JPH02121270A - Sodium-sulphur cell and its manufacture - Google Patents
Sodium-sulphur cell and its manufactureInfo
- Publication number
- JPH02121270A JPH02121270A JP63275084A JP27508488A JPH02121270A JP H02121270 A JPH02121270 A JP H02121270A JP 63275084 A JP63275084 A JP 63275084A JP 27508488 A JP27508488 A JP 27508488A JP H02121270 A JPH02121270 A JP H02121270A
- Authority
- JP
- Japan
- Prior art keywords
- sodium
- insulator ring
- metal container
- glass
- container
- 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
- BNOODXBBXFZASF-UHFFFAOYSA-N [Na].[S] Chemical compound [Na].[S] BNOODXBBXFZASF-UHFFFAOYSA-N 0.000 title claims description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000012212 insulator Substances 0.000 claims abstract description 55
- 229910052751 metal Inorganic materials 0.000 claims abstract description 52
- 239000002184 metal Substances 0.000 claims abstract description 52
- 239000011521 glass Substances 0.000 claims abstract description 51
- 239000011734 sodium Substances 0.000 claims description 15
- 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 description 13
- 229910052708 sodium Inorganic materials 0.000 claims description 13
- 229910000873 Beta-alumina solid electrolyte Inorganic materials 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- 239000011593 sulfur Substances 0.000 claims description 8
- 239000011247 coating layer Substances 0.000 claims description 6
- 229910001415 sodium ion Inorganic materials 0.000 claims description 6
- 239000002043 β-alumina solid electrolyte Substances 0.000 claims description 4
- 230000002093 peripheral effect Effects 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 3
- 238000007789 sealing Methods 0.000 abstract description 3
- 238000003466 welding Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 11
- 150000004703 alkoxides Chemical class 0.000 description 10
- 238000010304 firing Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- 239000010409 thin film Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 2
- 239000006183 anode active material Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 235000019524 disodium tartrate Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 description 1
- 239000001433 sodium tartrate Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent 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】
「産業上の利用分野］
本発明はナトリウム−硫黄電池およびその製造方法に係
り、更に詳しくは、少なくとも絶縁体リンクと陰極金属
容器との接合部においてナトリウム等のリーク防止を確
実にし、接合部の耐ナトリウム性を向上させたナトリウ
ム−硫黄電池およびその製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a sodium-sulfur battery and a method for manufacturing the same. The present invention relates to a sodium-sulfur battery and a method for manufacturing the same, which ensure the stability of the sodium-sulfur battery and improve the sodium resistance of the joint.
［従来の技術］
ナトリウム−Ｗｔ黄主電池、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
性を有するベータアルミナ固体重解質て陥離し、３００
〜３５０°Ｃて作動させる高温二次電池である。[Prior art] A sodium-Wt yellow main battery, with molten metal sodium as a cathode active material on one side and molten sulfur as an anode active material on the other side, and making both of them selectively permeable to sodium ions. Beta alumina solid decomposition with 300
It is a high-temperature secondary battery that operates at ~350°C.
このようなナトリウム−硫黄電池の構成は、例えば第３
図に示すように、陽極活物質である溶融硫黄Ｓを含浸し
たカーボンフェルト等の陽極用導電材ｌを収容する円筒
状の陽極金属容器２と、該陽極金属容器２の上端部と例
えばアルファアルミナ製の絶縁体リング３を介して連結
され、且つ溶融金属ナトリウムＮａを貯留する陰極金属
容器４と、前記絶縁体リンク３の内周部に接合され、且
つナトリウムイオンＮａ＋を選択的に透過させる機走を
有する有底円筒状のベータアルミナ管５とからなってい
る。また、前記陰極金属容器４の上４６の中央部には、
陰極金属容器４を通して下方向にベータアルミナ管５の
底部付近まで延びた陰極管７か貢通支持されている。The configuration of such a sodium-sulfur battery is, for example,
As shown in the figure, there is a cylindrical anode metal container 2 that accommodates an anode conductive material l such as carbon felt impregnated with molten sulfur S, which is an anode active material, and an upper end of the anode metal container 2 and an alpha alumina material such as alpha alumina. A cathode metal container 4 which is connected via an insulator ring 3 made of aluminum and which stores molten metal sodium Na; It consists of a cylindrical beta alumina tube 5 with a bottom. Moreover, in the center of the upper part 46 of the cathode metal container 4,
A cathode tube 7 extending downward through the cathode metal container 4 to near the bottom of the beta alumina tube 5 is supported through the cathode tube.
以北の構成を有するナトリウム−硫黄電池において、放
電時には溶融金属ナトリウムは電子を放出してナトリウ
ムイオンとなり、これがベータアルミナ固体電解質中を
透過して陽極側に移動し、陽極の硫黄と外部回路を通っ
てきた電子とが反応して多硫化ナトリウムを生成し、２
Ｖ程度の電圧を発生する。一方、充電時には放電とは逆
にす１−リウム及び硫黄の生成反応か起こる。In a sodium-sulfur battery with a configuration similar to the above, during discharge, molten metal sodium releases electrons and becomes sodium ions, which pass through the beta-alumina solid electrolyte and move to the anode side, where they interact with the sulfur at the anode and the external circuit. The passing electrons react with each other to produce sodium polysulfide, and 2
Generates a voltage of about V. On the other hand, during charging, a reaction for producing 1-lium and sulfur occurs, which is the opposite of discharging.
以上のように、従来のナトリウム−硫黄電池はアルファ
アルミナ絶縁体リングと陰極金属容器間か直接熱圧接合
により接合されている。As described above, in the conventional sodium-sulfur battery, the alpha alumina insulator ring and the cathode metal container are directly bonded by thermopressure bonding.
［発明が解決しようとする課題］
このようなナトリウム−硫黄電池において一現在の大き
な課題として、アルファアルミナ絶縁体リングと陰極金
属容器との接合部におけるリークと残留応力か挙げられ
ている。即も、従来の電池においては、アルファアルミ
ナ絶縁体リングと陰極金属容器とか直接接合されている
か、アルファアルミナ絶縁体リング表面には微小な凹凸
（表面欠陥）か存在することの他、アルファアルミナと
金属（Ｆｅ又はＡｌを通常陰陽極金属容器として用いる
。）はその熱膨張係数に大きな差かあるため、室温から
使用温度（３００〜３５０°Ｃ）まて環境温度か変化す
ることにより、上記材質間の熱膨張差に基き絶縁体リン
クと陰極金属容器の接合部に歪か発生して亀裂か生じる
ことがあり、このため加圧されている陰極容器内の金属
ナトリウムかリークし、電池か使用不可となる事態が起
こるという欠点かあった。[Problems to be Solved by the Invention] Current major problems in such sodium-sulfur batteries include leakage and residual stress at the joint between the alpha alumina insulator ring and the cathode metal container. In conventional batteries, the alpha alumina insulator ring and the cathode metal container are directly bonded, or there are minute irregularities (surface defects) on the alpha alumina insulator ring surface. Since metals (Fe or Al are usually used as the cathode and anode metal containers) have large differences in their coefficients of thermal expansion, changes in the environmental temperature from room temperature to the operating temperature (300 to 350°C) will affect the quality of the above materials. Due to the difference in thermal expansion between the insulator link and the cathode metal container, the joint between the insulator link and the cathode metal container may become strained and cracked, causing the metal sodium in the pressurized cathode container to leak and prevent the battery from being used. The drawback was that something impossible happened.
［課題を解決するための手段］
そこて、本発明者らは、上記接合部におけるリーク等の
問題を解決すべく、種々検討を重ねた結果、本発明を完
成したものである。[Means for Solving the Problems] Therefore, the present inventors have completed the present invention as a result of various studies in order to solve the problems such as leaks in the joints.
即ち、本発明によれば、溶融硫黄を収容する陽極金属容
器と、該陽極金属容器の上端部と絶縁体リンクを介して
接合され且つ溶融金属ナトリウムを貯留する陰極金属容
器と、■ｊ記絶絶縁体リング内周部に接合され且つナト
リウムイオンを選択的に透過させる機能を有するベータ
アルミナ固体電解質管とからなるナトリウム−硫黄電池
において前記絶縁体リングと少なくとも陰極金属容器の
下端部とか、ガラスを介して接合されてなることを特徴
とするナトリウム−硫黄電池、か提供される。That is, according to the present invention, an anode metal container that accommodates molten sulfur, a cathode metal container that is connected to the upper end of the anode metal container via an insulator link and that stores molten metal sodium; In a sodium-sulfur battery consisting of a beta alumina solid electrolyte tube that is bonded to the inner periphery of an insulator ring and has a function of selectively transmitting sodium ions, the insulator ring and at least the lower end of the cathode metal container or glass A sodium-sulfur battery is provided, characterized in that the sodium-sulfur battery is bonded via a sodium-sulfur battery.
さらに、本発明によれば、溶融硫黄を収容する陽極金属
容器と、該陽極金属容器のＬ端部と絶縁体リンクを介し
て接合されＲつ溶融金属ナトリウムを貯留する陰極接合
容器と、前記絶縁体リングの内周部に接合され且つナト
リウムイオンを選択的に透過させる機能を有するベータ
アルミナ固体電解ｙｊｉ管とからなるナトリウム−硫黄
電池を製造する方法において、前記絶縁体リンクの少な
くとも陰極金属容器と接する面上にツル状態としたガラ
ス成分を塗布後焼成してガラス被覆層を形成し、次いで
該絶縁体リングと陰極金属容器の下端部とを熱圧接合す
ることを特徴とするナトリウム硫黄電池の製造方法、か
提供される。Further, according to the present invention, there is provided an anode metal container for storing molten sulfur, a cathode joint container connected to the L end of the anode metal container via an insulator link and storing R pieces of molten metal sodium; A method for manufacturing a sodium-sulfur battery comprising a beta alumina solid electrolytic YJI tube joined to the inner circumference of a body ring and having a function of selectively permeating sodium ions, wherein at least the cathode metal container of the insulator link and A sodium-sulfur battery characterized in that a glass component in a vine state is applied and fired on the contacting surfaces to form a glass coating layer, and then the insulator ring and the lower end of the cathode metal container are bonded under heat and pressure. manufacturing method, or provided.
［作用］
本発す１では、少なくとも陰極容器と接する絶縁体リン
グの面上にゾル状７８としたガラス成分の、好ましくは
アルコキシドを塗布後焼成してガラス被覆層を形成し、
次いで絶縁体リンクと陰極金属容器の下端部とを熱圧接
合することにより、絶縁体リングと金属との熱膨張の差
を吸収・緩和させるとともに、絶縁体リング表面の微小
な凹凸をなくして滑らかにすることにより、接合部のシ
ール性を向上させ、その結果、接合部におけるリークか
防止てき、しかも熱圧接合の際に容器の接合部の伸びを
良くすることができ、接合部の耐ナトリウム性を向上さ
せることができたのである。[Function] In 1 of the present invention, a glass component, preferably an alkoxide, in the form of a sol 78 is applied on at least the surface of the insulator ring in contact with the cathode container, and then baked to form a glass coating layer,
Next, by thermopressure bonding the insulator link and the lower end of the cathode metal container, the difference in thermal expansion between the insulator ring and the metal is absorbed and alleviated, and minute irregularities on the surface of the insulator ring are eliminated to make it smooth. This improves the sealing performance of the joint, thereby preventing leaks at the joint, and also improves the elongation of the joint of the container during thermo-pressure joining, making the joint more resistant to sodium. I was able to improve my sexuality.
尚、本発明のように、絶縁体リング上にゾル状態とした
ガラス成分の例えばアルコキシドを塗布した後、焼成す
ることによりガラス被覆層を形成することをしないで、
ガラスフリットのパウダーを用いてガラス層を形成する
場合には、絶縁体リング表面の微小な凹凸はなくせても
、形成されるガラス層厚さが１１００ｐ以上となりその
後熱圧接合しても接合強度はアルコキシドを用いたもの
ほど向上は望めない。Note that, as in the present invention, the glass coating layer is not formed by applying a glass component in a sol state, such as an alkoxide, onto the insulator ring and then firing it.
When forming a glass layer using glass frit powder, even if minute irregularities on the surface of the insulator ring can be eliminated, the thickness of the formed glass layer will be more than 1100p, and the bonding strength will be poor even after subsequent thermo-pressure bonding. Improvements cannot be expected compared to those using alkoxides.
本発明では、上記した如く、ゾル−ゲル法によるガラス
層形成方法を利用し、絶縁体リング上に好ましくはガラ
スゾルを塗布した後焼成することにより、数ＩＬｍ程度
という極めて薄いガラス被膜を絶縁体リンク上に形成さ
せることかできたのである。その結果、絶縁体リンクと
少なくとも陰極金属容器、好ましくは絶縁体リングの両
面にアルコキシドよ、りなるガラスゾルを塗布し、焼成
後陰極容器および陽極容器とを熱圧接合すると、大きな
接合強度を有する接合部を得ることかできる。In the present invention, as described above, by using the glass layer forming method using the sol-gel method, preferably by applying a glass sol onto the insulator ring and then firing it, an extremely thin glass coating of about several ILm is formed on the insulator link. It was possible to form it on top. As a result, if a glass sol made of alkoxide is applied to both sides of the insulator link and at least the cathode metal container, preferably the insulator ring, and the cathode container and the anode container are bonded by heat and pressure after firing, the bond has a high bonding strength. Is it possible to get a division?
本発明で、絶縁体リング上に塗布するガラス成分は、ア
ルコキシドとして用いることが好ましい。具体的には、
ガラスの主成分である金属元素をアルコキシドとしだ金
属アルコキシドを用い、これを酸、水などでゾル状態と
し、絶縁体リング上にディウピング、スプレー等により
塗１ｔｉする。In the present invention, the glass component coated on the insulator ring is preferably used as an alkoxide. in particular,
The metal alkoxide, which is a main component of the glass, is used as an alkoxide.The metal alkoxide is made into a sol state with acid, water, etc., and coated on the insulating ring by dipping, spraying, or the like.
この塗布厚さは約５０〜８０ｐｍがよい。塗布後、焼成
してガラス被膜を形成するか、焼成は酸素雰囲気下、９
００〜１ｏｏｏ”ｃの温度で１〜２時間行なわれる。The coating thickness is preferably about 50 to 80 pm. After coating, it is baked to form a glass film, or the baking is done in an oxygen atmosphere.
It is carried out for 1 to 2 hours at a temperature of 0.00 to 1 ooo"c.
上記のようにして形成されるガラス被１漠（層）は、そ
の組成か、５ｉ０２３０〜４０重量％、Ｎａ、０ １０
〜２０重量％、８２０３２０〜３０重量％、ＡＭ２０３
２０〜３０屯量％であるホウケイ酸ガラスが好ましい。The glass layer formed as described above has a composition of 5i0230 to 40% by weight, Na, 010
~20% by weight, 820320~30% by weight, AM203
Borosilicate glass having a volume content of 20 to 30% is preferred.
また、このガラス層は薄く形成され、１０ｕＬｍ以下と
なる。さらに、このガラス層は中心線平均粗さか０．２
〜１．ｏｐｍ程度であり、その後の熱圧接合により接合
部は完全にシールされる。Further, this glass layer is formed thinly, with a thickness of 10 uLm or less. Furthermore, this glass layer has a center line average roughness of 0.2
~1. opm, and the bonded portion is completely sealed by subsequent thermopressure bonding.
本発明においては、次に、絶縁体リング上にガラス層を
形成した後、熱圧接合する。In the present invention, a glass layer is then formed on the insulator ring and then thermo-pressure bonded.
熱圧接合は、通常、温度５４０〜６５０°Ｃ１好ましく
は６００〜６２０℃で、約２秒〜３０分間好ましくは約
１０秒、圧力５〜５０ Ｍ Ｐ ａ、好ましくは３５〜
４５ＭＰａで行なわれる。この熱圧接合の場合、本発明
では上記のように、薄いガラス層が形成されているので
、容器の接合部の伸びを良くすることができ、その結果
、接合部の耐ナトリウム性を向上させることができる。The thermopressure bonding is usually performed at a temperature of 540 to 650°C, preferably 600 to 620°C, for about 2 seconds to 30 minutes, preferably about 10 seconds, and a pressure of 5 to 50 MPa, preferably 35 to 30 minutes.
It is carried out at 45 MPa. In the case of this thermopressure bonding, as described above, in the present invention, since a thin glass layer is formed, the elongation of the joint of the container can be improved, and as a result, the sodium resistance of the joint can be improved. be able to.
上記したような方法により形成される絶縁体リングと少
なくとも陰極金属容器の接合部は、シール性に優れ、し
かも中間のガラス層か薄く形成されるため、接合強度を
２０ＭＰａ以上に大きくすることができる。The joint between the insulator ring and at least the cathode metal container formed by the method described above has excellent sealing properties, and since the intermediate glass layer is formed thinly, the joint strength can be increased to 20 MPa or more. .
［実施例］
以下、未発ＩＩを実施例に基きさらに詳細に説明するか
１本発明はこれらの実施例に限られるものてはない。[Examples] Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples.
第１図はアルファアルミナよりなる絶縁体リンクヒヘガ
ラス層を形成した後熱圧接合する方法の一例を示すフロ
ーチャートである。FIG. 1 is a flowchart showing an example of a method of forming an insulator link glass layer made of alpha alumina and then bonding with heat and pressure.
まず、ガラス成分のアルコキシドを水、酸などと混合し
、ガラスゾルな調合する・。First, the glass component alkoxide is mixed with water, acid, etc. to form a glass sol.
次いで、粘度調整剤をガラスゾルに混合して粘度調整を
行なった後、この混合液を絶縁体リングの接合面上へ塗
布し、５０〜１００℃で０．５〜１時間乾燥する。さら
に、その上に上記混合液を塗布し、５０〜１００℃て１
〜５時間乾燥する。Next, a viscosity modifier is mixed with the glass sol to adjust the viscosity, and then this mixed solution is applied onto the joint surface of the insulator ring and dried at 50 to 100°C for 0.5 to 1 hour. Furthermore, apply the above mixed solution on top of it and heat it at 50 to 100°C for 1
Dry for ~5 hours.
次に９００〜ｔｏｏｏ℃にて１〜２時間焼成することに
より、絶縁体リンク上にｌ Ｏ４ｍ以下の厚さのガラス
層を形成する。その後、絶縁体リングと陰極容器および
陽極容器とを熱圧接合する。Next, a glass layer having a thickness of 1 O 4 m or less is formed on the insulator link by firing at 900° C. to 100° C. for 1 to 2 hours. Thereafter, the insulator ring, the cathode container, and the anode container are bonded together by thermopressure.
次に、更に具体的な実施結果を説明する。Next, more specific implementation results will be explained.
（実施例１）
トリメチルポライド１５ｇ、テトラオルトシリケート１
４ｇ、水１８．５ｇ、クエン酸２０ｇ、クエン酸ナトリ
ウム４ｇを混合して、ガラスゾルを調合した。(Example 1) 15 g of trimethyl poride, 1 portion of tetraorthosilicate
4 g, water 18.5 g, citric acid 20 g, and sodium citrate 4 g were mixed to prepare a glass sol.
次いで、このガラスゾルと同体積のイソプロピルアルコ
ールを混合して粘度を調整した後、スプレー装置により
ｔ記の混合液を絶縁体リング上に被覆した。これを８０
℃、１時間で乾燥させた後さらにその上に前記混合液を
スプレー装置にて被覆し、８０°Ｃ，４時間乾燥させた
。絶縁体リンク上に作製されたガラスゾル層の厚さは６
０ｇｍであった。Next, this glass sol and the same volume of isopropyl alcohol were mixed to adjust the viscosity, and then the insulator ring was coated with the liquid mixture described in t using a spray device. This is 80
After drying at 80° C. for 1 hour, the mixture was further coated with the above mixture using a spray device and dried at 80° C. for 4 hours. The thickness of the glass sol layer produced on the insulator link is 6
It was 0 gm.
次に、第２図に示す焼成スケジュールにより焼成を行な
った。その結果、アルファアルミナよりなる絶縁体リン
ク上に作製されたガラス表面は。Next, firing was performed according to the firing schedule shown in FIG. As a result, the glass surface is fabricated on an insulator link made of alpha alumina.
中心線平均粗さ（Ｒａ）０．５ｇｍ、最大高さ（Ｒｍａ
ｘ ） ４．０ ｇｍであって平滑となった。又、ガラ
ス＠膜の厚さは４ｇｍであった。Center line average roughness (Ra) 0.5gm, maximum height (Rma
x) 4.0 gm and became smooth. Further, the thickness of the glass@membrane was 4 gm.
一方、ガラス薄膜の組成分析を行なったところ８２０３
１６．３重量％、Ｎａ２０１２．６重量％、Ａ１．０３
２０．６重量％、Ｓ ｉ ０２４２８屯量％てあった。On the other hand, when we analyzed the composition of the glass thin film, we found that 8203
16.3% by weight, Na2012.6% by weight, A1.03
It was 20.6% by weight and S i 02428% by weight.
次いで、このように表面上にガラス薄層を形成した絶縁
体リンクと陰極金属容器とを６２０°Ｃ１４０ＭＰａで
１０秒間熱圧接合した。その結果、接合部における接合
強度は２０ Ｍ Ｐ ａを示した。Next, the insulator link with the thin glass layer formed on its surface and the cathode metal container were bonded under heat and pressure at 620° C. and 140 MPa for 10 seconds. As a result, the bonding strength at the bonded portion was 20 MPa.
（実施例２）
トリエチルポライド２０ｇ、テトラメトキシシランｌｏ
ｇ、酒石酸１４ｇ、酒石酸２ナトリウム６ｇ？：混合し
てガラスツルを調合した。(Example 2) 20 g of triethylpolide, tetramethoxysilane lo
g, tartaric acid 14g, disodium tartrate 6g? : Mixed to prepare glass vine.
次いで、このガラスゾルと同体積のエチルアルコールを
混合して粘度を調整した後、上記の混合液をアルファア
ルミナよりなる絶縁体リンクの両面上にへヶで塗った。Next, this glass sol and the same volume of ethyl alcohol were mixed to adjust the viscosity, and then the above mixed solution was applied on both sides of an insulator link made of alpha alumina.
これを８０６Ｃ，１時間て乾燥させた後、さらにその上
に前記混合液をへケて塗布し、ａｏ’ｃ、４時間乾燥し
た。絶縁体リング上に被覆されたガラスゾル層の厚さは
６５７ｚｍであった。After drying this at 806C for 1 hour, the above-mentioned liquid mixture was further applied thereon and dried at 806C for 4 hours. The thickness of the glass sol layer coated on the insulator ring was 657 zm.
次に第２図に示す焼成スケジュールにより焼成を行った
。その結果、アルファアルミナ絶縁体リング上に形成さ
れたガラス表面は、中心線モ均粗さ０．５μｍ、最大高
さ４．０ｇｍてあって平滑となった。又、ガラス薄膜の
厚さは４７ｚｍてあった。Next, firing was performed according to the firing schedule shown in FIG. As a result, the glass surface formed on the alpha alumina insulator ring was smooth with a center line average roughness of 0.5 μm and a maximum height of 4.0 gm. Further, the thickness of the glass thin film was 47 zm.
−・方、ガラス薄膜の組成分析を行ったところ、Ｂ２０
，１８．５重量％、Ｎａ２０１３．７重量％、Ａｌ２Ｏ
３２２，３重量％、５ｉ０２４３重刊％であった。- On the other hand, when we analyzed the composition of the glass thin film, we found that B20
, 18.5% by weight, Na2013.7% by weight, Al2O
It was 322.3% by weight and 5i0243% by weight.
次いでこのように表面上にガラス薄膜を形成したアルフ
ァアルミナ絶縁体リングとステンレスよりなる陰極金属
容器および陽極金属容器とを６２０°Ｃ１４０ＭＰａて
１０秒間熱圧接合した。Next, the alpha alumina insulator ring with the glass thin film formed on its surface and a cathode metal container and an anode metal container made of stainless steel were bonded under heat and pressure at 620 DEG C. and 140 MPa for 10 seconds.
その結果、接合部における接合強度は２０ＭＰａを示し
、又Ｈｅリーク試験および３５０℃に１００時間加熱後
のＨｅリーク試験においても、全くリークは認められな
かった。As a result, the joint strength at the joint was 20 MPa, and no leakage was observed in the He leak test and the He leak test after heating at 350° C. for 100 hours.
［発明の効果］
以上説明したように、請求項１記佐のナトリウム−硫黄
電池によれば、絶縁体リングと少なくとも陰極金属容器
とをガラスを介して接合するのて、絶縁体リング表面の
凹凸を滑らかにできるため熱圧接合の際の容器の接合部
材の伸びを良くすることかＣき、接合部の耐ナトリウム
性を向上させることかてきる。[Effects of the Invention] As explained above, according to the sodium-sulfur battery of claim 1, the insulator ring and at least the cathode metal container are bonded via glass, thereby reducing the unevenness on the surface of the insulator ring. Since it can be made smoother, it is possible to improve the elongation of the container joining member during thermo-pressure joining, and improve the sodium resistance of the joint.
また、請求項２記載の製造方法によれば、絶縁体リンク
−１−にゾル状態としたガラス成分の好ましくはアルコ
キシドを塗布後焼成してガラス被覆層を形成し、次いで
熱圧接合しているので、薄いガラス被覆層を形成でき、
接合強度の大きな電池を（■することかてきる。さらに
絶縁体リング表面の凹凸か滑らかとなるので、熱圧接合
の際の容器の接合部の伸びを良くすることかでき、接合
部の耐ナトリウム性を向上させることかてきる。Further, according to the manufacturing method according to claim 2, a glass component, preferably an alkoxide, in a sol state is applied to the insulator link-1-, and then baked to form a glass coating layer, and then bonded under heat and pressure. Therefore, a thin glass coating layer can be formed,
It is possible to bond batteries with high bonding strength (■).In addition, since the surface of the insulator ring is smooth, the elongation of the container joint during thermo-pressure bonding can be improved, increasing the durability of the joint. It can improve sodium content.
第１し１は本発明方法の一例を示すフローチャート、第
２図は本発明の焼成スケジュールの一例を示すグラフ、
第３図はナトリウム−硫黄電池の構成を示す断面説ＩＪ
Ｉ図である。
２・・・陽極金属容器、３・・・絶縁体リング、４・・
・陰極金属容器、５・・・ベータアルミナ管。Fig. 1 is a flow chart showing an example of the method of the present invention, Fig. 2 is a graph showing an example of the firing schedule of the present invention,
Figure 3 is a cross-sectional diagram IJ showing the configuration of a sodium-sulfur battery.
This is an I diagram. 2... Anode metal container, 3... Insulator ring, 4...
- Cathode metal container, 5... beta alumina tube.
Claims (2)
容器の上端部と絶縁体リングを介して接合され且つ溶融
金属ナトリウムを貯留する陰極金属容器と、前記絶縁体
リングの内周部に接合され且つナトリウムイオンを選択
的に透過させる機能を有するベータアルミナ固体電解質
管とからなるナトリウム−硫黄電池において、前記絶縁
体リングと少なくとも陰極金属容器の下端部とが、ガラ
スを介して接合されてなることを特徴とするナトリウム
−硫黄電池。(1) An anode metal container that stores molten sulfur, a cathode metal container that is connected to the upper end of the anode metal container via an insulator ring and stores molten metal sodium, and an inner peripheral portion of the insulator ring. In a sodium-sulfur battery comprising a beta alumina solid electrolyte tube that is bonded to the tube and has a function of selectively permeating sodium ions, the insulator ring and at least the lower end of the cathode metal container are bonded via glass. A sodium-sulfur battery characterized by:
容器の上端部と絶縁体リングを介して接合され且つ溶融
金属ナトリウムを貯留する陰極金属容器と、前記絶縁体
リングの内周部に接合され且つナトリウムイオンを選択
的に透過させる機能を有するベータアルミナ固体電解質
管とからなるナトリウム−硫黄電池を製造する方法にお
いて、前記絶縁体リングの少なくとも陰極金属容器と接
する面上にゾル状態としたガラス成分を塗布後焼成して
ガラス被覆層を形成し、次いで該絶縁体リングと陰極金
属容器の下端部とを熱圧接合することを特徴とするナト
リウム−硫黄電池の製造方法。(2) an anode metal container that accommodates molten sulfur; a cathode metal container that is connected to the upper end of the anode metal container via an insulator ring and stores molten metal sodium; and an inner peripheral portion of the insulator ring. A method for manufacturing a sodium-sulfur battery comprising a beta-alumina solid electrolyte tube connected to the tube and having a function of selectively permeating sodium ions, wherein at least the surface of the insulator ring in contact with the cathode metal container is in a sol state. 1. A method for manufacturing a sodium-sulfur battery, which comprises applying and baking a glass component to form a glass coating layer, and then bonding the insulator ring and the lower end of the cathode metal container under heat and pressure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63275084A JP2541642B2 (en) | 1988-10-31 | 1988-10-31 | Sodium-sulfur battery and method of manufacturing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63275084A JP2541642B2 (en) | 1988-10-31 | 1988-10-31 | Sodium-sulfur battery and method of manufacturing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02121270A true JPH02121270A (en) | 1990-05-09 |
| JP2541642B2 JP2541642B2 (en) | 1996-10-09 |
Family
ID=17550588
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63275084A Expired - Lifetime JP2541642B2 (en) | 1988-10-31 | 1988-10-31 | Sodium-sulfur battery and method of manufacturing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2541642B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001035527A (en) * | 1999-07-22 | 2001-02-09 | Ngk Spark Plug Co Ltd | Insulating ring and manufacture thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5961480U (en) * | 1982-10-18 | 1984-04-21 | 株式会社ユアサコーポレーション | sodium-sulfur battery |
| JPS6017870A (en) * | 1983-07-11 | 1985-01-29 | Yuasa Battery Co Ltd | Sodium-sulfur battery |
| JPS6366862A (en) * | 1986-09-05 | 1988-03-25 | Ngk Insulators Ltd | Sodium-sulfur battery |
-
1988
- 1988-10-31 JP JP63275084A patent/JP2541642B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5961480U (en) * | 1982-10-18 | 1984-04-21 | 株式会社ユアサコーポレーション | sodium-sulfur battery |
| JPS6017870A (en) * | 1983-07-11 | 1985-01-29 | Yuasa Battery Co Ltd | Sodium-sulfur battery |
| JPS6366862A (en) * | 1986-09-05 | 1988-03-25 | Ngk Insulators Ltd | Sodium-sulfur battery |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001035527A (en) * | 1999-07-22 | 2001-02-09 | Ngk Spark Plug Co Ltd | Insulating ring and manufacture thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2541642B2 (en) | 1996-10-09 |
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