JP3355377B2 - Sodium / molten salt battery - Google Patents
Sodium / molten salt batteryInfo
- Publication number
- JP3355377B2 JP3355377B2 JP31988695A JP31988695A JP3355377B2 JP 3355377 B2 JP3355377 B2 JP 3355377B2 JP 31988695 A JP31988695 A JP 31988695A JP 31988695 A JP31988695 A JP 31988695A JP 3355377 B2 JP3355377 B2 JP 3355377B2
- Authority
- JP
- Japan
- Prior art keywords
- container
- negative electrode
- soft metal
- solid electrolyte
- safety
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Secondary Cells (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ナトリウム／溶融
塩電池に係り、特に、夜間電力貯蔵用や電気自動車用な
どの大電力貯蔵用電池の安全性と信頼性の向上に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sodium / molten salt battery, and more particularly, to an improvement in safety and reliability of a large power storage battery for nighttime power storage and electric vehicles.
【０００２】[0002]
【従来の技術】ナトリウム／溶融塩電池としては、Ｎａ
／Ｓ電池，Ｎａ／ＦｅＣｌ電池，Ｎａ／Ｓｅ電池等多数
存在するが、本発明は、負極にＮａを使う電池に共通す
る問題点を解決しょうとするもので、以下Ｎａ／Ｓ電池
を例に取り上げて説明する。従来のＮａ／Ｓ電池は、図
２に示すように、固体電解質容器１、例えばβーアルミ
ナ、β”ーアルミナ等を介して負極活物質(Ｎａ)６と正
極活物質(Ｓ)５が対峙している。正極(Ｓ極)は、Ｓと電
子伝導体の役割を果たす補助導電材(グラファイトフェ
ルト)で構成される。負極(Ｎａ極)では、負極容器４に
溶接され宙吊りされた安全容器８内にＮａが貯蔵され、
電池反応に必要なＮａは安全容器８の底部に設けられた
Ｎａ供給孔７から流出させ、固体電解質容器１に供給す
る。2. Description of the Related Art As a sodium / molten salt battery, Na
Although there are many such batteries as Na / S batteries, Na / FeCl batteries, and Na / Se batteries, the present invention is intended to solve the problems common to batteries using Na for the negative electrode. Take it up and explain. In the conventional Na / S battery, as shown in FIG. 2, a negative electrode active material (Na) 6 and a positive electrode active material (S) 5 face each other via a solid electrolyte container 1, for example, β-alumina, β ″ -alumina or the like. The positive electrode (S-pole) is composed of S and an auxiliary conductive material (graphite felt) serving as an electronic conductor, while the negative electrode (Na-pole) is inside a safety container 8 that is welded to the negative electrode container 4 and suspended in the air. Na is stored in
The Na required for the battery reaction flows out of the Na supply hole 7 provided at the bottom of the safety container 8 and is supplied to the solid electrolyte container 1.
【０００３】従って、安全容器の役割は、電池反応に不
要な大半のＮａを貯蔵し、仮に固体電解質容器が破損し
てもＮａとＳの直接反応に寄与するＮａ量を抑制して、
電池の安全性を確保することである。上記目的から、安
全容器と固体電解質容器とのギャップは狭いほどＮａと
Ｓの直接反応に寄与するＮａ量が少なくなり安全であ
る。さらに、図２の構造では、安全容器は電池で発生す
る電力を取り出す電極の機能も果たしている。尚、安全
容器が固体電解質容器内に収納されているのは、電池の
体積エネルギー密度をできるだけ大きく維持するためで
ある。Therefore, the role of the safety container is to store most of the Na unnecessary for the battery reaction, and to suppress the amount of Na that contributes to the direct reaction between Na and S even if the solid electrolyte container is damaged,
It is to ensure the safety of the battery. For the above purpose, the narrower the gap between the safety container and the solid electrolyte container, the smaller the amount of Na contributing to the direct reaction between Na and S, which is safe. Further, in the structure of FIG. 2, the safety container also functions as an electrode for extracting electric power generated by the battery. The reason why the safety container is housed in the solid electrolyte container is to maintain the volume energy density of the battery as large as possible.
【０００４】しかしながら、安全性確保のために設けた
安全容器が、図２のように負極容器と溶接で剛接合(金
属材料の持つ剛性を保持して接合と定義)されている
と、溶接時の熱変形によって、安全容器と固体電解質容
器間のギャップ２２は一様にはならず、したがって、安
全容器が固体電解質容器に接触しないギャップ寸法とし
て１．６ｍｍ前後が必要であり、ギャップ寸法を１ｍｍ
以下に縮小することは困難である。However, if the safety container provided for ensuring safety is rigidly joined to the negative electrode container by welding as shown in FIG. 2 (defined as joining while maintaining the rigidity of the metal material), the The gap 22 between the safety container and the solid electrolyte container is not uniform due to the thermal deformation of the solid container. Therefore, the gap size where the safety container does not contact the solid electrolyte container needs to be around 1.6 mm, and the gap size is 1 mm.
It is difficult to reduce to below.
【０００５】このような状態で電池運転のために電池温
度を300〜350℃に昇温したり、降温すると安全容器及び
負極容器が熱応力によって変形し、安全容器に接触した
固体電解質容器には不適切な応力が印加される場合があ
る。この傾向は、真直度や真円度の悪い固体電解質容器
において顕著である。固体電解質容器は、焼結体であり
金属加工のようには製作精度が上がらず、真直度や真円
度の向上が、困難である。固体電解質容器に印加される
応力が許容応力を越えれば、固体電解質容器は破損する
ことになる。When the battery temperature is raised to 300 to 350 ° C. or the temperature is lowered for the operation of the battery in such a state, the safety container and the negative electrode container are deformed by thermal stress, and the solid electrolyte container in contact with the safety container is Improper stress may be applied. This tendency is remarkable in a solid electrolyte container having poor straightness or roundness. Since the solid electrolyte container is a sintered body, its manufacturing accuracy is not improved as in the case of metal processing, and it is difficult to improve straightness and roundness. If the stress applied to the solid electrolyte container exceeds the allowable stress, the solid electrolyte container will be damaged.
【０００６】更に、安全容器にからむ固体電解質容器の
破損原因として、負極端子１６の変形による応力が考え
られる。これは、ナトリウム／溶融塩電池を電力貯蔵用
に使用する場合には、多数本の電池を直・並列に接続す
る必要があり、かつ、大電力となるため、低抵抗のブス
バーが必要となり、勢い太く剛性の強い材料となる。以
上のように、従来のように剛接合した安全容器では固体
電解質破損後のＮａとＳの直接反応を抑制するには効果
があるが、固体電解質の破損確率を高めてしまう虞れが
あった。Further, as a cause of breakage of the solid electrolyte container wrapped around the safety container, a stress due to deformation of the negative electrode terminal 16 is considered. This is because when using a sodium / molten salt battery for power storage, it is necessary to connect a number of batteries in series and parallel, and the power becomes large, so a low-resistance busbar is required. The material becomes thick and strong. As described above, the conventional rigidly joined safety container is effective in suppressing the direct reaction between Na and S after the breakage of the solid electrolyte, but may increase the probability of breakage of the solid electrolyte. .
【０００７】一方、安全性を向上させるため特開昭60-1
2681号公報に開示された技術では、固体電解質内にＮａ
の入った安全容器を置かずに、Ｎａの入ったナトリウム
リザーバーを固体電解質外部に設置し、固体電解質内に
はガスを充填した金属容器を設置している。これは、固
体電解質が破損しても金属容器内のガスがナトリウムリ
ザーバーからのＮａ供給を抑え、ＮａとＳの直接反応量
を抑制して安全を確保するためである。そして、電池容
量に応じて必要となるＮａを固体電解質外部のナトリウ
ムリザーバー内に貯蔵しているため、電池の発電の重要
な要素項目である体積エネルギー密度は、図２に示すよ
うな従来電池に比べ４０％程度である。On the other hand, in order to improve safety,
In the technique disclosed in Japanese Patent No. 2681, Na is contained in the solid electrolyte.
The sodium reservoir containing Na is installed outside the solid electrolyte without a safety container containing the gas, and a metal container filled with gas is installed inside the solid electrolyte. This is because even if the solid electrolyte is broken, the gas in the metal container suppresses the supply of Na from the sodium reservoir and suppresses the direct reaction amount between Na and S to ensure safety. And, since the Na required according to the battery capacity is stored in the sodium reservoir outside the solid electrolyte, the volume energy density which is an important element item of the power generation of the battery is different from that of the conventional battery as shown in FIG. It is about 40% in comparison.
【０００８】[0008]
【発明が解決しようとする課題】上記したように従来技
術では、安全性と高い体積エネルギー密度とを両立させ
ることができなかった。すなわち、Ｎａ／Ｓ電池のＮａ
の貯蔵された安全容器が負極容器と剛接合されている場
合には、電池の温度上昇時あるいは下降時に安全容器の
熱変形によって、固体電解質を破損させる問題点があっ
た。また、安全を向上するために、Ｎａの貯蔵されたナ
トリウムリザーバーを固体電解質容器外に設置すれば、
電池の寸法が大きくなり、体積エネルギー密度が低下す
るという問題点があった。As described above, in the prior art, it was not possible to achieve both safety and high volume energy density. That is, the Na / S battery Na
When the safety container in which the battery is stored is rigidly connected to the negative electrode container, there is a problem that the solid electrolyte is damaged by thermal deformation of the safety container when the temperature of the battery rises or falls. In addition, in order to improve safety, if a sodium reservoir storing Na is installed outside the solid electrolyte container,
There is a problem that the size of the battery is increased and the volume energy density is reduced.
【０００９】さらに、Ｎａ／Ｓ電力貯蔵装置では、数多
くの電池を直並列に接続して使用することになるが、１
本の電池の固体電解質が破損して、電池内部が短絡する
と、これらの電池に接続された他の集合電池から大きな
短絡電流が流れ、他の健全な電池の破損にも繋がる心配
があった。さらにまた、正極と負極の電気絶縁をする電
気絶縁材と負極容器及び正極容器とのあいだの電池シー
ル部、即ち熱圧接部が安全容器の熱変形で破損した場
合、シール部からは電池活物質が漏出し、電池内部で短
絡する。その結果、電池内部に短絡電流が流れ、電池内
は大きなジュール発熱により高温となり、電池容器の破
損に繋がる虞れがあった。Further, in the Na / S power storage device, many batteries are connected in series and used in parallel.
If the solid electrolyte of the battery is damaged and the inside of the battery is short-circuited, a large short-circuit current flows from other assembled batteries connected to these batteries, which may lead to damage of other healthy batteries. Furthermore, when the battery seal portion between the electric insulating material for electrically insulating the positive electrode and the negative electrode and the negative electrode container and the positive electrode container, that is, the heat-pressed portion is damaged by thermal deformation of the safety container, the battery active material is removed from the seal portion. Leaks and short-circuits inside the battery. As a result, a short-circuit current flows inside the battery, and the inside of the battery becomes high temperature due to large Joule heat, which may lead to damage to the battery container.
【００１０】したがって本発明の目的は、固体電解質の
破損と体積エネルギー密度の低下がなく、安全性と信頼
性の高いナトリウム／溶融塩電池を提供することにあ
る。Accordingly, it is an object of the present invention to provide a safe and reliable sodium / molten salt battery without breakage of the solid electrolyte and reduction in volume energy density.
【００１１】[0011]
【課題を解決するための手段】上記目的を達成する本発
明の特徴は、固体電解質容器と負極容器とで負極活物質
を収納するために形成された負極側空間の固体電解質容
器内に配設された安全容器が、固体電解質容器に対面
し、対面している該安全容器の外面形状が、固体電解質
容器の内面形状に相対し両面間に一様なる狭い間隙を形
成し、該間隙に充填され形成された負極活物質の薄膜
が、当該安全容器を浮遊支持していることにある。A feature of the present invention that achieves the above object is that a solid electrolyte container and a negative electrode container are provided in a solid electrolyte container in a space on the negative electrode side formed for housing a negative electrode active material. The formed safety container faces the solid electrolyte container, and the outer shape of the safety container facing the inner surface shape of the solid electrolyte container forms a uniform narrow gap between both surfaces opposite to the inner shape of the solid electrolyte container. The formed thin film of the negative electrode active material floats and supports the safety container.
【００１２】また本発明の別の特徴は、正極容器と負極
容器とで形成される空間内に固体電解質容器を配設し、
前記正極容器と前記固体電解質容器とで囲まれた正極側
空間内に正極活物質を収納し、前記負極容器と前記固体
電解質容器とで囲まれた負極側空間内に負極活物質を収
納し、前記固体電解質容器が固体電解質として機能する
ように電気絶縁材を介し前記３つの容器を絶縁接合して
成る電池容器を有し、該電池容器は、前記負極側空間の
前記固体電解質容器内に安全容器を有し、該安全容器
は、前記固体電解質容器と対面している当該安全容器の
下部周囲において前記固体電解質容器と前記安全容器間
に介在している前記負極活物質の薄膜によって浮遊支持
され、かつ、当該安全容器の上部に導電性を有する軟金
属を溜める軟金属溜めを有し、前記負極容器と対面して
いる該軟金属溜めにおいて前記負極容器と前記軟金属溜
め間に介在している前記軟金属によって浮遊支持されて
いることにある。本発明によれば、固体電解質の破損と
体積エネルギー密度の低下が回避され、安全性と信頼性
の高いナトリウム／溶融塩電池が提供される。Another feature of the present invention is that a solid electrolyte container is disposed in a space formed by a positive electrode container and a negative electrode container,
A positive electrode active material is stored in a positive electrode side space surrounded by the positive electrode container and the solid electrolyte container, and a negative electrode active material is stored in a negative electrode side space surrounded by the negative electrode container and the solid electrolyte container. A battery container formed by insulatingly joining the three containers via an electrical insulating material so that the solid electrolyte container functions as a solid electrolyte; and the battery container is securely disposed in the solid electrolyte container in the negative electrode side space. A container, and the safety container is floatingly supported by a thin film of the negative electrode active material interposed between the solid electrolyte container and the safety container around a lower portion of the safety container facing the solid electrolyte container. And, having a soft metal reservoir for storing a soft metal having conductivity in the upper part of the safety container, in the soft metal reservoir facing the negative electrode container interposed between the negative electrode container and the soft metal reservoir Is In that it is floating supported by Ki軟 metal. ADVANTAGE OF THE INVENTION According to this invention, a sodium / molten salt battery with high safety and high reliability which avoids breakage of a solid electrolyte and lowering of volume energy density is avoided.
【００１３】[0013]
【発明の実施の形態】以下、本発明の実施の形態につい
て、図面を参照し説明する。図１は、本発明による一実
施例のナトリウム／溶融塩電池を示す縦断面図である。
本実施例のナトリウム／溶融塩電池としてのＮａ／Ｓ電
池は、「金属材料」等から成る正極容器３と「金属材料」等
から成る負極容器４の内部に、「β"−アルミナ」等から
成る固体電解質容器１を配設し、正極容器３と固体電解
質容器１とで囲まれた正極側空間に、「Ｓ＋Ｎａ2Ｓｘ」
等からなる正極活物質５を収納し、負極容器４と固体電
解質容器１とで囲まれた負極側空間に、「Ｎａ」等からな
る負極活物質６を収納し、該固体電解質容器１がセパレ
ータとしての固体電解質を形成するように、「α−アル
ミナ」等から成る電気絶縁材２を介し、前述の３つの容
器を熱圧接部１２などの部位にて絶縁接合してなる電池
容器である。Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 is a longitudinal sectional view showing a sodium / molten salt battery according to an embodiment of the present invention.
The Na / S battery as a sodium / molten salt battery according to the present embodiment has a structure in which a positive electrode container 3 made of a “metal material” and the like and a negative electrode container 4 made of a “metal material” and the like contain “β” -alumina and the like. The solid electrolyte container 1 is disposed, and “S + Na 2 Sx” is placed in a positive electrode side space surrounded by the positive electrode container 3 and the solid electrolyte container 1.
The negative electrode active material 6 made of “Na” or the like is stored in a negative electrode side space surrounded by the negative electrode container 4 and the solid electrolyte container 1, and the solid electrolyte container 1 is This is a battery container formed by insulatingly joining the above-described three containers at a portion such as the heat-pressing portion 12 via an electric insulating material 2 made of “α-alumina” or the like so as to form a solid electrolyte as follows.
【００１４】かつ、固体電解質容器１内には、負極活物
質６の大部分の量を収納する安全容器８が固体電解質容
器１に対面して配設される。このとき、安全容器８の外
面形状８ａが固体電解質容器１の内面形状１ａに相対し
両面間にほぼ一様なる狭い間隙を形成するように対面し
ている。そして、該安全容器８の底部には、安全容器８
から固体電解質容器１の表面へ負極活物質６としてのＮ
ａを適宜供給するための、Ｎａ供給孔７が設けられてい
る。このＮａ供給孔７から供給された負極活物質６が前
述の狭い間隙であるギャップ２２に充填され、負極活物
質６の薄膜が形成されている。従って、負極活物質６側
から見れば、負極活物質６の薄膜が安全容器８を支持し
ている。In the solid electrolyte container 1, a safety container 8 containing a large amount of the negative electrode active material 6 is disposed so as to face the solid electrolyte container 1. At this time, the outer surface shape 8a of the safety container 8 is opposed to the inner surface shape 1a of the solid electrolyte container 1 so as to form a substantially uniform narrow gap between both surfaces. The bottom of the safety container 8 has a safety container 8
From the surface of the solid electrolyte container 1 to N as the negative electrode active material 6
A Na supply hole 7 for appropriately supplying a is provided. The negative electrode active material 6 supplied from the Na supply hole 7 is filled in the gap 22, which is the narrow gap, and a thin film of the negative electrode active material 6 is formed. Therefore, when viewed from the negative electrode active material 6 side, the thin film of the negative electrode active material 6 supports the safety container 8.
【００１５】一方、正極側空間内は、正極活物質５と正
極カバーガス空間１４とで占められる。また負極側空間
内は、負極活物質６と安全容器８と負極カバーガス空間
１３とで占められる。そして、充填されている負極活物
質６のイオンが固体電解質容器１を通過移動することに
より発生した電気が、正極容器３に接続されている正極
端子１７及び負極容器４に接続されている負極端子１６
から取り出される。なお、正極端子を正極電極、負極端
子を負極電極と呼称する場合があるが同じものを指して
いる。On the other hand, the space on the positive electrode side is occupied by the positive electrode active material 5 and the positive electrode cover gas space 14. The negative electrode side space is occupied by the negative electrode active material 6, the safety container 8, and the negative electrode cover gas space 13. Then, the electricity generated by the ions of the filled negative electrode active material 6 passing through the solid electrolyte container 1 is used to generate a positive electrode terminal 17 connected to the positive electrode container 3 and a negative electrode terminal connected to the negative electrode container 4. 16
Taken out of The positive terminal may be referred to as a positive electrode and the negative terminal may be referred to as a negative electrode.
【００１６】ところで、本実施例のナトリウム／溶融塩
電池においては、負極容器４の略中央であって安全容器
８の上部に対応する部位に、負極容器４の一部が突出し
た凸部４ａが設けられている。また、安全容器８の上部
であって負極容器４の該凸部４ａに対応する部位に、軟
金属溜め１０が設けられている。そして、凸部４ａの寸
法より軟金属溜め１０の寸法が大きく、凸部４ａが軟金
属溜め１０に収められる構造となっている。さらに、軟
金属溜め１０には、導電性を有する軟金属２４が溜めら
れている。そして、軟金属溜め１０に溜められた軟金属
２４の上に負極容器４の凸部４ａが載っている状態とな
っている。換言すれば、負極容器４の凸部４ａと安全容
器８の軟金属溜め１０、即ち、負極容器４と安全容器８
とが、軟金属２４を介し対面している状態となってい
る。換言して軟金属２４側からみれば、軟金属２４が安
全容器８を支持している。また、安全容器８側からみれ
ば、安全容器８は、前述のギャップ２２に充填されてい
る負極活物質６と、軟金属溜め１０に溜められている軟
金属２４とによって、浮遊支持されていると言える。こ
の浮遊支持された状態においては、負極端子１６，負極
容器４の凸部４ａ，軟金属２４，軟金属溜め１０，安全
容器８が電気的に接続されている。従って、この場合の
負極の電流は、固体電解質容器１からギャップ２２に存
在する負極活物質６の薄膜を経て、安全容器８，軟金属
２４を介し凸部４ａ，負極端子１６へと流れ、電池の充
放電に必要な電流パスが形成されている。Incidentally, in the sodium / molten salt battery of the present embodiment, a convex part 4a from which a part of the negative electrode container 4 protrudes is provided at a position substantially at the center of the negative electrode container 4 and corresponding to the upper part of the safety container 8. Is provided. Further, a soft metal reservoir 10 is provided at a position above the safety container 8 and corresponding to the convex portion 4a of the negative electrode container 4. The size of the soft metal reservoir 10 is larger than the size of the convex portion 4a, so that the convex portion 4a is housed in the soft metal reservoir 10. Further, in the soft metal reservoir 10, a soft metal 24 having conductivity is stored. Then, the convex portion 4a of the negative electrode container 4 is placed on the soft metal 24 stored in the soft metal reservoir 10. In other words, the convex portion 4a of the negative electrode container 4 and the soft metal reservoir 10 of the safety container 8, that is, the negative electrode container 4 and the safety container 8
Are facing each other via the soft metal 24. In other words, when viewed from the soft metal 24 side, the soft metal 24 supports the safety container 8. When viewed from the side of the safety container 8, the safety container 8 is suspended and supported by the negative electrode active material 6 filled in the gap 22 and the soft metal 24 stored in the soft metal reservoir 10. It can be said. In this floating supported state, the negative electrode terminal 16, the convex portion 4a of the negative electrode container 4, the soft metal 24, the soft metal reservoir 10, and the safety container 8 are electrically connected. Therefore, the current of the negative electrode in this case flows from the solid electrolyte container 1 through the thin film of the negative electrode active material 6 existing in the gap 22, flows through the safety container 8, the soft metal 24, to the convex portion 4 a, and the negative electrode terminal 16. A current path necessary for charging / discharging is formed.
【００１７】本発明によれば、上記構造のように安全容
器８が負極容器４に剛接合されずに電気的に接続されつ
つ浮遊支持されているので、熱変形によって固体電解質
容器の許容応力を越えるような安全容器と固体電解質容
器との接触は回避される。この結果、安全容器８と固体
電解質容器１とのギャップ２２のギャップ寸法を、例え
ば、0.1mm以下までにも狭くすることが可能となった。
前述のように従来技術では１ｍｍ以下に狭くすることは
困難であった。According to the present invention, as in the above structure, the safety container 8 is not rigidly joined to the negative electrode container 4 but is supported in a floating manner while being electrically connected to the negative electrode container 4. Therefore, the allowable stress of the solid electrolyte container is reduced by thermal deformation. Such contact between the safety container and the solid electrolyte container is avoided. As a result, the gap size of the gap 22 between the safety container 8 and the solid electrolyte container 1 can be reduced to, for example, 0.1 mm or less.
As described above, it is difficult to reduce the width to 1 mm or less in the conventional technology.
【００１８】したがって、ギャップ２２に保有させる電
池反応に必要なＮａ量を、非常に少ない最低量とするこ
とができ、固体電解質容器１が破損した場合のＮａとＳ
の直接反応が抑制されるので、電池の安全性を十分に確
保することができる。また、ギャップ２２に保有させる
Ｎａ量が必要最低量になることは、電池の小型化に繋が
るものである。Therefore, the amount of Na required for the battery reaction to be held in the gap 22 can be made a very small minimum amount, and Na and S in the case where the solid electrolyte container 1 is broken can be reduced.
Since the direct reaction of the battery is suppressed, the safety of the battery can be sufficiently ensured. Further, the fact that the amount of Na held in the gap 22 becomes the necessary minimum amount leads to the miniaturization of the battery.
【００１９】以上を纏めれば、本発明の特徴は、固体電
解質容器と負極容器とで負極活物質を収納するために形
成された負極側空間の固体電解質容器内に配設された安
全容器は、負極活物質としてのＮａの薄膜を介して固体
電解質容器と接触対面し、かつ、軟金属を介して負極容
器と接触対面することによって、安全容器が負極容器に
剛接合されることなく浮遊支持されている点にある。こ
のとき、負極は固体電解質からＮａの薄膜を経て安全容
器へ、さらに軟金属を介して負極容器へと電流パスが形
成され電池反応が円滑に進行する。また、軟金属として
代用され得る負極活物質が存在するので該負極活物質を
軟金属として兼用することも可であり、換言すれば、負
極活物質としてのＮａを保有する安全容器を、該負極活
物質の薄膜を介して宙吊りにして負極容器とは剛接合し
ないで浮遊支持する点にあるとも言える。In summary, the feature of the present invention is that the safety container disposed in the solid electrolyte container in the space on the negative electrode side formed for storing the negative electrode active material in the solid electrolyte container and the negative electrode container is provided. By contacting and facing the solid electrolyte container via a thin film of Na as a negative electrode active material and contacting the negative electrode container via a soft metal, the safety container is floatingly supported without being rigidly joined to the negative electrode container. In that it is. At this time, a current path is formed from the solid electrolyte to the safety container via the Na thin film through the thin film of Na, and further to the negative electrode container via the soft metal, so that the battery reaction proceeds smoothly. In addition, since there is a negative electrode active material that can be substituted as a soft metal, the negative electrode active material can also be used as a soft metal.In other words, a safety container holding Na as a negative electrode active material is used as the negative electrode. It can also be said that it is suspended in the air through a thin film of the active material and is not rigidly joined to the negative electrode container but is supported by floating.
【００２０】具体的には、安全容器を負極活物質と軟金
属(または軟金属として代用され得る負極活物質)を使っ
て浮遊支持するものである。ここで、軟金属とは、常温
において、剛性が低く、電池運転温度では更に剛性が低
下しあるいは液化する、導電性を有する金属であると定
義する。また、浮遊支持とは、流体中に浮遊し、かつ、
空間的位置が決定される支持法と定義する。上記に基づ
いて安全容器の上端部に安全容器と負極容器間を電気的
に接続するための軟金属溜めを設けている。Specifically, the safety container is suspended and supported by using a negative electrode active material and a soft metal (or a negative electrode active material that can be used as a soft metal). Here, the soft metal is defined as a conductive metal that has low rigidity at normal temperature and further lowers or liquefies at the battery operating temperature. In addition, the floating support means that it is suspended in a fluid and
It is defined as a support method whose spatial position is determined. Based on the above, a soft metal reservoir for electrically connecting the safety container and the negative electrode container is provided at the upper end of the safety container.
【００２１】本発明によって、安全容器の熱変形による
固体電解質や熱圧接の破損が防止され、かつ、万一固体
電解質や熱圧接が破損し電池の短絡や異常温度上昇が発
生した場合でも、破損電池を他の健全な直並列電池から
電気的に切り離し、安全でかつ体積エネルギー密度の低
下がなく安全性と信頼性が向上するナトリウム／溶融塩
電池が提供される。According to the present invention, the solid electrolyte and the thermal pressure welding due to the thermal deformation of the safety container are prevented from being damaged, and even if the solid electrolyte or the thermal welding is damaged and the battery is short-circuited or an abnormal temperature rise occurs, the damage is prevented. A sodium / molten salt battery is provided that is electrically isolated from other healthy series-parallel batteries, and that is safe, has no reduction in volumetric energy density, and has improved safety and reliability.
【００２２】なお、本実施例では、軟金属２４としてナ
トリウム元素を用いたが、リチウム元素、またはカリウ
ム元素、または鉛元素などの金属、あるいはこれらの元
素を主成分とする複合金属など、前述の定義に合う材料
であれば適用可能である。一方、例えばナトリウムのよ
うに、軟金属の定義に合う負極活物質６であれば軟金属
２４を当該負極活物質６と同材料とすることが、製作上
から有利であると言える。In the present embodiment, the sodium element is used as the soft metal 24. However, the above-mentioned metals such as the lithium element, the potassium element, and the lead element, and the composite metals containing these elements as main components are used. Any material that meets the definition is applicable. On the other hand, if the anode active material 6 meets the definition of the soft metal, such as sodium, for example, it is advantageous from the viewpoint of manufacturing that the soft metal 24 is made of the same material as the anode active material 6.
【００２３】ところで、本実施例では、固体電解質容器
１の上部である負極側空間に負極カバーガス空間１３を
設け、該負極カバーガス空間１３に不活性ガスを封入し
ている。このような構造の電池容器とし、電気絶縁材２
と負極容器４との接合部である熱圧接部１２が、Ｎａと
接触しＮａによって腐食を受けないようにする、また
は、固体電解質容器１などが、電池運転の昇降温時に発
生する熱変形によって破損しないようにするものであ
る。In this embodiment, a negative electrode cover gas space 13 is provided in the negative electrode side space, which is the upper part of the solid electrolyte container 1, and an inert gas is sealed in the negative electrode cover gas space 13. The battery container having such a structure is formed by using an electric insulating material 2
The heat-pressed portion 12, which is a junction between the anode and the negative electrode container 4, comes into contact with Na so as not to be corroded by Na, or the solid electrolyte container 1 or the like is deformed due to thermal deformation generated at the time of temperature rise and fall during battery operation. This is to prevent damage.
【００２４】すなわち、不活性ガスを保有する負極カバ
ーガス空間１３がないと、電池運転の昇温時に膨張した
Ｎａが熱圧接部１２まで容易に到達し、Ｎａが熱圧接部
１２に接触し、熱圧接部１２を腐食する。また、負極カ
バーガス空間１３がなくＮａで充満された状態になって
いると、昇温時にＮａが固体から液体に相変化すること
によって、Ｎａの体積が膨脹し、熱圧接部１２や負極容
器４に異常な応力が発生し、熱圧接部１２や負極容器４
が破損する可能性がある。 これに対し、負極カバー
ガス空間１３があると、不活性ガスのガス圧によってＮ
ａの膨張が阻止され、あるいは負極カバーガス空間１３
が緩衝体となり、接触や破損が回避されるものである。That is, if there is no negative electrode cover gas space 13 holding an inert gas, Na expanded at the time of raising the temperature of the battery operation easily reaches the thermal pressure contact portion 12, and Na comes into contact with the thermal pressure contact portion 12, Corrosion of the heat welding part 12 is performed. Further, when the negative electrode cover gas space 13 is not filled and filled with Na, the volume of Na expands due to the phase change of Na from a solid to a liquid at the time of temperature rise, so that the thermal pressure contact portion 12 and the negative electrode container 4, an abnormal stress is generated, and the heat-pressed portion 12 and the negative electrode container 4
May be damaged. On the other hand, if there is the negative electrode cover gas space 13, N gas is generated by the gas pressure of the inert gas.
a is prevented, or the negative electrode cover gas space 13
Serves as a buffer, and contact and breakage are avoided.
【００２５】すなわち、本実施例は、安全容器８を内包
する負極容器４と固体電解質容器１とで形成される負極
側空間に、負極カバーガス空間１３を設けることによっ
て、負極側空間に充填した負極活物質６あるいは本発明
による軟金属２４が昇温時に膨脹した場合の、負極容器
４や固体電解質容器１への悪影響(例えば破損)を防止す
るものである。That is, in the present embodiment, the negative electrode side space formed by the negative electrode container 4 containing the safety container 8 and the solid electrolyte container 1 is provided with the negative electrode cover gas space 13 to fill the negative electrode side space. When the negative electrode active material 6 or the soft metal 24 according to the present invention expands when the temperature is raised, the negative electrode container 4 and the solid electrolyte container 1 are prevented from being adversely affected (for example, damaged).
【００２６】図３は、本発明によるナトリウム／溶融塩
電池の第２の実施例を示す縦断面図である。第２の実施
例は、該安全容器８と負極容器４とを電気的に接続する
軟金属２４を溜める軟金属溜め１０の形状と、安全容器
８の浮遊支持とを改善したものである。ナトリウム／溶
融塩電池を自動車のような可搬用途に用いた場合の振動
に耐えるように、軟金属溜め１０の上端部を絞り、該上
端部に蓋の機能を持たせ、軟金属２４の振動による液漏
れを防止し、電気伝導性を確実なものとすると共に、蓋
が一体で加工されコストの低減に繋がるものである。FIG. 3 is a longitudinal sectional view showing a second embodiment of the sodium / molten salt battery according to the present invention. In the second embodiment, the shape of the soft metal reservoir 10 for storing the soft metal 24 for electrically connecting the safety container 8 and the negative electrode container 4 and the floating support of the safety container 8 are improved. The upper end of the soft metal reservoir 10 is squeezed so as to withstand vibration when the sodium / molten salt battery is used in a portable application such as an automobile, and the upper end has a function of a lid. In addition to preventing liquid leakage due to the above, the electric conductivity is ensured, and the lid is integrally processed, which leads to a reduction in cost.
【００２７】例えば、安全容器８の上端部と負極容器４
との間を、0.2mm以下の狭い寸法とする。これによっ
て、振動によって上端部と負極容器４の両者が接触して
も点接触となり、本発明における固体電解質容器１に掛
かる応力は、従来の安全容器８が剛接合されていた場合
に発生する応力と比べれば遥かに小さい。即ち、固体電
解質容器１の固体電解質の許容応力200MPaと比べれば、
無視できる20〜30MPa程度の応力である。従って、液漏
れの防止と浮遊支持との両機能が確保される。即ち、本
実施例は、走行振動や地震に耐えられる構造とするもの
であり、負極容器４と安全容器８との電気的接続を維持
しつつ、安全容器８の上端部に設けた軟金属溜め１０内
の軟金属２４が流出しないように安全容器の上端部を絞
り加工し、蓋の機能を持たせたものである。For example, the upper end of the safety container 8 and the negative electrode container 4
And a narrow dimension of 0.2 mm or less. As a result, even if both the upper end portion and the negative electrode container 4 come into contact with each other due to vibration, point contact occurs, and the stress applied to the solid electrolyte container 1 in the present invention is the stress generated when the conventional safety container 8 is rigidly joined. It is much smaller than. That is, compared with the allowable stress of the solid electrolyte of the solid electrolyte container 1 of 200 MPa,
The stress is about 20 to 30 MPa which can be ignored. Therefore, both functions of preventing liquid leakage and floating support are ensured. That is, the present embodiment has a structure that can withstand running vibrations and earthquakes. The soft metal reservoir provided at the upper end of the safety container 8 while maintaining the electrical connection between the negative electrode container 4 and the safety container 8. The upper end of the safety container is drawn so as to prevent the soft metal 24 inside 10 from flowing out, and has a function as a lid.
【００２８】図４は、本発明によるナトリウム／溶融塩
電池の第３の実施例を示す縦断面図である。第３の実施
例は、負極容器４と軟金属２４との電気的接触を良くす
るもので、軟金属と接する負極容器の軟金属に対する濡
れ性を改善したものである。FIG. 4 is a longitudinal sectional view showing a third embodiment of the sodium / molten salt battery according to the present invention. In the third embodiment, the electrical contact between the negative electrode container 4 and the soft metal 24 is improved, and the wettability of the negative electrode container in contact with the soft metal to the soft metal is improved.
【００２９】負極容器４(即ち、凸部４ａ)の軟金属２４
と接触する表面に、Ｎａに濡れ易い材料をコーティング
したコーティング層１８を設けたものである。コーティ
ング材としては、例えば、軟金属としてＮａを使用すれ
ば、金，白金，鉛等のようなＮａと金属間化合物を形成
するものが有効である。具体的に説明すれば、負極容器
が軟金属に濡れる前の接触抵抗は数Ωであるが、本発明
により濡れると1mΩ以下に低下する。本実施例は、負極
容器の軟金属に接触する表面部位が当該軟金属に対し濡
れ易い材質で被覆されているものである。これによっ
て、内部抵抗を低減し、電池効率を向上することができ
る。The soft metal 24 of the negative electrode container 4 (ie, the projection 4a)
Is provided with a coating layer 18 coated with a material that easily wets Na. As the coating material, for example, if Na is used as a soft metal, a material that forms an intermetallic compound with Na, such as gold, platinum, or lead, is effective. More specifically, the contact resistance before the negative electrode container is wetted by the soft metal is several Ω, but when wetted by the present invention, the contact resistance is reduced to 1 mΩ or less. In this embodiment, the surface portion of the negative electrode container that contacts the soft metal is coated with a material that is easily wetted by the soft metal. Thereby, the internal resistance can be reduced and the battery efficiency can be improved.
【００３０】図５は、本発明によるナトリウム／溶融塩
電池の第４の実施例を示す縦断面図である。第４の実施
例は、安全容器や負極電極の変形による固体電解質の破
損、あるいは電池容器のシール部の破損等によって電池
が故障した際に、他の集合電池から流れる短絡電流また
は電池単体内に発生する短絡電流を遮断する手段を、負
極容器の内または外または内と外に設けたものである。FIG. 5 is a longitudinal sectional view showing a fourth embodiment of the sodium / molten salt battery according to the present invention. In the fourth embodiment, when the battery breaks down due to the damage of the solid electrolyte due to the deformation of the safety container or the negative electrode, or the breakage of the sealing portion of the battery container, the short-circuit current flowing from another assembled battery or the inside of the battery alone The means for interrupting the generated short-circuit current is provided inside, outside, or inside and outside of the negative electrode container.
【００３１】図５の実施例では、負極容器４の凸部４ａ
の先端部に負極内ヒューズ２１を設け、また、外部ブス
バーとしての負極端子１６に負極外ヒューズ２０を設け
た例が示されている。負極内ヒューズ２１は、負極容器
４と軟金属２４との間に流れるシール部の短絡や電池内
部の短絡による内部循環電流に対して、温度または／お
よび電流を感知し遮断するヒューズ機能を持ったものと
して設けられている。負極外ヒューズ２０は、外部の他
の集合電池からの異常電流を遮断するものとして設けら
れている。すなわち、負極外ヒューズ２０と負極内ヒュ
ーズ２１とは分業している。なお、ヒューズ材として
は、Ｎａとの共存性から、Ａｌ基合金が好ましい。ま
た、負極内ヒューズ２１にコーティング層１８を設けて
も良い。In the embodiment shown in FIG. 5, the projection 4a of the negative electrode container 4 is formed.
An example is shown in which an in-negative fuse 21 is provided at the tip end of the device, and an in-negative fuse 20 is provided in the negative terminal 16 as an external bus bar. The fuse 21 within the negative electrode has a fuse function of detecting and / or interrupting temperature and / or current with respect to an internal circulating current due to a short circuit of a seal portion flowing between the negative electrode container 4 and the soft metal 24 or a short circuit inside the battery. It is provided as a thing. The fuse 20 outside the negative electrode is provided to interrupt an abnormal current from another external battery pack. That is, the fuse 20 outside the negative electrode and the fuse 21 inside the negative electrode are part of a division of labor. Note that, as the fuse material, an Al-based alloy is preferable from the viewpoint of coexistence with Na. Further, the coating layer 18 may be provided on the fuse 21 in the negative electrode.
【００３２】即ち、本実施例は、電池が故障した場合の
短絡電流を遮断するために、当該負極容器の軟金属と接
触する軟金属側部位に負極内ヒューズ２１を、または、
該軟金属側部位に負極内ヒューズ２１及び当該負極容器
の負極端子部位に負極外ヒューズ２０を、電流遮断手段
として設けるものである。これによって、一段と安全性
が向上する。なお、負極容器の負極端子が外部ブスバー
であっても可である。That is, in this embodiment, in order to cut off the short-circuit current in the event of a battery failure, the negative electrode fuse 21 is provided at the soft metal side of the negative electrode container in contact with the soft metal, or
A fuse 21 inside the negative electrode is provided at the soft metal side portion and a fuse 20 outside the negative electrode is provided at the negative terminal portion of the negative electrode container as a current interrupting means. This further improves safety. The negative terminal of the negative container may be an external bus bar.
【００３３】図６は、本発明によるナトリウム／溶融塩
電池の第５の実施例を示す縦断面図である。第５の実施
例は、負極容器４に、Ｎａ注入機能とヒューズ機能と負
極機能を具備した注入管２５を設けたものである。図に
おいて、Ｎａは、電池容器内の負極側空間を真空または
不活性状態にして、注入管２５と軟金属溜め１０を経
て、安全容器８と固体電解質容器１のギャップ２２を通
り、Ｎａ供給孔７から安全容器８内へと、液体状態で外
から注入される。Ｎａ注入後に、注入管２５は栓２５ａ
で密封される。あるいは、栓２５ａの代わりに負極外ヒ
ューズ２０を用いて密封される。あるいは、注入管２５
を溶かし溶封されても可である。FIG. 6 is a longitudinal sectional view showing a fifth embodiment of the sodium / molten salt battery according to the present invention. In the fifth embodiment, an injection tube 25 having a Na injection function, a fuse function, and a negative electrode function is provided in the negative electrode container 4. In the figure, Na is placed in a vacuum or inactive state in the negative electrode side space in the battery container, passes through the injection tube 25 and the soft metal reservoir 10, passes through the gap 22 between the safety container 8 and the solid electrolyte container 1, and passes through the Na supply hole. The liquid is injected from outside into the safety container 8 from 7. After the Na injection, the injection tube 25 is plugged
Sealed. Alternatively, sealing is performed using a fuse 20 outside the negative electrode instead of the plug 25a. Alternatively, the injection tube 25
Can be melted and sealed.
【００３４】また、軟金属２４の注入は、Ｎａ注入後、
同様な方法で注入可能である。さらに、注入管２５にコ
ーティング層１８を設けても良い。本実施例によれば、
安全容器８と軟金属溜め１０にＮａや軟金属を、酸化さ
せずにかつ簡便に充填することが可能である。すなわ
ち、本実施例は、軟金属溜めへの軟金属注入の効率化で
あり、軟金属溜めを経由してＮａや軟金属を注入する注
入孔の機能を負極端子に持たせたものである。換言すれ
ば、負極容器は、軟金属溜めに軟金属を注入するため
の、または軟金属溜めを経由して負極活物質を注入する
ための注入管を有すると言える。The injection of the soft metal 24 is performed after the Na injection.
It can be injected in a similar manner. Further, the coating layer 18 may be provided on the injection tube 25. According to the present embodiment,
The safety container 8 and the soft metal reservoir 10 can be easily filled with Na or soft metal without being oxidized. That is, in the present embodiment, the efficiency of soft metal injection into the soft metal reservoir is improved, and the function of an injection hole for injecting Na or soft metal through the soft metal reservoir is provided to the negative electrode terminal. In other words, it can be said that the negative electrode container has an injection tube for injecting the soft metal into the soft metal reservoir or for injecting the negative electrode active material via the soft metal reservoir.
【００３５】図７は、本発明によるナトリウム／溶融塩
電池の第６の実施例を示す縦断面図である。第６の実施
例は、安全容器８と固体電解質容器１とのギャップ２２
に多孔質体からなるスペーサ２３を設けたものである。
スペーサ２３を設けることによって、ギャップ２２のギ
ャップ寸法を均一に製作すること、ならびに均一に維持
することが可能となる。またスペーサ２３が、安全容器
８と固体電解質容器１との直接接触を防止し、接触によ
る破損というような弊害を無くす働きもする。FIG. 7 is a longitudinal sectional view showing a sixth embodiment of the sodium / molten salt battery according to the present invention. In the sixth embodiment, a gap 22 between the safety container 8 and the solid electrolyte container 1 is set.
Is provided with a spacer 23 made of a porous material.
By providing the spacers 23, it is possible to make the gap size of the gap 22 uniform and to keep it uniform. Further, the spacer 23 also functions to prevent direct contact between the safety container 8 and the solid electrolyte container 1 and to eliminate adverse effects such as breakage due to the contact.
【００３６】スペーサ２３としては、発泡金属やガラス
繊維などのように、負極活物質６が流動するための孔を
有する多孔質体が採用される。そして、電池運転の高出
力時や固体電解質破損による異常高温時の熱変形、ある
いは、外部からの力による変形を吸収するために、多孔
質体としての発泡金属には「つぶれ代」がある方が好まし
い。従って、スペーサ２３としては、ＡｌやＮｉ材から
なる発泡金属が最適である。また、スペーサ２３は必ず
しも導電体でなくガラス繊維またはアルミナ繊維などで
も良い。As the spacer 23, a porous body having holes for the anode active material 6 to flow, such as foamed metal or glass fiber, is employed. In order to absorb thermal deformation at the time of high output of battery operation or abnormally high temperature due to breakage of the solid electrolyte, or deformation due to external force, foamed metal as a porous body has a “crush allowance”. Is preferred. Therefore, as the spacer 23, a foam metal made of an Al or Ni material is optimal. The spacer 23 is not necessarily a conductor, but may be glass fiber or alumina fiber.
【００３７】本実施例は、電池容器において、安全容器
が固体電解質容器と対面している当該安全容器の下部周
囲に多孔質体を有し、安全容器が該多孔質体で支持され
ているものであり、安全容器と固体電解質容器の間のギ
ャップ寸法が均一になり、さらに安全性と信頼性が向上
するものである。This embodiment is directed to a battery container in which the safety container has a porous body around the lower part of the safety container facing the solid electrolyte container, and the safety container is supported by the porous body. In this case, the gap size between the safety container and the solid electrolyte container becomes uniform, and the safety and reliability are further improved.
【００３８】[0038]
【発明の効果】本発明によれば、固体電解質に不必要な
荷重が加わることなく固体電解質を健全に維持でき安全
であるばかりでなく、常に低抵抗で電流を取り出し可能
であり体積エネルギー密度の低下がなく、安全性と信頼
性の高いナトリウム／溶融塩電池が得られる効果があ
る。According to the present invention, the solid electrolyte can be maintained in a healthy state without applying an unnecessary load to the solid electrolyte, and it is not only safe, but also it is possible to always take out a current with low resistance and to obtain a low volume energy density. There is an effect that a sodium / molten salt battery with high safety and high reliability can be obtained without reduction.
【図１】本発明による一実施例のナトリウム／溶融塩電
池を示す縦断面図である。FIG. 1 is a longitudinal sectional view showing an embodiment of a sodium / molten salt battery according to the present invention.
【図２】従来のナトリウム／溶融塩電池を示す縦断面図
である。FIG. 2 is a longitudinal sectional view showing a conventional sodium / molten salt battery.
【図３】本発明によるナトリウム／溶融塩電池の第２の
実施例を示す縦断面図である。FIG. 3 is a longitudinal sectional view showing a second embodiment of the sodium / molten salt battery according to the present invention.
【図４】本発明によるナトリウム／溶融塩電池の第３の
実施例を示す縦断面図である。FIG. 4 is a longitudinal sectional view showing a third embodiment of the sodium / molten salt battery according to the present invention.
【図５】本発明によるナトリウム／溶融塩電池の第４の
実施例を示す縦断面図である。FIG. 5 is a longitudinal sectional view showing a fourth embodiment of the sodium / molten salt battery according to the present invention.
【図６】本発明によるナトリウム／溶融塩電池の第５の
実施例を示す縦断面図である。FIG. 6 is a longitudinal sectional view showing a fifth embodiment of the sodium / molten salt battery according to the present invention.
【図７】本発明によるナトリウム／溶融塩電池の第６の
実施例を示す縦断面図である。FIG. 7 is a longitudinal sectional view showing a sixth embodiment of the sodium / molten salt battery according to the present invention.
１…固体電解質容器、１ａ…内面形状、２…電気絶縁
材、３…正極容器、４…負極容器、４ａ…凸部、５…正
極活物質、６…負極活物質、７…Ｎａ供給孔８…安全容
器、８ａ…外面形状、１０…軟金属溜め、１１…充電末
期Ｎａ液面、１２…熱圧接部、１３…負極カバーガス空
間、１４…正極カバーガス空間、１５…安全容器内カバ
ーガス空間、１６…負極端子、１７…正極端子、１８…
コーティング層、２０…負極外ヒューズ、２１…負極内
ヒューズ、２２…ギャップ２３…スペーサ、２４…軟金
属、２５…注入管、２５ａ…栓。DESCRIPTION OF SYMBOLS 1 ... Solid electrolyte container, 1a ... Inner surface shape, 2 ... Electric insulating material, 3 ... Positive electrode container, 4 ... Negative electrode container, 4a ... Convex part, 5 ... Positive electrode active material, 6 ... Negative electrode active material, 7 ... Na supply hole 8 ... Safety container, 8a ... Outer surface shape, 10 ... Soft metal reservoir, 11 ... Na liquid level at the end of charging, 12 ... Heat contact part, 13 ... Negative electrode cover gas space, 14 ... Positive electrode cover gas space, 15 ... Cover gas inside safety container Space, 16: negative terminal, 17: positive terminal, 18:
Coating layer, 20: fuse outside negative electrode, 21: fuse inside negative electrode, 22: gap 23: spacer, 24: soft metal, 25: injection tube, 25a: stopper.
フロントページの続き (72)発明者 根本 清光 茨城県日立市大みか町七丁目２番１号 株式会社 日立製作所 電力・電機開発 本部内 (72)発明者 綿引 直久 茨城県日立市大みか町七丁目２番１号 株式会社 日立製作所 電力・電機開発 本部内 (56)参考文献 特開 平６−342672（ＪＰ，Ａ) 特開 平２−201874（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 10/39 Continuing from the front page (72) Inventor Kiyomitsu Nemoto 7-2-1, Omika-cho, Hitachi City, Ibaraki Prefecture Within Hitachi, Ltd. Power & Electricity Development Division (72) Inventor Naohisa Watahiki 7-2, Omika-cho, Hitachi City, Ibaraki Prefecture No. 1 Hitachi, Ltd. Electric Power & Electric Equipment Development Division (56) References JP-A-6-342672 (JP, A) JP-A-2-201874 (JP, A) (58) Fields surveyed (Int. 7 , DB name) H01M 10/39
Claims (9)
で構成される正極側空間に正極活物質を収納して成るナ
トリウム／溶融塩電池において、固体電解質容器と負極
活物質を収納するために形成された前記固体電解質容器
内に配設され、前記固体電解質容器の内面に対面する外
面とでほぼ一様な狭い空間を形成する安全容器であっ
て、下部周囲において前記負極活物質による薄膜により
浮遊支持され、上部は負極容器の凸部に対応する部位に
設けられ導電性を有する軟金属溜めとの間に介在する軟
金属によって浮遊支持される安全容器を有し，前記安全
容器の上部が前記負極容器の凸部と前記軟金属を介して
対面配置されていることを特徴とするナトトリウム／溶
融塩電池。1. A sodium / molten salt battery comprising a positive electrode active material contained in a positive electrode side space comprising a negative electrode container, a positive electrode container and a solid electrolyte container, for accommodating the solid electrolyte container and the negative electrode active material. A safety container that is disposed in the solid electrolyte container formed to form a substantially uniform narrow space with an outer surface facing an inner surface of the solid electrolyte container, and a thin film formed of the negative electrode active material around a lower portion. A safety container provided at a position corresponding to the convex portion of the negative electrode container, the upper portion of the safety container being floatingly supported by a soft metal interposed between the conductive soft metal reservoir and the upper portion of the safety container. Is disposed facing the convex portion of the negative electrode container via the soft metal.
リウム元素またはリチウム元素またはカリウム元素また
は鉛元素であることを特徴とするナトリウム／溶融塩電
池。2. A sodium / molten salt battery according to claim 1, wherein said soft metal is sodium, lithium, potassium, or lead.
負極活物質と同材料であることを特徴とするナトリウム
／溶融塩電池。3. The sodium / molten salt battery according to claim 1, wherein the soft metal is the same material as the negative electrode active material.
端部に絞り部を有し前記軟金属の流失を防ぐ蓋部を構成
した安全容器であることを特徴とするナトリウム／溶融
塩電池。4. The sodium / molten salt battery according to claim 1, wherein the safety container is a safety container having a throttle at an upper end portion of the safety container and having a lid for preventing the soft metal from flowing away.
記軟金属に接触する表面部位は前記軟金属に対し濡れ易
い材料で被覆されていることを特徴とするナトリウム／
溶融塩電池。5. A method according to claim 1, wherein said negative electrode container has a surface portion in contact with said soft metal coated with a material which is easily wetted by said soft metal.
Molten salt battery.
金属と接触する凸部位端部または負極端子に異常電流遮
断手段を設けて成る負極容器であることを特徴とするナ
トリウム／溶融塩電池。6. A sodium / molten salt battery according to claim 1, wherein said negative electrode container is a negative electrode container provided with an abnormal current interrupting means at an end of a protruding portion in contact with a soft metal or a negative electrode terminal. .
記軟金属溜めに前記軟金属を注入するため、または前記
軟金属溜めを経由して前記負極空間に負極活物質を注入
する注入管を設けて成る負極容器であることを特徴とす
るナトリウム／溶融塩電池。7. The negative electrode container according to claim 1, further comprising an injection tube for injecting the soft metal into the soft metal reservoir or for injecting a negative electrode active material into the negative electrode space via the soft metal reservoir. sodium / molten salt battery, characterized in that it is a negative electrode container made provided.
極側空間に負極カバーガス空間を有することを特徴とす
るナトリウム／溶融塩電池。8. The sodium / molten salt battery according to claim 1, wherein a negative electrode cover gas space is provided in a negative electrode side space of the battery container.
に固体電解質容器を配設し、前記正極容器と前記固体電
解質容器とで囲まれた正極側空間内に正極活物質を収納
し、前記負極容器と前記固体電解質容器とで囲まれた負
極側空間内に負極活物質を収納し、前記固体電解質容器
が固体電解質として機能するように電気絶縁材を介して
前記３つの容器を絶縁接合して成る電池容器と、前記電
池容器は前記負極側空間の前記固体電解質容器内に設け
た安全容器と、前記安全容器は前記固体電解質と対面し
ている下部および上部周囲に設けられた多孔質体スペー
サと、上部は前記負極容器の凸部に対応する部位に設け
られた導電性を有する軟金属の溜め部とを有し、前記負
極容器と前記軟金属を介して対面するとともに前記軟金
属によって浮遊支持される安全容器であることを特徴と
するナトリウム／溶融塩電池。9. A solid electrolyte container is disposed in a space formed by a positive electrode container and a negative electrode container, and a positive electrode active material is stored in a positive electrode side space surrounded by the positive electrode container and the solid electrolyte container. the negative electrode Katsubutsu quality accommodated surrounded by negative-side space at the negative electrode container and the solid electrolyte container, the three containers through an electrically insulating material as the solid electrolyte container functioning as a solid electrolyte A battery container formed by insulation bonding, the battery container is provided with a safety container provided in the solid electrolyte container in the negative electrode side space, and the safety container is provided around a lower portion and an upper portion facing the solid electrolyte . Porous body space
And the upper portion is provided at a portion corresponding to the convex portion of the negative electrode container.
And a reservoir of a soft metal having conductivity.
And an electrode container and the soft metal facing each other through the soft metal.
It is a safety container that is suspended and supported by the genus
Sodium / molten salt battery .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31988695A JP3355377B2 (en) | 1995-12-08 | 1995-12-08 | Sodium / molten salt battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31988695A JP3355377B2 (en) | 1995-12-08 | 1995-12-08 | Sodium / molten salt battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09161843A JPH09161843A (en) | 1997-06-20 |
| JP3355377B2 true JP3355377B2 (en) | 2002-12-09 |
Family
ID=18115342
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31988695A Expired - Fee Related JP3355377B2 (en) | 1995-12-08 | 1995-12-08 | Sodium / molten salt battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3355377B2 (en) |
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| Publication number | Publication date |
|---|---|
| JPH09161843A (en) | 1997-06-20 |
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