は、試験片Ａと試験片Ｂとをそれぞれ４
３０℃に加熱した高温の溶融ナトリウムに浸漬し、陰極
金具と絶縁リングとの接合面において、試験時間の経過
とともに進行する陰極金具のフランジ部の浸食距離を測
定するという方法で行い、その結果を図５に示した。The test pieces A and B thus obtained were subjected to a test for examining the corrosion resistance of the cathode fitting at the junction between the cathode fitting and the insulating ring at a high temperature. In this test, test piece A and test piece B
It is immersed in high-temperature molten sodium heated to 30 ° C and measures the erosion distance of the flange part of the cathode fitting that progresses with the lapse of the test time at the joint surface between the cathode fitting and the insulating ring. As shown in FIG.
【００３８】 この図より、本発明の実施例に係る試験
片Ａは、従来例に係る試験片Ｂに比して、陰極金具と絶
縁リングとの接合面における陰極金具のフランジ部の浸
食の進行が遅く、高温下でのナトリウムに対する耐腐食
性に優れていることがわかる。From this figure, it is seen that the test piece A according to the example of the present invention has a greater erosion of the flange portion of the cathode metal fitting at the joint surface between the cathode metal fitting and the insulating ring than the test piece B according to the conventional example. It is clear that the corrosion resistance to sodium at high temperatures is excellent.
【００３９】（実施例２）前記実施例１と同様の試験片
Ａと試験片Ｂとについて、腐食環境下での陽極金具の疲
労耐久性を調べる試験を実施した。この試験は、試験片
Ａと試験片Ｂとをそれぞれ多硫化ナトリウムに浸漬し、
これを２８０℃から３６０℃へと２時間で昇温するとい
うヒートサイクルを２５００サイクル繰り返し、その後
の各試験片について、陽極金具の円筒部に破断が生じて
いるかどうか調べるという方法で行った。なお、試験個
数は試験片Ａ、試験片Ｂとも２０個ずつとした。(Example 2) A test for examining the fatigue durability of the anode fitting in a corrosive environment was performed on the test piece A and the test piece B similar to the above-mentioned Example 1. In this test, the test piece A and the test piece B were each immersed in sodium polysulfide,
A heat cycle of raising the temperature from 280 ° C. to 360 ° C. in 2 hours was repeated 2500 times, and each of the subsequent test pieces was examined to determine whether or not the cylindrical portion of the anode fitting was broken. The number of test pieces was set to 20 for each of the test pieces A and B.
【００４０】 結果は下表に示すとおりであり、従来例
に係る試験片Ｂでは２割の試験片について破断が生じて
いたのに対し、本発明の実施例に係る試験片Ａでは何れ
の試験片においても破断の発生は認められず、多硫化ナ
トリウムが存在する腐食環境下において、高い疲労耐久
性を有することがわかる。The results are as shown in the following table. In the test piece B according to the conventional example, breakage occurred in 20% of the test pieces, whereas in the test piece A according to the example of the present invention, No fracture was observed in the piece, indicating that the piece had high fatigue durability in a corrosive environment in which sodium polysulfide was present.
【００４１】[0041]
【表１】 [Table 1]
【００４２】（実施例３）冷間鍛造の際の加工率を制御
することにより、絶縁リングとの熱圧接合後における陽
極金具の円筒部と陰極金具の円筒部との金属組織中の結
晶粒子の粒径を、１００〜５００μｍの範囲で変化させ
た複数の試験片を作製し、これら試験片について、前記
実施例２と同様に腐食環境下での陽極金具の疲労耐久性
を調べる試験を実施した。結果は図６に示すとおりであ
り、熱圧接合後における円筒部の金属組織中の結晶粒子
の粒径が３００μｍ以下となるようにすることにより、
陽極金具は多硫化ナトリウムが存在する腐食環境下にお
いて、高い疲労耐久性を示すことがわかる。(Example 3) Crystal grains in the metallographic structure of the cylindrical part of the anode fitting and the cylindrical part of the cathode fitting after hot press bonding with the insulating ring by controlling the working ratio during cold forging A plurality of test pieces were prepared in which the particle size of the sample was changed in the range of 100 to 500 μm, and a test was conducted on these test pieces to examine the fatigue durability of the anode fitting in a corrosive environment in the same manner as in Example 2. did. The results are as shown in FIG. 6. By making the crystal grains in the metallographic structure of the cylindrical portion after the heat and pressure bonding have a particle size of 300 μm or less,
It can be seen that the anode fitting shows high fatigue durability in a corrosive environment where sodium polysulfide exists.
【００４３】（実施例４）熱圧接合の際の温度と加圧力
を制御することにより、絶縁リングとの熱圧接合後にお
ける陽極金具のフランジ部と陰極金具のフランジ部との
金属組織中の結晶粒子の粒長を、１〜５ｍｍの範囲で変
化させた複数の試験片を作製した。これら試験片を、そ
れぞれ４３０℃に加熱した高温の溶融ナトリウムに４０
００時間浸漬し、陰極金具と絶縁リングとの接合面にお
いて進行した陰極金具のフランジ部の浸食距離を測定し
た。結果は図７に示すとおりであり、熱圧接合後におけ
るフランジ部の金属組織中の結晶粒子の粒長が３ｍｍ以
下となるようにすることにより、陰極金具はナトリウム
が存在する高温腐食環境下において、高い耐腐食性を示
すことがわかる。(Embodiment 4) By controlling the temperature and the pressing force at the time of hot-press bonding, the metal structure between the flange portion of the anode fitting and the flange portion of the cathode fitting after the hot-pressure joining with the insulating ring is performed. A plurality of test pieces were prepared in which the grain length of the crystal particles was changed in the range of 1 to 5 mm. Each of these test pieces was placed in hot molten sodium heated to 430 ° C. for 40 minutes.
It was immersed for 00 hours, and the erosion distance of the flange portion of the cathode metal fitting advanced at the joint surface between the cathode metal fitting and the insulating ring was measured. The results are as shown in FIG. 7. By setting the grain length of the crystal grains in the metal structure of the flange portion after the heat and pressure bonding to 3 mm or less, the cathode metal fitting can be used in a high-temperature corrosive environment where sodium is present. It shows that it shows high corrosion resistance.
【００４４】[0044]
【発明の効果】 以上説明したように、本発明の陽極金
具と陰極金具は、その製造過程において、冷間鍛造によ
り金属組織に高ひずみが与えられており、この金属組織
中の結晶が絶縁リングとの熱圧接合工程における加熱に
より微細化されるため、ナトリウム−硫黄電池の活物質
であるナトリウムや放電時に生成される多硫化ナトリウ
ムが存在する腐食環境下において、優れた耐腐食性と疲
労耐久性を示す。また、本発明の接合方法においては、
このような陽極金具及び陰極金具を使用し、接合後にお
けるこれら金具のフランジ部の金属組織中の結晶粒が、
所定の粒長以下となるように熱圧接合することにより、
接合部においてフランジ部が浸食されにくくなり、長期
にわたって良好な接合状態が得られる。As described above, in the anode fitting and the cathode fitting of the present invention, during the manufacturing process, high strain is given to the metal structure by cold forging, and the crystals in the metal structure are formed by the insulating ring. Excellent corrosion resistance and fatigue durability in a corrosive environment where sodium, which is the active material of a sodium-sulfur battery, and sodium polysulfide generated at the time of discharge are present, because of the miniaturization by heating in the hot-press bonding process Shows sex. Further, in the joining method of the present invention,
Using such an anode fitting and a cathode fitting, crystal grains in the metal structure of the flange portion of these fittings after joining,
By hot-press bonding so as to be less than the specified grain length,
The flange portion is less likely to be eroded at the joined portion, and a good joined state can be obtained for a long time.
【図１】 陽極金具の一例を示す断面図である。FIG. 1 is a sectional view showing an example of an anode fitting.
【図２】 陽極金具の他の一例を示す断面図である。FIG. 2 is a sectional view showing another example of the anode fitting.
【図３】 陰極金具の一例を示す断面図である。FIG. 3 is a sectional view showing an example of a cathode fitting.
【図４】 本発明の接合方法一例を示す断面図で、(ａ)
が熱圧接合の加圧前の状態を示し、(ｂ)は熱圧接合後の
接合体を示している。FIG. 4 is a cross-sectional view showing an example of a bonding method according to the present invention;
Shows a state before pressurization of the thermo-compression bonding, and (b) shows a joined body after thermo-compression bonding.
【図５】 実施例１の結果を示すグラフである。FIG. 5 is a graph showing the results of Example 1.
【図６】 実施例３の結果を示すグラフである。FIG. 6 is a graph showing the results of Example 3.
【図７】 実施例４の結果を示すグラフである。FIG. 7 is a graph showing the results of Example 4.
【図８】 ナトリウム−硫黄電池の全体構造を示す断面
図である。FIG. 8 is a sectional view showing the overall structure of a sodium-sulfur battery.
【図９】 陽極金具及び陰極金具と絶縁リングとの接合
状態を示す要部拡大図である。FIG. 9 is an enlarged view of a main part showing a bonding state between an anode fitting, a cathode fitting, and an insulating ring.
１…陽極金具、３…陰極金具、５…絶縁リング、７…陽
極容器、９…固体電解質管、１１…陰極蓋、１３…陽極
側端子、１５…陰極側端子、１７…上側接合治具、１９
…下側接合治具。DESCRIPTION OF SYMBOLS 1 ... Anode fitting, 3 ... Cathode fitting, 5 ... Insulation ring, 7 ... Anode container, 9 ... Solid electrolyte tube, 11 ... Cathode lid, 13 ... Anode side terminal, 15 ... Cathode side terminal, 17 ... Upper joining jig, 19
... Lower joining jig.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開2000−231932（ＪＰ，Ａ) 特開 平６−163073（ＪＰ，Ａ) 特開 平８−329980（ＪＰ，Ａ) 特開2000−58109（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 10/39 ──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-2000-231932 (JP, A) JP-A-6-163073 (JP, A) JP-A-8-329980 (JP, A) JP-A-2000-58109 ( JP, A) (58) Field surveyed (Int. Cl. 7 , DB name) H01M 10/39
Claims (12)
に張り出したフランジ部とを有し、当該フランジ部の上
面を絶縁リングの下端面に熱圧接合して使用されるナト
リウム−硫黄電池の陽極金具であって、当該陽極金具
は、金属素材を冷間鍛造により金具の概略形状に成形し
た後、これを所定の金具形状にまで加工することによっ
て得られたものであり、少なくとも絶縁リングに熱圧接
合するフランジ部の上面についての前記加工が切削加工
にて行われていることを特徴とするナトリウム−硫黄電
池の陽極金具。1. A sodium-sulfur battery having a cylindrical portion and a flange portion projecting inward from a lower end of the cylindrical portion, wherein an upper surface of the flange portion is hot-press bonded to a lower end surface of an insulating ring for use. The anode fitting is obtained by forming a metal material into a rough shape of a fitting by cold forging, and then processing it into a predetermined fitting shape, and at least an insulating ring. Wherein the above-mentioned processing on the upper surface of the flange portion to be hot-pressed is performed by cutting.
結晶粒の粒径が３００μｍ以下となる請求項１記載の陽
極金具。2. The anode fitting according to claim 1, wherein the grain size of the crystal grains in the metal structure of the cylindrical portion after the thermocompression bonding is 300 μm or less.
結晶粒の粒径が２００μｍ以下となる請求項１記載の陽
極金具。3. The anode fitting according to claim 1, wherein the grain size of crystal grains in the metal structure of the cylindrical portion after the hot-press bonding is 200 μm or less.
結晶粒の粒径が１００μｍ以下となる請求項１記載の陽
極金具。4. The anode fitting according to claim 1, wherein the grain size of the crystal grains in the metal structure of the cylindrical portion after the thermocompression bonding is 100 μm or less.
肉厚が異なる段付き形状を有し、上方部分の肉厚に対し
て下方部分の肉厚が薄肉となるように形成されたた請求
項１記載の陽極金具。5. The cylindrical portion has a stepped shape in which the upper portion and the lower portion have different thicknesses, and is formed such that the thickness of the lower portion is thinner than the thickness of the upper portion. The anode fitting according to claim 1.
に張り出したフランジ部とを有し、当該フランジ部の下
面を絶縁リングの上端面に熱圧接合して使用されるナト
リウム−硫黄電池の陰極金具であって、当該陰極金具
は、金属素材を冷間鍛造により金具の概略形状に成形し
た後、これを所定の金具形状にまで加工することによっ
て得られたものであり、少なくとも絶縁リングに熱圧接
合するフランジ部の下面についての前記加工が切削加工
にて行われていることを特徴とするナトリウム−硫黄電
池の陰極金具。6. A sodium-sulfur battery having a cylindrical portion and a flange portion projecting outward from an outer periphery of the cylindrical portion, wherein a lower surface of the flange portion is hot-pressed to an upper end surface of an insulating ring for use. The cathode metal fitting, the cathode metal fitting is obtained by forming a metal material into a general shape of the metal fitting by cold forging, and then processing it into a predetermined metal fitting shape, at least an insulating ring The lower surface of the flange portion that is to be thermally and pressure-bonded to the lower surface is cut by cutting.
結晶粒の粒径が３００μｍ以下となる請求項６記載の陰
極金具。7. The cathode metal fitting according to claim 6, wherein the grain size of the crystal grains in the metal structure of the cylindrical portion after the thermocompression bonding is 300 μm or less.
結晶粒の粒径が２００μｍ以下となる請求項６記載の陰
極金具。8. The cathode metal fitting according to claim 6, wherein the grain size of the crystal grains in the metal structure of the cylindrical portion after the heat and pressure bonding is 200 μm or less.
結晶粒の粒径が１００μｍ以下となる請求項６記載の陰
極金具。9. The cathode metal fitting according to claim 6, wherein the grain size of the crystal grains in the metal structure of the cylindrical portion after the thermocompression bonding is 100 μm or less.
れた陽極金具のフランジ部の上面を絶縁リングの下端面
に、また、請求項６ないし９に記載された陰極金具のフ
ランジ部の下面を絶縁リングの上端面に同時に熱圧接合
する方法であって、熱圧接合後の陽極金具のフランジ部
及び陰極金具のフランジ部の金属組織中の結晶粒の粒長
が３ｍｍ以下となるように熱圧接合を行うことを特徴と
するナトリウム−硫黄電池の陽極金具及び陰極金具と絶
縁リングとの接合方法。10. The lower surface of the flange of the cathode metal fitting according to claim 6, the upper surface of the flange of the anode metal fitting according to any one of claims 1 to 5, and the lower surface of the flange of the cathode metal fitting according to claim 6 to 9. Is simultaneously bonded to the upper end surface of the insulating ring by heat and pressure so that the grain length of the crystal grains in the metal structure of the flange portion of the anode metal fitting and the flange portion of the cathode metal fitting after the hot pressure bonding is 3 mm or less. A method for joining an insulating ring to an anode and a cathode of a sodium-sulfur battery, wherein the joining is performed by thermal pressure.
部及び陰極金具のフランジ部の金属組織中の結晶粒の粒
長が２ｍｍ以下となるように熱圧接合を行う請求項１０
記載の接合方法。11. The heat and pressure bonding is performed such that the grain length of the crystal grains in the metal structure of the flange portion of the anode metal fitting and the flange of the cathode metal fitting after the heat and pressure bonding is 2 mm or less.
The joining method described.
部及び陰極金具のフランジ部の金属組織中の結晶粒の粒
長が１ｍｍ以下となるように熱圧接合を行う請求項１０
記載の接合方法。12. The hot-pressure bonding so that the grain length of the crystal grains in the metal structure of the flange portion of the anode fitting and the flange portion of the cathode fitting after the hot-pressure joining is 1 mm or less.
The joining method described.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03193799A JP3325238B2 (en) | 1999-02-09 | 1999-02-09 | Anode and cathode fittings for sodium-sulfur battery and method of joining these to insulating ring |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03193799A JP3325238B2 (en) | 1999-02-09 | 1999-02-09 | Anode and cathode fittings for sodium-sulfur battery and method of joining these to insulating ring |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000231931A JP2000231931A (en) | 2000-08-22 |
| JP3325238B2 true JP3325238B2 (en) | 2002-09-17 |
Family
ID=12344898
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03193799A Expired - Lifetime JP3325238B2 (en) | 1999-02-09 | 1999-02-09 | Anode and cathode fittings for sodium-sulfur battery and method of joining these to insulating ring |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3325238B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101554336B1 (en) | 2013-12-26 | 2015-09-21 | 재단법인 포항산업과학연구원 | Sodium-sulfur rechargeable battery and method for manufacturing the same |
-
1999
- 1999-02-09 JP JP03193799A patent/JP3325238B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP2000231931A (en) | 2000-08-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4530151A (en) | Manufacture method of a sodium-sulfur storage battery | |
| EP0196221B1 (en) | Method of making ceramic composites | |
| JP3325238B2 (en) | Anode and cathode fittings for sodium-sulfur battery and method of joining these to insulating ring | |
| US9735401B2 (en) | Sealed sodium-based thermal batteries and methods of sealing same | |
| JP3353102B2 (en) | Method for manufacturing sodium-sulfur battery | |
| USRE31568E (en) | Composite substrate for rotating x-ray anode tube | |
| JPH07284989A (en) | Brazing filler metal for high-temperature brazing | |
| CN109763006A (en) | A kind of magnalium composite component forming connecting integration method | |
| JP3526229B2 (en) | Bonding method and bonding structure of insulating ring and cathode metal fitting for sodium-sulfur battery | |
| JPS58128281A (en) | Diffusion bonding method of sintered hard alloy and steel | |
| US3160480A (en) | Refractory articles bonded to a metal base | |
| JP3481643B2 (en) | Vacuum container using beryllium foil for windows | |
| JP2997697B2 (en) | High melting point metal joined body, ion gun component for ion implantation apparatus, and method of manufacturing these | |
| JP2000327442A (en) | Ceramic-metal joined body, its production and high temperature type secondary battery | |
| JP2002056887A (en) | Method for manufacturing thermo-compression joining member for insulating ring constituting sodium-sulfur battery and positive electrode metal fitting | |
| US9105896B2 (en) | Metal rings for active brazing in sodium-based thermal batteries | |
| JP4574196B2 (en) | Joining structure of insulating ring and anode cylindrical fitting in sodium-sulfur battery | |
| JP4170627B2 (en) | Sodium-sulfur battery | |
| JP2000323167A (en) | Manufacture and manufacturing device of sodium-sulfur battery | |
| JP2545153B2 (en) | Glass bonded body and manufacturing method thereof | |
| JP3376242B2 (en) | Method for joining ceramic insulator and metal parts of sodium-sulfur battery | |
| JP3532457B2 (en) | Bonding structure between an insulating ring and an anode cylindrical metal fitting in a sodium-sulfur battery | |
| JP2000090967A (en) | Joint structure of insulation ring and positive electrode cylindrical fitting for sodium-sulfur battery | |
| JPS6027665A (en) | Manufacture of bonded body of ceramic and metal | |
| JP4253216B2 (en) | Composite material of copper-tungsten alloy and copper and method for producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20020618 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080705 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090705 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100705 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100705 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110705 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120705 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120705 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130705 Year of fee payment: 11 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| EXPY | Cancellation because of completion of term |