JPH02278671A - Sodium-sulphur cell - Google Patents
Sodium-sulphur cellInfo
- Publication number
- JPH02278671A JPH02278671A JP1099803A JP9980389A JPH02278671A JP H02278671 A JPH02278671 A JP H02278671A JP 1099803 A JP1099803 A JP 1099803A JP 9980389 A JP9980389 A JP 9980389A JP H02278671 A JPH02278671 A JP H02278671A
- Authority
- JP
- Japan
- Prior art keywords
- sodium
- ring
- alumina
- lid
- cathode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- BNOODXBBXFZASF-UHFFFAOYSA-N [Na].[S] Chemical compound [Na].[S] BNOODXBBXFZASF-UHFFFAOYSA-N 0.000 title claims description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 12
- 239000011521 glass Substances 0.000 claims abstract description 5
- 230000002093 peripheral effect Effects 0.000 claims abstract description 4
- 230000000630 rising effect Effects 0.000 claims abstract description 4
- 239000007769 metal material Substances 0.000 claims description 5
- 239000003779 heat-resistant material Substances 0.000 claims description 3
- 229910010272 inorganic material Inorganic materials 0.000 claims description 2
- 239000011147 inorganic material Substances 0.000 claims description 2
- 229910001415 sodium ion Inorganic materials 0.000 claims description 2
- 229910000978 Pb alloy Inorganic materials 0.000 claims 1
- -1 aluminum-oxygen-sodium-silicon Chemical compound 0.000 claims 1
- 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 abstract description 13
- 229910052708 sodium Inorganic materials 0.000 abstract description 13
- 239000011734 sodium Substances 0.000 abstract description 13
- 229910000679 solder Inorganic materials 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 238000010276 construction Methods 0.000 abstract description 2
- 238000009421 internal insulation Methods 0.000 abstract 1
- 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 abstract 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000000835 fiber Substances 0.000 description 3
- 239000006183 anode active material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/39—Accumulators not provided for in groups H01M10/05-H01M10/34 working at high temperature
- H01M10/3909—Sodium-sulfur cells
-
- 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−硫黄電池に関するもので、さらに
詳しく言えば陽極活物質の利用率が向上できる電池の構
造に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a sodium-sulfur battery, and more particularly to a battery structure that can improve the utilization rate of anode active material.
従来技術とその問題点
ナトリウム−硫黄電池は、陰極活物質としてのナトリウ
ムと、陽極活物質としての硫黄とをβ′−アルミナの如
きナトリウムイオン伝導性の固体電解質管により分離さ
せてなる完全密閉構造の高温型二次電池である。Conventional technology and its problems Sodium-sulfur batteries have a completely sealed structure in which sodium as a cathode active material and sulfur as an anode active material are separated by a sodium ion conductive solid electrolyte tube such as β'-alumina. This is a high-temperature secondary battery.
このようなナトリウム−硫黄電池の従来の横造を第２図
により説明する。固体電解質管１の上端にα−アルミナ
リング２がガラス半田接合され、このα−アルミナリン
グ２の上面に陰極蓋３が、下面に陽ｆＭ蓋４がそれぞれ
熱圧接合されている。前面陰極蓋６には陰極端子５が溶
接されるとともに、その中央部を貫通して陽極集電体と
しての陰極バイブロが溶接され、その下方は前記固体電
解質管１内に挿入されている。The conventional horizontal construction of such a sodium-sulfur battery will be explained with reference to FIG. An α-alumina ring 2 is bonded to the upper end of the solid electrolyte tube 1 by glass soldering, and a cathode cover 3 is bonded to the upper surface of the α-alumina ring 2, and a positive fM cover 4 is bonded to the lower surface thereof by thermopressure. A cathode terminal 5 is welded to the front cathode lid 6, and a cathode vibro serving as an anode current collector is welded to pass through the center of the cathode lid 6, and the lower part thereof is inserted into the solid electrolyte tube 1.
この固体電解質管１内には金属繊維７が配され、約１５
０℃の保湿下において前記陰極バイブロより固体電解質
管１内を排気した後、同温度で溶融させたナトリウム８
が真空充填され、充填後＠極端子５の上端は封止される
。このような陰極室構成体は、円筒形の硫黄成型体１０
が内挿され、陽極集電端子１１が溶接された陽極集電体
を兼ねる電槽９内に挿入され、陽極集電端子１１を外側
に折り曲げるとともに、その上端は前記陽極Ｍ４と真空
溶接されて完全密閉される。Metal fibers 7 are disposed inside this solid electrolyte tube 1, and approximately 15
After evacuating the inside of the solid electrolyte tube 1 from the cathode vibro in a moist environment at 0°C, sodium 8 melted at the same temperature.
is vacuum filled, and after filling, the upper end of the electrode terminal 5 is sealed. Such a cathode chamber structure consists of a cylindrical sulfur molded body 10.
is inserted into the battery case 9, which also serves as an anode current collector, to which the anode current collector terminal 11 is welded.The anode current collector terminal 11 is bent outward, and its upper end is vacuum welded to the anode M4. Completely sealed.
上記の如き構造のナトリウム−硫黄電池では、長期に渡
って運転を続けると、α−アルミナリング２と陰極蓋３
との熱圧接合部がナトリウム８によって腐食され、気密
性か低下してナトリウム８が漏出しやすくなるという欠
点があった。In a sodium-sulfur battery with the above structure, if the operation continues for a long time, the α-alumina ring 2 and the cathode lid 3
There was a drawback that the hot-pressure joint with the metal was corroded by the sodium 8, and the airtightness deteriorated, making it easy for the sodium 8 to leak out.
こうしてナトリウム８が漏出すると、発火したり、陽極
側と接触して電気的に短緒するなどして集合された他の
正常な電池４にも悪影箒な及ぼす可能性があった。If the sodium 8 leaked in this way, there was a possibility that it would catch fire, or that it would come in contact with the anode side and shorten the electrical connection, which would have an adverse effect on the other normal batteries 4 that were assembled together.
発明の目的
本発明は上記欠点を解消するもので、α−アルミナリン
グの内周縁部に円筒部側をガラス半田接合することによ
り、陰極蓋とα−アルミナリングとの熱圧接合部のナト
リウムによる腐食防止を目的とするものである。Purpose of the Invention The present invention solves the above-mentioned drawbacks by bonding the cylindrical part side to the inner circumferential edge of the α-alumina ring with glass solder, thereby reducing the heat-pressure joint between the cathode lid and the α-alumina ring due to sodium. The purpose is to prevent corrosion.
発明の構成
本発明のナトリウム−硫黄電池は、α−アルミナリング
の内周縁部に円筒部利なガラス半田接合するとともに、
前記α−アルミナリングの上面に熱圧接合された陰極蓋
の立ち上がり部の内側と前記円筒部材の外側との間隙に
耐熱側斜と金属材料とを充填し、前記円筒部材の上縁部
を陰極端子の下面に接触させる如く陰極蓋を陰極端子に
溶接したものである。Structure of the Invention The sodium-sulfur battery of the present invention has a cylindrical portion joined to the inner peripheral edge of an α-alumina ring with a glass solder,
The gap between the inside of the rising part of the cathode lid bonded to the upper surface of the α-alumina ring by heat pressure and the outside of the cylindrical member is filled with a heat-resistant side slope and a metal material, and the upper edge of the cylindrical member is used as a cathode. The cathode cover is welded to the cathode terminal so that it contacts the bottom surface of the terminal.
実施例
以下実施例により説明する。第１図は本発明のナトリウ
ム−硫黄電池の断面図で、第２図と共通する部分には同
じ符号を付している。固体電解質管１は、その上部が開
放された外径４５關、内径６８咽、長さ４００馴のβ′
−アルミナからなり、その上部開放端に外径５６ａｍ、
内径６８闘、高さ１０朋のα−アルミナリング２をガラ
ス半田接合する。さらに、前記α−アルミナリング２の
内周縁部に外径６７闘、内径６３朋、高す２０ｆ１ｍの
α−アルミナ製の円筒部１１２ｉその上縁部が前記α−
アルミナリング２の上面から約１０咽の位置にくるよう
にガラス半Ｈ］１６によって接合する。次に、前記α−
アルミナリング２の上面に内ａ４１ｆｉ？＋１、外径５
６＋＋ｕａ、高さ１５ｍｍの断面かＬ字状の陰極蓋６を
熱圧接合し、この陰極蓋６の立ち上かり部の内側と前記
円筒部材１２の外側との間に間隙を形成する。また、＝
５−
同時に前記α−アルミナリング２の下面に陽極蓋４を熱
圧接合する。こうして前記間隙にアルミニウムー酸素−
すＦリウムーシリコン系の無機材料からなる耐熱材料１
４を約５ｍｍの高さまで充填し、約１００℃、約１時間
の予備加熱によって水分を除去した後、約２５０ ′Ｃ
，約２時間の加熱によって固化させた。次に、固体電解
質管１内に金属繊維７を、後述する硫黄成型体１０と同
一の高さまで充填するとともに、固化した耐熱側斜１４
の上に金属材料１５としての鉛リングを配した後、前記
円筒部材１２の上縁部を、陰極バイブロを貫通させた陰
極端子５の下面に接触させる如く、陰極蓋３を陰極端子
５に溶接し、従来と同様にナトリウム８を真空充填して
＠極端子５の上端を封止する。こうして得られた陰極室
構成体を、硫黄成型体１０が内挿された電槽？内に装着
し、電槽９の上端を前記陽極蓋４に溶接して完成電池と
する。なお、前記金属材料１５としての鉛リングは、電
池を作動温度まで昇温させると溶融して熱圧接合部に生
じている微小な空隙を埋める作用をする。EXAMPLES The present invention will be explained below using examples. FIG. 1 is a sectional view of the sodium-sulfur battery of the present invention, and parts common to FIG. 2 are designated by the same reference numerals. The solid electrolyte tube 1 has an outer diameter of 45 mm, an inner diameter of 68 mm, and a length of 400 mm, with its top open.
- made of alumina, with an outer diameter of 56 am at its upper open end;
An α-alumina ring 2 with an inner diameter of 68mm and a height of 10mm is joined with glass solder. Further, on the inner peripheral edge of the α-alumina ring 2, an α-alumina cylindrical portion 112i having an outer diameter of 67 mm, an inner diameter of 63 mm, and a height of 20 f1 m is attached to the upper edge of the α-alumina ring 2.
The alumina ring 2 is joined with a glass half-hole 16 so as to be located about 10 degrees from the top surface. Next, the α-
A41fi inside on the top surface of alumina ring 2? +1, outer diameter 5
A cathode lid 6 having an L-shaped cross section and a height of 15 mm and a height of 6++ ua is bonded under heat and pressure, and a gap is formed between the inside of the rising portion of the cathode lid 6 and the outside of the cylindrical member 12. Also, =
5- At the same time, the anode cover 4 is bonded to the lower surface of the α-alumina ring 2 by thermopressure. In this way, aluminum-oxygen-
Heat-resistant material 1 made of F-silicon based inorganic material
4 to a height of approximately 5 mm, and after removing moisture by preheating at approximately 100°C for approximately 1 hour, heat to approximately 250'C.
, and was solidified by heating for about 2 hours. Next, metal fibers 7 are filled into the solid electrolyte tube 1 to the same height as a sulfur molded body 10, which will be described later, and the solidified heat-resistant side slope 14 is filled with metal fibers 7.
After placing a lead ring as a metal material 15 on top, the cathode lid 3 is welded to the cathode terminal 5 so that the upper edge of the cylindrical member 12 contacts the lower surface of the cathode terminal 5 through which the cathode vibro is passed. Then, the upper end of the @electrode terminal 5 is sealed by vacuum filling with sodium 8 as in the conventional case. The cathode chamber structure obtained in this way is used as a battery case in which the sulfur molded body 10 is inserted. The upper end of the battery case 9 is welded to the anode cover 4 to complete the battery. Note that the lead ring as the metal material 15 melts when the temperature of the battery is raised to the operating temperature, and acts to fill the minute voids formed in the thermopressure joint.
今、第１図のような本発明電池と第２図のような従来電
池とをそれぞれ１０セルずつ製作し、３５０℃において
１日１サイクルの充放電サイクル試験を行い、６か月、
１年、２年経過後に無作為に所定数を抜き取ってナトリ
ウムの漏出の有無を調査した結果を表−１に示す。Now, we fabricated 10 cells each of the inventive battery as shown in Figure 1 and the conventional battery as shown in Figure 2, and conducted a charge/discharge cycle test at 350°C for 6 months.
Table 1 shows the results of randomly sampling a predetermined number of samples after 1 or 2 years to check for sodium leakage.
表 −１
表−１から従来電池はナトリウムの漏出が認められたの
に対し１本発明電池では詔められなかった。また、ナト
リウムの漏出が詔められた電池はすべて短絡または短終
に近い状態であった。Table 1 From Table 1, leakage of sodium was observed in the conventional battery, but not in the battery of the present invention. Additionally, all of the batteries that were suspected of leaking sodium were short-circuited or near-terminated.
発明の効果
実施例において詳述した如く、本発明のナトリウム−硫
黄電池はナトリウムの漏出が防止できるので、電池の毒
命を長くすることができる。Effects of the Invention As described in detail in the embodiments, the sodium-sulfur battery of the present invention can prevent sodium leakage, thereby extending the battery life.
第１図は本発明のナトリウム−硫黄′ＦＪＡ、油の断面
図、第２図は従来のナトリウム−硫１１Ｊ電油の陶８面
図である。FIG. 1 is a sectional view of the sodium-sulfur 'FJA' oil of the present invention, and FIG. 2 is a sectional view of the conventional sodium-sulfur 11J electric oil.
Claims (3)
α−アルミナリングがガラス半田接合され、このα−ア
ルミナリングの上面に断面がＬ字状の陰極蓋が熱圧接合
され、この陰極蓋に溶接された陰極端子によって前記固
体電解質管内に陰極室を形成するとともに、前記α−ア
ルミナリングの下面に陽極蓋が熱圧接合され、この陽極
蓋に前記固体電解質管を下方から被包する如く電槽を溶
接し、固体電解質管と電槽との間隙に陽極室を形成して
なるナトリウム−硫黄電池において、前記α−アルミナ
リングの内周縁部に円筒部材をガラス半田接合するとと
もに、前記α−アルミナリングの上面に熱圧接合された
陰極蓋の立ち上がり部の内側と前記円筒部材の外側との
間隙に耐熱材料と金属材料とを充填し、前記円筒部材の
上縁部を陰極端子の下面に接触させる如く陰極蓋を陰極
端子に溶接したことを特徴とするナトリウム−硫黄電池
。(1) An α-alumina ring is glass soldered to the upper end of a solid electrolyte tube that conducts sodium ions, and a cathode lid with an L-shaped cross section is heat-pressure joined to the top surface of this α-alumina ring. A cathode chamber is formed in the solid electrolyte tube by the welded cathode terminal, and an anode cover is thermo-pressure bonded to the lower surface of the α-alumina ring, and the anode cover is fitted with an electrode so as to cover the solid electrolyte tube from below. In a sodium-sulfur battery in which a tank is welded and an anode chamber is formed in the gap between the solid electrolyte tube and the battery case, a cylindrical member is glass soldered to the inner peripheral edge of the α-alumina ring, and the α- A heat-resistant material and a metal material are filled in the gap between the inside of the rising part of the cathode lid, which is thermo-pressure bonded to the top surface of the alumina ring, and the outside of the cylindrical member, and the upper edge of the cylindrical member is attached to the bottom surface of the cathode terminal. 1. A sodium-sulfur battery characterized in that a cathode lid is welded to a cathode terminal so that they are in contact with each other.
リコン系の無機材料である請求項第１項記載のナトリウ
ム−硫黄電池。(2) The sodium-sulfur battery according to claim 1, wherein the heat-resistant material is an inorganic material based on aluminum-oxygen-sodium-silicon.
載のナトリウム−硫黄電池。(3) The sodium-sulfur battery according to claim 1, wherein the metal material is lead or a lead alloy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1099803A JPH02278671A (en) | 1989-04-19 | 1989-04-19 | Sodium-sulphur cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1099803A JPH02278671A (en) | 1989-04-19 | 1989-04-19 | Sodium-sulphur cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02278671A true JPH02278671A (en) | 1990-11-14 |
Family
ID=14257037
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1099803A Pending JPH02278671A (en) | 1989-04-19 | 1989-04-19 | Sodium-sulphur cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02278671A (en) |
-
1989
- 1989-04-19 JP JP1099803A patent/JPH02278671A/en active Pending
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