JPH02244564A - Manufacture of sodium-sulfur battery - Google Patents
Manufacture of sodium-sulfur batteryInfo
- Publication number
- JPH02244564A JPH02244564A JP1063696A JP6369689A JPH02244564A JP H02244564 A JPH02244564 A JP H02244564A JP 1063696 A JP1063696 A JP 1063696A JP 6369689 A JP6369689 A JP 6369689A JP H02244564 A JPH02244564 A JP H02244564A
- Authority
- JP
- Japan
- Prior art keywords
- glass
- alumina
- thermal expansion
- sodium
- strength
- 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 8
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000011521 glass Substances 0.000 claims abstract description 31
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 5
- RPMPQTVHEJVLCR-UHFFFAOYSA-N pentaaluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3] RPMPQTVHEJVLCR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000010292 electrical insulation Methods 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 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 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 2
- 239000010405 anode material Substances 0.000 claims description 2
- 239000010406 cathode material Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229910001415 sodium ion Inorganic materials 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 10
- 230000007797 corrosion Effects 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 5
- 229910052681 coesite Inorganic materials 0.000 abstract description 4
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 4
- 239000000377 silicon dioxide Substances 0.000 abstract description 4
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 4
- 229910052682 stishovite Inorganic materials 0.000 abstract description 4
- 229910052905 tridymite Inorganic materials 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 238000009413 insulation Methods 0.000 abstract 1
- 239000000843 powder Substances 0.000 abstract 1
- 239000002002 slurry Substances 0.000 abstract 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 101100348017 Drosophila melanogaster Nazo gene Proteins 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
- H01M50/183—Sealing members
- H01M50/186—Sealing members characterised by the disposition of the sealing members
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/39—Accumulators not provided for in groups H01M10/05-H01M10/34 working at high temperature
- H01M10/3909—Sodium-sulfur cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
- H01M50/183—Sealing members
- H01M50/184—Sealing members characterised by their shape or structure
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
- H01M50/183—Sealing members
- H01M50/19—Sealing members characterised by the material
- H01M50/191—Inorganic material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はナトリウム−硫黄電池に係り、特に固体電解質
β“−アルミナ管と電気絶縁用α−アルミナリングとの
ガラス接合に好適な製法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a sodium-sulfur battery, and more particularly to a manufacturing method suitable for glass bonding a solid electrolyte β"-alumina tube and an electrically insulating α-alumina ring.
従来の固体電解質β′−アルミナ管と電気絶縁用α−ア
ルミナリングとの接合は、特開昭５５−１４０７３２号
公報に記載のように、主成分が２８〜４８モル％ＢｚＯ
３０〜２０モル％Ｓｉ○２−１６〜２８モル％Ａｌ２２
０２１にＢａＯ，ＣａＯ等のアルカリ土類酸化物１８〜
３３モル％の組成からなる、熱膨張係数く２０〜５００
℃）が５゜７９〜６．４０ Ｘ １０”−８／ ’Ｃの
ガラスを用いて接合し密封していた。Conventional bonding between a solid electrolyte β'-alumina tube and an electrically insulating α-alumina ring is performed using a method in which the main component is 28 to 48 mol% BzO, as described in JP-A-55-140732.
30-20 mol% Si○2-16-28 mol% Al22
021 with alkaline earth oxides such as BaO and CaO 18~
Composed of 33 mol%, thermal expansion coefficient 20-500
They were bonded and sealed using glass with a temperature of 5°79 to 6.40 x 10''-8/'C.
上記従来技術は溶融ナトリウム、多硫化ナトリウムとの
耐食性及び接合体のガラスに圧縮応力を残留させること
を主体としており、接合体の接合強度と熱膨張係数差と
の関係については配慮されておらず、接合体としての適
正熱膨張係数差については不明であり、ガラスの組成も
リング状に成形するための成形性を考慮して７成分系と
多成分系であり、ガラス作成上成分調整がはん雑である
などの問題があった。The above conventional technology mainly focuses on corrosion resistance with molten sodium and sodium polysulfide and leaving compressive stress in the glass of the bonded body, but does not consider the relationship between the bonding strength of the bonded body and the difference in coefficient of thermal expansion. However, the appropriate difference in coefficient of thermal expansion for a bonded body is unknown, and the composition of the glass is a 7-component system and a multi-component system in consideration of the formability for forming into a ring shape, and it is difficult to adjust the components when making the glass. There were problems such as being sloppy.
本発明の目的は接合強度面から最も好ましい熱膨張係数
を有し、かつ耐食性に優れた３成分系ガラスを用いて固
体電解質β′−アルミナと電気絶縁用α−アルミナリン
グとを気密接合することにある。The purpose of the present invention is to airtightly bond a solid electrolyte β'-alumina and an electrically insulating α-alumina ring using a three-component glass having the most preferable coefficient of thermal expansion from the viewpoint of bonding strength and excellent corrosion resistance. It is in.
上記目的は熱膨張係数を少なくともβ′−アルミナとα
−アルミナより小さくかつ接合時にβ”−アルミナに働
く力が極力少なく、かつ耐食性の面からＳｉＯ２の上限
を６３モル％としたＳ ｉ Ｏ２−Ｂ ｚ○５−Ｎａｚ
Ｏの３組成系ガラスの適正組成のものを用いることによ
り達成される。The above purpose is to increase the coefficient of thermal expansion at least between β′-alumina and α
- Smaller than alumina, the force acting on β''-alumina during bonding is as small as possible, and the upper limit of SiO2 is set to 63 mol% from the viewpoint of corrosion resistance.S i O2-B z○5-Naz
This can be achieved by using a three-component O glass having an appropriate composition.
すなわち本発明は、陽極物質が硫黄、陰極物質がナトリ
ウムからなり作動温度で液状となるナトリウム−硫黄二
次電池であって、ナトリウムイオン伝導性固体電解質β
“−アルミナ袋管開放端と電気絶縁用α−アルミナリン
グとをガラスで密封するす１−リウムー硫黄屯池の製法
において、α−アルミナ、β′−アルミナの熱膨張係数
よりも１〜ｌ０ＸＩＯ””／’Ｃ（室温から３５０℃の
はん囲において）小さい熱膨張係数を有するガラスを用
いることを特徴とする。尚、５０〜６３モル％ＳｉＯｘ
、２’１〜４０モル％Ｂ ｘ Ｏａ％ １０〜】：３モ
ル％Ｎ ａ ２０−の組成からなるガラスを用いること
が望ましい。That is, the present invention provides a sodium-sulfur secondary battery in which the anode material is sulfur and the cathode material is sodium, which becomes liquid at operating temperature, and which comprises a sodium ion conductive solid electrolyte β.
“-In the method of manufacturing a 1-lium-sulfur tube in which the open end of an alumina bag tube and an α-alumina ring for electrical insulation are sealed with glass, the coefficient of thermal expansion of α-alumina and β’-alumina is 1 to 10XIO.” It is characterized by using glass having a small coefficient of thermal expansion (in the range from room temperature to 350°C).In addition, 50 to 63 mol% SiOx
, 2'1 to 40 mol% B x Oa% 10 to]: 3 mol% Na 20- It is desirable to use a glass having the following composition.
す［・ワウ１１−硫黄電池に用いられている固体電解質
用のβ１−アルミナ及び電気絶縁用のα−アルミナの熱
膨張係数は室温から５００℃の範囲で７２ ｘ １０−
′／℃である。これらを接合するガラスの熱膨張係数が
両アルミナのそれより大きい場合は接合後ガラスの表面
に引張り応力が残留する。The coefficient of thermal expansion of β1-alumina for solid electrolyte and α-alumina for electrical insulation used in sulfur batteries is 72 x 10- in the range from room temperature to 500°C.
'/°C. If the coefficient of thermal expansion of the glass to which these are bonded is greater than that of both aluminas, tensile stress remains on the surface of the glass after bonding.
通営ガラスの強度はガラス表面の極微少のキズや欠陥に
対して極めて敏感であり、特に引張り応力が残留した場
合は、強度を著しく低下させる。−方、ガラスの熱膨張
係数が両アルミナより小さい場合は接合後ガラスの表面
に圧縮応力が残留して接合体の強度を向上させるが、あ
まりｔ’Ｓさくなるとガラス内部に割れが発生して強度
を低下させると共に気密性不良を発生するため好ましく
なく画然膨張係数の差が１〜ｌ０ＸＩＯ”／”Ｃの範囲
で良好な強度及び気密性が得られる。」１記の熱膨張係
数を有するガラスは耐食性からＳｉＯ２を最大６３ ｒ
ｎ ｏ Ｑ％に押え、ぬれ性、接合温度等から、５０〜
６０ ｍ ｏ ２％ＳｉＯｘ −２７〜４０ ｒｎ ｏ
１２％Ｂ２Ｏ３−１０〜１３モル％ＮａｚＯ絹成のガ
ラスを用いることにより達成される。The strength of conventional glass is extremely sensitive to minute scratches and defects on the glass surface, and especially when tensile stress remains, the strength decreases significantly. On the other hand, if the coefficient of thermal expansion of the glass is smaller than that of both aluminas, compressive stress will remain on the surface of the glass after bonding, improving the strength of the bonded body, but if the t'S becomes too low, cracks will occur inside the glass. Good strength and airtightness can be obtained when the difference in expansion coefficient is in the range of 1 to 10XIO"/"C, which is not preferable because it lowers the strength and causes poor airtightness. Glasses with a thermal expansion coefficient of 1 are able to hold SiO2 up to 63 r
No: 50 to Q%, based on wettability, bonding temperature, etc.
60 m o 2%SiOx -27~40 rno
This is achieved by using a glass made of 12% B2O3-10-13 mol% NazO.
以下、本発明の一実施例を図により説明する。 Hereinafter, one embodiment of the present invention will be described with reference to the drawings.
第２図にナトリウム−硫黄電池のガラス接合部の縦断面
図を示す。電気絶縁用α−アルミナリング１の内周面に
テーパ加工を施した外径１５ｍ。FIG. 2 shows a longitudinal cross-sectional view of the glass joint of a sodium-sulfur battery. The inner circumferential surface of an α-alumina ring 1 for electrical insulation is tapered and has an outer diameter of 15 m.
Claims (1)
動温度で液状となるナトリウム−硫黄二次電池であつて
、ナトリウムイオン伝導性固体電解質β″−アルミナ袋
管開放端と電気絶縁用α−アルミナリングとをガラスで
密封するナトリウム−硫黄電池の製法において、α−ア
ルミナ及びβ″−アルミナの熱膨張係数よりも１〜１０
×１０＾−＾７／℃（室温から３５０℃のはん囲におい
て）小さい熱膨張係数を有するガラスを用いることを特
徴とするナトリウム−硫黄電池の製法。 ２、５０〜６３モル％ＳｉＯ＿２、２７〜４０モル％Ｂ
＿２Ｏ＿３、１０〜１３モル％Ｎａ＿２Ｏ、の組成から
なるガラスを用いることを特徴とする請求項１記載のナ
トリウム−硫黄電池の製法。[Claims] 1. A sodium-sulfur secondary battery whose anode material is sulfur and whose cathode material is sodium and becomes liquid at operating temperature, comprising a sodium ion conductive solid electrolyte β″-alumina bag tube at the open end; In the manufacturing method of sodium-sulfur batteries in which an α-alumina ring for electrical insulation is sealed with glass, the thermal expansion coefficient is 1 to 10 higher than that of α-alumina and β″-alumina.
A method for manufacturing a sodium-sulfur battery characterized by using glass having a small coefficient of thermal expansion x10^-^7/°C (in the range from room temperature to 350°C). 2, 50-63 mol% SiO_2, 27-40 mol% B
2. The method for manufacturing a sodium-sulfur battery according to claim 1, characterized in that glass having a composition of _2O_3 and 10 to 13 mol% Na_2O is used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1063696A JP2928530B2 (en) | 1989-03-17 | 1989-03-17 | Sodium-sulfur battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1063696A JP2928530B2 (en) | 1989-03-17 | 1989-03-17 | Sodium-sulfur battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02244564A true JPH02244564A (en) | 1990-09-28 |
| JP2928530B2 JP2928530B2 (en) | 1999-08-03 |
Family
ID=13236801
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1063696A Expired - Lifetime JP2928530B2 (en) | 1989-03-17 | 1989-03-17 | Sodium-sulfur battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2928530B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0355768A (en) * | 1989-07-21 | 1991-03-11 | Tokyo Electric Power Co Inc:The | Joint glass to form sodium-sulfur battery and joint of cylindrical solid electrolyte with bottom to insulation ring using same |
| EP0482785A2 (en) * | 1990-10-25 | 1992-04-29 | Ngk Insulators, Ltd. | Sodium-sulfur cell and method of joining solid electrolyte tube and insulative ring |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55140732A (en) * | 1979-04-19 | 1980-11-04 | Chloride Silent Power Ltd | Sealing glass |
| JPS59150176U (en) * | 1983-03-28 | 1984-10-06 | 株式会社ユアサコーポレーション | sodium-sulfur battery |
-
1989
- 1989-03-17 JP JP1063696A patent/JP2928530B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55140732A (en) * | 1979-04-19 | 1980-11-04 | Chloride Silent Power Ltd | Sealing glass |
| JPS59150176U (en) * | 1983-03-28 | 1984-10-06 | 株式会社ユアサコーポレーション | sodium-sulfur battery |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0355768A (en) * | 1989-07-21 | 1991-03-11 | Tokyo Electric Power Co Inc:The | Joint glass to form sodium-sulfur battery and joint of cylindrical solid electrolyte with bottom to insulation ring using same |
| EP0482785A2 (en) * | 1990-10-25 | 1992-04-29 | Ngk Insulators, Ltd. | Sodium-sulfur cell and method of joining solid electrolyte tube and insulative ring |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2928530B2 (en) | 1999-08-03 |
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