JPH10284119A - Sodium-sulfur battery - Google Patents

Sodium-sulfur battery

Info

Publication number
JPH10284119A
JPH10284119A JP9090511A JP9051197A JPH10284119A JP H10284119 A JPH10284119 A JP H10284119A JP 9090511 A JP9090511 A JP 9090511A JP 9051197 A JP9051197 A JP 9051197A JP H10284119 A JPH10284119 A JP H10284119A
Authority
JP
Japan
Prior art keywords
sodium
heat
carbon
battery
sulfur
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
Application number
JP9090511A
Other languages
Japanese (ja)
Other versions
JP3253888B2 (en
Inventor
Michitaka Hidaka
道孝 日高
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
NGK Insulators Ltd
Original Assignee
NGK Insulators Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by NGK Insulators Ltd filed Critical NGK Insulators Ltd
Priority to JP09051197A priority Critical patent/JP3253888B2/en
Publication of JPH10284119A publication Critical patent/JPH10284119A/en
Application granted granted Critical
Publication of JP3253888B2 publication Critical patent/JP3253888B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

PROBLEM TO BE SOLVED: To provide a sodium-sulfur battery equipped with a protection plate, excellent in heat resistance and corrosion resistance, having an electric insulation property, and high in mechanical strength and simple in handling. SOLUTION: A battery 7 made by connecting a plurality of sodium-sulfur cells 6 is housed in a heat insulating container 1 and a protection plate 8 composed of a material having heat resistance and corrosion resistance is disposed in the heat insulating container 1 so as to confront at least an upper surface of the battery 7. The protection plate 8 comprizes a multilayer plate of inorganic heat-resistant insulation sheets made up of carbon paper, carbon cloth, carbon felt, or a graphite mat as base material and by impregnating a mixture containing an electrically insulating substance into the base material.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【0001】[0001]

【発明の属する技術分野】 本発明は、無機耐熱絶縁シ
ートを保護板として使用したナトリウム−硫黄電池に関
するものである。
[0001] The present invention relates to a sodium-sulfur battery using an inorganic heat-resistant insulating sheet as a protective plate.

【0002】[0002]

【従来の技術】 ナトリウム−硫黄電池は、例えば夜間
電力貯蔵に用いられる高温電池であり、通常は断熱容器
内に単電池を複数接続して集合電池とする構造を採って
いる。この種のナトリウム−硫黄電池においては、事故
短絡電流等の過電流が流れると、単電池内部の固体電解
質管が破壊されるため、当該固体電解質管により内外に
区分されていた溶融金属ナトリウムと溶融硫黄が直接接
触し、互いに混合して化学反応を起こすことがある。
2. Description of the Related Art A sodium-sulfur battery is, for example, a high-temperature battery used for nighttime power storage, and usually employs a structure in which a plurality of cells are connected in an insulated container to form a collective battery. In this type of sodium-sulfur battery, when an overcurrent such as an accidental short-circuit current flows, the solid electrolyte tube inside the unit cell is destroyed, so that the molten metal sodium separated from the inside and outside by the solid electrolyte tube melts. Sulfur may come into direct contact and mix with each other to cause a chemical reaction.

【0003】 このような場合には、反応熱により単電
池自体のカバーが破壊され、高温の火炎や高温腐食性の
活物質が集合電池を収容した断熱容器を溶融破壊して外
部に放出されることにより、火災事故が容器外に波及す
る危険性があった。そこで、溶融金属ナトリウムと溶融
硫黄の化学反応に伴う反応熱、高温の火炎、若しくは高
温腐食性の活物質による断熱容器の破壊を防止するた
め、集合電池の少なくとも上面に対応するように、例え
ばカーボンやグラファイト等の耐食性、耐熱性材料より
なる保護板を配置することが提案されている(特開平5
−062708号公報)。
In such a case, the cover of the unit cell itself is destroyed by the reaction heat, and a high-temperature flame or a high-temperature corrosive active material melts and destroys the heat-insulating container housing the assembled battery and is released to the outside. As a result, there was a risk that a fire accident would spread outside the container. Therefore, in order to prevent the heat of reaction associated with the chemical reaction between molten metal sodium and molten sulfur, a high-temperature flame, or a high-temperature corrosive active material from destruction of the heat-insulating container, at least corresponding to at least the upper surface of the battery pack, for example, carbon It has been proposed to dispose a protective plate made of a corrosion-resistant or heat-resistant material such as graphite or graphite (Japanese Patent Application Laid-Open No. Hei 5 (1993) -207).
-062708).

【0004】[0004]

【発明が解決しようとする課題】 しかしながら、カー
ボン又はグラファイト材は、耐食性、耐熱性には優れる
ものの導電性を有しており、断熱容器と単電池との電気
的絶縁を確保するために、前記カーボン又はグラファイ
ト材の上面及び下面に例えばマイカシート等の絶縁材料
を配置しなければならなかった。この場合、保護板の構
造が複雑となる上、生産時の不具合や輸送時の振動によ
って前記マイカシートの位置がずれ、電気的絶縁が破壊
されることによって、電池に悪影響を生じるケースがあ
った。
However, the carbon or graphite material is excellent in corrosion resistance and heat resistance, but has conductivity, and in order to ensure electrical insulation between the heat insulating container and the unit cell, the carbon or graphite material is used. For example, an insulating material such as a mica sheet has to be disposed on the upper and lower surfaces of the carbon or graphite material. In this case, the structure of the protective plate becomes complicated, and the position of the mica sheet shifts due to a problem during production or vibration during transportation, and electrical insulation is destroyed, which may cause a bad influence on the battery. .

【0005】 また、カーボン又はグラファイト材は材
質的に脆く割れ易いため、機械的強度が保持できず、電
池組立時や電池輸送時の取扱いが困難であり、また、破
損等があった場合には、カーボン又はグラファイト材の
破片が電池上に落下して短絡の原因ともなっていた。本
発明は、このような従来技術の問題に鑑みてなされたも
のであって、その目的とするところは、耐熱性、耐食性
に優れ、電気絶縁性を有し、かつ、機械的強度が高く、
取扱いが簡易な保護板を備えたナトリウム−硫黄電池を
提供することにある。
[0005] In addition, carbon or graphite materials are brittle and fragile in terms of material, cannot maintain mechanical strength, and are difficult to handle during battery assembly and battery transport. Also, fragments of carbon or graphite material fell on the battery, causing a short circuit. The present invention has been made in view of such problems of the prior art, and aims at having excellent heat resistance, excellent corrosion resistance, electrical insulation, and high mechanical strength,
An object of the present invention is to provide a sodium-sulfur battery provided with a protection plate that is easy to handle.

【0006】[0006]

【課題を解決するための手段】 本発明によれば、断熱
容器内に複数のナトリウム−硫黄単電池を接続した集合
電池を収納し、前記集合電池の少なくとも上面と対応す
るように、前記断熱容器内に耐熱性、耐食性を有する材
料よりなる保護板を配置したナトリウム−硫黄電池であ
って、前記保護板が、カーボンペーパー、カーボンクロ
ス、カーボンフェルト、若しくはグラファイトマットを
基材とし、前記基材に電気絶縁性物質を含有する混合物
を含浸してなる無機耐熱絶縁シートの積層板により構成
されることを特徴とするナトリウム−硫黄電池が提供さ
れる。
According to the present invention, a battery pack in which a plurality of sodium-sulfur single cells are connected is housed in a heat insulating container, and the heat insulating container is arranged so as to correspond to at least the upper surface of the battery pack. A sodium-sulfur battery in which a protective plate made of a material having heat resistance and corrosion resistance is arranged, wherein the protective plate is made of carbon paper, carbon cloth, carbon felt, or graphite mat as a base material, and the base material A sodium-sulfur battery is provided, which is constituted by a laminate of an inorganic heat-resistant insulating sheet impregnated with a mixture containing an electrically insulating substance.

【0007】 また、本発明においては、前記保護板
が、基材に電気絶縁性物質を含有する混合物を均一に散
布、若しくは塗布した後に、温度100〜200℃、圧
力5〜100Kgf/cm2の条件で熱圧プレスするこ
とにより含浸してなる無機耐熱絶縁シートの積層板によ
り構成されることが好ましい。さらに、本発明において
は、電気絶縁性物質を含有する混合物が、シリコーン樹
脂100部に対し、酸化マグネシウム50〜350部を
混合した組成物であることが好ましい。
Further, in the present invention, after the protective plate uniformly scatters or applies a mixture containing an electrically insulating substance to a substrate, the protective plate has a temperature of 100 to 200 ° C. and a pressure of 5 to 100 kgf / cm 2 . It is preferable to be constituted by a laminated plate of an inorganic heat-resistant insulating sheet impregnated by hot pressing under conditions. Further, in the present invention, the mixture containing the electrically insulating substance is preferably a composition in which 50 to 350 parts of magnesium oxide is mixed with 100 parts of the silicone resin.

【0008】[0008]

【発明の実施の形態】 本発明のナトリウム−硫黄電池
では、カーボン又はグラファイト等の耐食性、耐熱性に
優れた基材に電気絶縁性物質を含有する混合物を含浸さ
せた無機耐熱絶縁シートの積層板を保護板として使用す
る。こうすることにより、耐熱性と耐食性は基材のカー
ボン又はグラファイト等により、電気絶縁性と機械的強
度はカーボン又はグラファイト等の組織間に含浸させた
電気絶縁性物質を含有する混合物により保持されるた
め、耐熱性、耐食性に優れ、かつ、電気絶縁性と機械的
強度が高い保護板を備えたナトリウム−硫黄電池を製造
することができる。
BEST MODE FOR CARRYING OUT THE INVENTION In the sodium-sulfur battery of the present invention, a laminate of an inorganic heat-resistant insulating sheet in which a mixture containing an electrically insulating substance is impregnated into a substrate having excellent corrosion resistance and heat resistance such as carbon or graphite. Is used as a protective plate. By doing so, heat resistance and corrosion resistance are maintained by carbon or graphite or the like of the base material, and electrical insulation and mechanical strength are maintained by a mixture containing an electrically insulating material impregnated between tissues such as carbon or graphite. Therefore, it is possible to manufacture a sodium-sulfur battery excellent in heat resistance and corrosion resistance and provided with a protective plate having high electrical insulation and high mechanical strength.

【0009】 以下、本発明のナトリウム−硫黄電池の
構成について図面を参照しながら詳細に説明する。ナト
リウム−硫黄電池は、通常、図1に示すように、断熱容
器1は四角箱型に形成され、外壁2と内壁3の間に断熱
材4を介装して構成されており、該断熱容器1の側面開
口部は前記断熱容器1と同様に外壁2と内壁3の間に断
熱材4を介装した断熱プラグ5により閉鎖される。さら
に、前記断熱容器1内には集合電池7を形成する複数個
のナトリウム−硫黄単電池6が立設配置される。
Hereinafter, the configuration of the sodium-sulfur battery of the present invention will be described in detail with reference to the drawings. In a sodium-sulfur battery, as shown in FIG. 1, a heat insulating container 1 is generally formed in a rectangular box shape, and a heat insulating material 4 is interposed between an outer wall 2 and an inner wall 3. The side opening 1 is closed by a heat insulating plug 5 in which a heat insulating material 4 is interposed between an outer wall 2 and an inner wall 3 similarly to the heat insulating container 1. Further, a plurality of sodium-sulfur single cells 6 forming a collective battery 7 are arranged upright in the heat insulating container 1.

【0010】 該ナトリウム−硫黄単電池6内には、活
物質である金属ナトリウム及び硫黄が固体電解質管によ
り隔離収納されており、前記断熱容器の内底部に収容配
置された電気ヒータにより断熱容器の内部を300〜3
50℃に加熱し、両活物質を溶融してイオンを移動させ
ることにより電気化学反応を行わせて所定のエネルギー
を得る構造となっている。なお、図1において、10は
内部フレーム、11は支持部材、12は支持ピンを示す
ものとする。
In the sodium-sulfur single cell 6, metallic sodium and sulfur as active materials are separated and stored by a solid electrolyte tube, and an electric heater disposed at the inner bottom of the heat insulating container is used to cool the heat insulating container. 300-3 inside
Heating to 50 ° C., melting both the active materials and moving the ions causes an electrochemical reaction to be performed to obtain a predetermined energy. In FIG. 1, reference numeral 10 denotes an internal frame, 11 denotes a support member, and 12 denotes a support pin.

【0011】 従来は、図2に示すように、集合電池7
の少なくとも上面に、好ましくは上面及び下面に対応し
て、カーボン若しくはグラファイトよりなる保護板8を
配置し、断熱容器内での火災が発生した際の高温の火炎
や高温腐食性の活物質により断熱容器が破壊されるのを
防止するとともに、前記保護板の上面及び下面に、例え
ばマイカシート等の絶縁材料9を配置して断熱容器と集
合電池との電気的絶縁を確保していた。
Conventionally, as shown in FIG.
A protective plate 8 made of carbon or graphite is arranged on at least the upper surface, preferably corresponding to the upper surface and the lower surface, and is insulated by a high-temperature flame or a high-temperature corrosive active material when a fire occurs in the heat insulating container. In addition to preventing the container from being destroyed, an insulating material 9 such as a mica sheet is disposed on the upper and lower surfaces of the protection plate to ensure electrical insulation between the heat insulating container and the battery pack.

【0012】 本発明においては、前記保護板と絶縁材
料に代えて、カーボンペーパー、カーボンクロス、カー
ボンフェルト、若しくはグラファイトマットを基材と
し、該基材に電気絶縁性物質を含有する混合物を含浸し
た無機耐熱絶縁シートの積層板からなる保護板8のみを
配設することを特徴とする。以下、無機耐熱絶縁シート
について詳細に説明する。
In the present invention, carbon paper, carbon cloth, carbon felt, or graphite mat is used as a base material instead of the protective plate and the insulating material, and the base material is impregnated with a mixture containing an electrically insulating substance. It is characterized in that only the protective plate 8 made of a laminate of inorganic heat-resistant insulating sheets is provided. Hereinafter, the inorganic heat-resistant insulating sheet will be described in detail.

【0013】 本発明において、無機耐熱絶縁シートの
基材としてはカーボンペーパー、カーボンクロス、カー
ボンフェルト、若しくはグラファイトマットを用いる。
これらの素材は、従来より保護板として用いられている
素材であって、耐食性、耐熱性に優れているため、溶融
金属ナトリウムと溶融硫黄の化学反応に伴う反応熱、高
温の火炎、若しくは高温腐食性の活物質による断熱容器
の破壊を防止するための基材として好適に用いることが
できる。
In the present invention, carbon paper, carbon cloth, carbon felt, or graphite mat is used as a base material of the inorganic heat-resistant insulating sheet.
These materials have been conventionally used as protective plates, and are excellent in corrosion resistance and heat resistance. Therefore, the heat of reaction associated with the chemical reaction between molten metal sodium and molten sulfur, high-temperature flame, or high-temperature corrosion It can be suitably used as a base material for preventing the destruction of the heat insulating container by the active material.

【0014】 また、本発明では、前記の基材に電気絶
縁性物質を含む混合物を含浸させる。こうすることによ
り、カーボン、グラファイト等の電気伝導体を基材とし
て用いた場合でも電気的絶縁は確保され、従前のように
保護板の上面及び下面に別途マイカシート等の絶縁材料
を配置することは不要となる。さらには、生産時、輸送
時におけるマイカシートのズレ、若しくはカーボン、グ
ラファイトシートの破損に伴うマイカシートの破損によ
って、電池内の電気的絶縁が破壊されることも防止でき
る。
In the present invention, the base material is impregnated with a mixture containing an electrically insulating substance. By doing so, electrical insulation is ensured even when an electric conductor such as carbon or graphite is used as a base material, and an insulating material such as a mica sheet is separately disposed on the upper and lower surfaces of the protective plate as before. Becomes unnecessary. Further, it is possible to prevent the electrical insulation in the battery from being broken due to the displacement of the mica sheet during production or transportation, or the damage of the mica sheet due to the damage of the carbon or graphite sheet.

【0015】 また、カーボン、グラファイトは、耐熱
性、耐食性に優れるものの、素材としては脆さがあり機
械的強度は低いという問題があるが、前記の含浸処理に
よって、カーボン、グラファイトの組織間に電気絶縁性
物質等が浸透するため、機械的強度をも高めることがで
きる。従って、保護板の破損による高温の火炎や高温腐
食性活物質の流出、さらには剥離片による電気的絶縁の
破壊が防止でき、取扱いも簡易なものとなる。さらに、
本発明においては、無機耐熱絶縁シートを積層板として
用いるため、仮に一のシートに破損があった場合でも、
他のシートにより上記の効果は保持される。
Although carbon and graphite are excellent in heat resistance and corrosion resistance, there is a problem that the material is brittle and has low mechanical strength. Since the insulating material or the like permeates, the mechanical strength can also be increased. Accordingly, it is possible to prevent a high-temperature flame or a high-temperature corrosive active material from flowing out due to breakage of the protection plate, and furthermore, to prevent the electrical insulation from being broken by the stripped pieces, and to simplify the handling. further,
In the present invention, since the inorganic heat-resistant insulating sheet is used as a laminate, even if one sheet is damaged,
The effect described above is maintained by the other sheets.

【0016】 含浸の方法としては、電気絶縁性物質を
含む混合物を基材となるカーボンペーパー、カーボンク
ロス、カーボンフェルト、若しくはグラファイトマット
に均一に散布又は塗布し、熱圧プレスする方法を用い
る。使用する電気絶縁性物質は特に限定されないが、例
えばシリコーン樹脂と酸化マグネシウムの混合物等を用
いることができる。この際の混合比率は、シリコーン樹
脂100部に対して酸化マグネシウム50〜350部を
混合することが好ましい。また、熱圧プレスの条件とし
ては、熱硬化性樹脂を使用するため、温度100〜20
0℃、圧力5〜100Kgf/cm2であることが好ま
しい。
As a method of impregnation, a method of uniformly spraying or applying a mixture containing an electrically insulating substance to a carbon paper, a carbon cloth, a carbon felt, or a graphite mat serving as a base material and performing hot-pressing is used. The electric insulating material to be used is not particularly limited. For example, a mixture of a silicone resin and magnesium oxide can be used. The mixing ratio at this time is preferably such that 50 to 350 parts of magnesium oxide are mixed with 100 parts of the silicone resin. In addition, as for the conditions of the hot pressing, a temperature of 100 to 20 is used because a thermosetting resin is used.
The temperature is preferably 0 ° C. and the pressure is 5 to 100 kgf / cm 2 .

【0017】 本発明に係る無機耐熱絶縁シートは、例
えば以下の如く製造する。まず、シリコーン樹脂100
部に対して、酸化マグネシウム50〜350部を混合し
てバインダーを調製する。次いで、当該バインダーの含
有量が35〜97%になるようにカーボンペーパーに塗
布し、温度100〜200℃、圧力5〜100Kgf/
cm2の条件で熱圧プレスを行ってバインダーを含浸
し、シート状とする。このシート状物を少なくとも2枚
以上重ね合わせ、温度100〜200℃、圧力5〜10
0Kgf/cm2の条件で、再度熱圧プレスを行って積
層板とし、無機耐熱絶縁シートとする。
The inorganic heat-resistant insulating sheet according to the present invention is manufactured, for example, as follows. First, silicone resin 100
The binder is prepared by mixing 50 to 350 parts of magnesium oxide per part. Next, it is applied to carbon paper so that the content of the binder is 35 to 97%, and the temperature is 100 to 200 ° C., the pressure is 5 to 100 kgf /
The binder is impregnated by hot pressing under the condition of cm 2 to form a sheet. At least two or more of these sheets are stacked, and the temperature is 100 to 200 ° C., the pressure is 5 to 10
Under the condition of 0 Kgf / cm 2 , hot press is performed again to obtain a laminated board, which is an inorganic heat-resistant insulating sheet.

【0018】(性能評価)上記のように製造した無機耐
熱絶縁シート及び他の材質の電気抵抗、ナトリウム−硫
黄強制燃焼試験、酸素−アセチレン燃焼試験、コストの
各項目について性能評価を行い比較した結果を表1に示
す。なお、ナトリウム−硫黄強制燃焼試験、酸素−アセ
チレン燃焼試験については、以下に説明する方法で行っ
た。
(Evaluation of Performance) Performance evaluation was performed for each item of the electrical resistance, the sodium-sulfur forced combustion test, the oxygen-acetylene combustion test, and the cost of the inorganic heat-resistant insulating sheet and other materials produced as described above, and the results of comparison were made. Are shown in Table 1. The sodium-sulfur forced combustion test and the oxygen-acetylene combustion test were performed by the methods described below.

【0019】(ナトリウム−硫黄強制燃焼試験)図3に
示すように、60φのSUS製反応管13内に断熱材1
4、砂15、マイカ坩堝16の順で装填した後に、33
gのナトリウム17と120g(60g×2)の硫黄1
8をサンドイッチ状に積層して充填し、反応管13の開
口端上方10mmの位置に250mm角の検討試料19
を水平に配置する。次いで前記反応管13を下方から約
250℃まで加熱し、検討試料19の外観及び孔の有無
について観察した。
(Sodium-Sulfur Forced Combustion Test) As shown in FIG. 3, a heat insulating material 1 was placed in a 60φ SUS reaction tube 13.
4, after loading sand 15 and mica crucible 16 in this order,
g of sodium 17 and 120 g (60 g × 2) of sulfur 1
8 are stacked and filled in a sandwich shape, and a 250 mm square examination sample 19 is placed 10 mm above the open end of the reaction tube 13.
Is placed horizontally. Next, the reaction tube 13 was heated from below to about 250 ° C., and the appearance of the examination sample 19 and the presence or absence of holes were observed.

【0020】(酸素−アセチレン燃焼試験)図4に示す
ように、火口径0.6φの中切り用切断吹管(No.
1)20を用い、吹管先端より50mmの位置に250
mm角の検討試料21を垂直に配置する。次いで、20
00℃以上のアセチレン炎で検討試料21を加熱し、貫
通孔が開くまでの時間を測定した。
(Oxygen-acetylene combustion test) As shown in FIG.
1) Use 20 and place 250 mm at a position 50 mm from the tip of the blowpipe.
The study sample 21 of mm square is arranged vertically. Then, 20
The test sample 21 was heated with an acetylene flame of 00 ° C. or higher, and the time until the through-hole was opened was measured.

【0021】[0021]

【表1】 [Table 1]

【0022】 表1に示すように、SUS板、石膏ボー
ド、アルミナコージェライト板、SIC板、マイカシー
ト等は燃焼試験で損傷が大きく、耐熱性、耐食性の面か
ら保護板として使用するのは不適である。また、燃焼試
験では、試料番号7のアルミナファイバーボード、カー
ボンフレキシブルシート、カーボンシートが良好な結果
を示したものの電気絶縁効果に乏しく、従前と同様に絶
縁材料を配置しなければならない。これに対し、本発明
の無機耐熱絶縁シートは、燃焼試験、電気抵抗とも問題
がなく、保護板として良好な性能を示した。
As shown in Table 1, SUS plate, gypsum board, alumina cordierite plate, SIC plate, mica sheet, etc. are greatly damaged in a combustion test and are unsuitable for use as a protective plate in terms of heat resistance and corrosion resistance. It is. In the combustion test, the alumina fiber board, carbon flexible sheet, and carbon sheet of Sample No. 7 showed good results, but had poor electrical insulation effect, and an insulating material had to be disposed as before. On the other hand, the inorganic heat-resistant insulating sheet of the present invention did not have any problem in the combustion test and the electric resistance, and showed good performance as a protective plate.

【0023】 以上のように、本発明に係る無機絶縁耐
熱シートにおいては、基材となるカーボン、グラファイ
トにより耐食性、耐熱性が担保され、含浸させた電気絶
縁性物質により断熱容器と単電池との絶縁が確保され
る。また、含浸により基材のカーボン、グラファイトの
組織間に電気絶縁性物質が浸透するため、機械的強度が
低く、脆さのあるカーボン、グラファイトを補強する効
果もある。従って、基材の破損を防止できるほか、基材
の剥離による絶縁不良も防止することができる。
As described above, in the inorganic insulating heat-resistant sheet according to the present invention, the corrosion resistance and heat resistance are ensured by carbon and graphite serving as the base material, and the heat insulating container and the unit cell are sealed by the impregnated electric insulating material. Insulation is ensured. In addition, since the electrically insulating substance permeates between the carbon and graphite structures of the base material due to the impregnation, it has the effect of reinforcing the brittle carbon and graphite having low mechanical strength. Therefore, not only can the base material be prevented from being damaged, but also insulation failure due to peeling of the base material can be prevented.

【0024】[0024]

【発明の効果】 以上説明したように、本発明のナトリ
ウム−硫黄電池によれば、従来通り保護板の耐食性、耐
熱性は担保され、かつ、電気絶縁性及び機械的強度が向
上するため、断熱容器内で火災が起こっても断熱容器が
破壊されないとともに、新たに絶縁材料を配置する必要
がなく、電池組立時、若しくは輸送時の取扱いも簡易な
ものとなる。
As described above, according to the sodium-sulfur battery of the present invention, the corrosion resistance and heat resistance of the protective plate are ensured, and the electrical insulation and the mechanical strength are improved as in the prior art. Even if a fire occurs in the container, the heat insulating container is not destroyed, and there is no need to newly provide an insulating material, so that handling during battery assembly or transportation is simplified.

【図面の簡単な説明】[Brief description of the drawings]

【図1】 本発明の一の実施例を示す断面図である。FIG. 1 is a sectional view showing one embodiment of the present invention.

【図2】 従来技術の一の実施例を示す断面図である。FIG. 2 is a cross-sectional view showing one embodiment of the prior art.

【図3】 ナトリウム−硫黄強制燃焼試験の試験方法を
示す概略図である。
FIG. 3 is a schematic diagram showing a test method of a sodium-sulfur forced combustion test.

【図4】 酸素−アセチレン燃焼試験の試験方法を示す
概略図である。
FIG. 4 is a schematic view showing a test method of an oxygen-acetylene combustion test.

【符号の説明】[Explanation of symbols]

1…断熱容器、2…外壁、3…内壁、4…断熱材、5…
断熱プラグ、6…単電池、7…集合電池、8…保護板、
9…絶縁材料、10…内部フレーム、11…支持部材、
12…支持ピン、13…反応管、14…断熱材、15…
砂、16…マイカ坩堝、17…ナトリウム、18…硫
黄、19…検討試料、20…切断吹管、21…検討試
料。
DESCRIPTION OF SYMBOLS 1 ... Insulated container, 2 ... Outer wall, 3 ... Inner wall, 4 ... Insulation material, 5 ...
Insulation plug, 6 ... unit cell, 7 ... collective battery, 8 ... protective plate,
9: insulating material, 10: inner frame, 11: support member,
12 ... support pin, 13 ... reaction tube, 14 ... heat insulating material, 15 ...
Sand, 16: mica crucible, 17: sodium, 18: sulfur, 19: examination sample, 20: cutting blow tube, 21: examination sample.

Claims (3)

【特許請求の範囲】[Claims] 【請求項1】 断熱容器内に複数のナトリウム−硫黄単
電池を接続した集合電池を収納し、 前記集合電池の少なくとも上面と対応するように、前記
断熱容器内に耐熱性、耐食性を有する材料よりなる保護
板を配置したナトリウム−硫黄電池であって、 前記保護板が、 カーボンペーパー、カーボンクロス、カーボンフェル
ト、若しくはグラファイトマットを基材とし、 該基材に電気絶縁性物質を含有する混合物を含浸してな
る無機耐熱絶縁シートの積層板により構成されることを
特徴とするナトリウム−硫黄電池。
1. A heat-resistant and corrosion-resistant material is housed in a heat-insulating container so as to correspond to at least the upper surface of the battery and accommodates a battery assembly in which a plurality of sodium-sulfur cells are connected. A protective plate, wherein the protective plate is made of carbon paper, carbon cloth, carbon felt, or graphite mat as a base material, and the base material is impregnated with a mixture containing an electrically insulating material. A sodium-sulfur battery comprising a laminate of an inorganic heat-resistant insulating sheet formed as described above.
【請求項2】 保護板が、基材に電気絶縁性物質を含有
する混合物を均一に散布、若しくは塗布した後に、温度
100〜200℃、圧力5〜100Kgf/cm2の条
件で熱圧プレスすることにより含浸してなる無機耐熱絶
縁シートの積層板により構成される請求項1に記載のナ
トリウム−硫黄電池。
2. A protective plate, after uniformly spraying or applying a mixture containing an electrically insulating substance to a substrate, hot pressing under a condition of a temperature of 100 to 200 ° C. and a pressure of 5 to 100 kgf / cm 2. The sodium-sulfur battery according to claim 1, which is constituted by a laminated plate of an inorganic heat-resistant insulating sheet impregnated thereby.
【請求項3】 電気絶縁性物質を含有する混合物が、シ
リコーン樹脂100部に対し、酸化マグネシウム50〜
350部を混合した組成物である請求項1又は2に記載
のナトリウム−硫黄電池。
3. A mixture containing an electrically insulating substance is mixed with 100 parts of a silicone resin based on 50 to 50 parts of magnesium oxide.
3. The sodium-sulfur battery according to claim 1, wherein the composition is a mixture of 350 parts.
JP09051197A 1997-04-09 1997-04-09 Sodium-sulfur battery Expired - Fee Related JP3253888B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP09051197A JP3253888B2 (en) 1997-04-09 1997-04-09 Sodium-sulfur battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP09051197A JP3253888B2 (en) 1997-04-09 1997-04-09 Sodium-sulfur battery

Publications (2)

Publication Number Publication Date
JPH10284119A true JPH10284119A (en) 1998-10-23
JP3253888B2 JP3253888B2 (en) 2002-02-04

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ID=14000505

Family Applications (1)

Application Number Title Priority Date Filing Date
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Country Status (1)

Country Link
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WO2014042149A1 (en) * 2012-09-12 2014-03-20 日本碍子株式会社 Sodium-sulfur battery
WO2014054633A1 (en) * 2012-10-02 2014-04-10 日本碍子株式会社 Coated cell and module battery
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WO2014042149A1 (en) * 2012-09-12 2014-03-20 日本碍子株式会社 Sodium-sulfur battery
JPWO2014042149A1 (en) * 2012-09-12 2016-08-18 日本碍子株式会社 Sodium sulfur battery
US9742040B2 (en) 2012-09-12 2017-08-22 Ngk Insulators, Ltd. Sodium-sulfur battery
WO2014054633A1 (en) * 2012-10-02 2014-04-10 日本碍子株式会社 Coated cell and module battery
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JPWO2014054633A1 (en) * 2012-10-02 2016-08-25 日本碍子株式会社 Coated cell and module battery
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US10468650B2 (en) 2014-10-29 2019-11-05 Lg Chem, Ltd. Lithium sulfur battery

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