JP2003223929A - Sodium-sulfur battery - Google Patents
Sodium-sulfur batteryInfo
- Publication number
- JP2003223929A JP2003223929A JP2002020874A JP2002020874A JP2003223929A JP 2003223929 A JP2003223929 A JP 2003223929A JP 2002020874 A JP2002020874 A JP 2002020874A JP 2002020874 A JP2002020874 A JP 2002020874A JP 2003223929 A JP2003223929 A JP 2003223929A
- Authority
- JP
- Japan
- Prior art keywords
- sodium
- sulfur
- active material
- battery
- electrode active
- 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.)
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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
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- Secondary Cells (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はナトリウム硫黄電池
に係り、例えば高温型二次電池に好適なナトリウム硫黄
電池に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sodium-sulfur battery, and more particularly to a sodium-sulfur battery suitable for a high temperature secondary battery.
【０００２】[0002]
【従来の技術】ナトリウム硫黄電池は、負極活物質にナ
トリウム、正極活物質に硫黄、及び多硫化ナトリウム等
溶融塩を、正極と負極の隔壁に、ナトリウムイオンに導
電性がある固体電解質が用いられる高温型二次電池であ
る。ナトリウムイオン導電性の固体電解質としては、ベ
ータアルミナが用いられ、袋管を用いる場合が多い。一
般に、ナトリウムイオン導電性の固体電解質とナトリウ
ムと硫黄を収納する１つの容器から１つの電池が構成さ
れる。これを単電池と呼ぶ。大電力を蓄えるには多数本
の単電池を直並列に接続して用いる。2. Description of the Related Art A sodium-sulfur battery uses sodium as a negative electrode active material, sulfur as a positive electrode active material, and molten salt such as sodium polysulfide, and a solid electrolyte having conductivity for sodium ions as a partition wall between the positive electrode and the negative electrode. It is a high temperature type secondary battery. As the sodium ion conductive solid electrolyte, beta alumina is used, and a bag tube is often used. In general, one battery is composed of one container containing a sodium ion conductive solid electrolyte and sodium and sulfur. This is called a unit cell. To store a large amount of electric power, a large number of cells are connected in series and parallel.
【０００３】ナトリウム硫黄電池の通常の運転温度は２
８０℃〜３７０℃と高温であるため、複数の単電池を断
熱容器に詰めてモジュールとする。１単電池当たりの電
池出力を増大するには、電池のジュール損失を低減して
大電流で放電運転する必要がある。電池のジュール損失
を低減するには電池の内部抵抗を極力低減する必要があ
る。The normal operating temperature of a sodium-sulfur battery is 2
Since the temperature is as high as 80 ° C. to 370 ° C., a plurality of unit cells are packed in a heat insulating container to form a module. In order to increase the battery output per single battery, it is necessary to reduce the Joule loss of the battery and perform discharge operation with a large current. In order to reduce the Joule loss of the battery, it is necessary to reduce the internal resistance of the battery as much as possible.
【０００４】ナトリウム硫黄電池の放電反応は次式で示
せる。The discharge reaction of a sodium-sulfur battery can be expressed by the following equation.
【０００５】 Ｎａ＋Ｓ → Ｎａ2Ｓx （ｘ＝３〜５） 充電反応は上式の逆反応である。Na + S → Na 2 S x (x = 3 to 5) The charging reaction is a reverse reaction of the above formula.
【０００６】上記した電池反応は硫黄極で生じる。従っ
て、電池の内部抵抗の大半は、Ｓ極の抵抗であり、内部
抵抗を極力低減するには、Ｓ極の抵抗を低減することが
最も有効である。The above-mentioned battery reaction occurs at the sulfur electrode. Therefore, most of the internal resistance of the battery is the resistance of the S pole, and in order to reduce the internal resistance as much as possible, it is most effective to reduce the resistance of the S pole.
【０００７】従来の電池の一例は、図２に示したように
袋管状の固体電解質１の外表面に形成した硫黄極（正
極）３には正極活物質である硫黄、及び多硫化ナトリウ
ムが充填され充電や放電の電池反応を可能にするため、
電子伝導性を持った補助導電材を装着する。硫黄極３の
全領域に補助導電材を装着する必要があるため、硫黄極
内での電池活物質の流動性は極めて小さい。In an example of a conventional battery, a sulfur electrode (positive electrode) 3 formed on the outer surface of a bag-shaped solid electrolyte 1 as shown in FIG. 2 is filled with sulfur as a positive electrode active material and sodium polysulfide. In order to allow battery reactions for charging and discharging,
Wear an auxiliary conductive material with electronic conductivity. Since it is necessary to attach the auxiliary conductive material to the entire area of the sulfur electrode 3, the fluidity of the battery active material in the sulfur electrode is extremely small.
【０００８】電池出力の増大（高出力運転）には電池の
放電電流を増大する必要があり、硫黄極内での電池活物
質の流動性が求められる。In order to increase the battery output (high output operation), it is necessary to increase the discharge current of the battery, and the fluidity of the battery active material in the sulfur electrode is required.
【０００９】そこで、従来電池発想を転換した図３のよ
うな集電極１０を用いて、電池活物質であるナトリウム
と硫黄のみを増大すれば電池容量が増大し、硫黄極９の
厚みを適切に選定することにより、電池の内部抵抗が低
減できる電池を提案した。Therefore, by using a collector electrode 10 as shown in FIG. 3 which has changed the idea of a conventional battery, and increasing only sodium and sulfur which are battery active materials, the battery capacity is increased and the thickness of the sulfur electrode 9 is appropriately adjusted. We have proposed a battery whose internal resistance can be reduced by selecting it.
【００１０】[0010]
【発明が解決しようとする課題】しかしながら、上記従
来技術では、高出力（例えば２倍出力以上）で電池を充
放電運転すると内部抵抗が上昇して電池の運転領域が狭
くなり、結果的に電池容量が充分取れない電池となるこ
とがあった。However, in the above-mentioned prior art, when the battery is charged / discharged at a high output (for example, double output or more), the internal resistance increases and the operating range of the battery is narrowed. The battery may not have sufficient capacity.
【００１１】本発明の目的は、電池の高出力運転が可能
で、かつ、電池容量の増大を安定して維持できるナトリ
ウム硫黄電池を提供することにある。An object of the present invention is to provide a sodium-sulfur battery capable of high-power operation and capable of stably maintaining an increase in battery capacity.
【００１２】[0012]
【課題を解決するための手段】上記目的を達成するため
に、本発明のナトリウム硫黄電池は、ナトリウムイオ
ン，硫黄，多硫化ナトリウムが円滑に集電極内で流動で
きる電池充放電方式を提案する。In order to achieve the above object, the sodium-sulfur battery of the present invention proposes a battery charging / discharging system in which sodium ions, sulfur and sodium polysulfide can smoothly flow in the collector electrode.
【００１３】具体的には集電極内にナトリウムイオン，
硫黄、並びに多硫化ナトリウムの適切な流路パスを設け
る。この適切な流路パスが形成されることによって、電
池反応に必要な活物質を電池反応領域へ供給し、さらに
反応生成物を排出することが容易となり、高出力で長期
間に渡って運転しても円滑な充放電が可能となる。Specifically, sodium ions in the collecting electrode,
Provide appropriate flow paths for sulfur as well as sodium polysulfide. By forming this appropriate flow path, it becomes easy to supply the active material necessary for the battery reaction to the battery reaction region and further discharge the reaction products, and to operate at high output for a long period of time. Even then, smooth charge and discharge can be performed.
【００１４】[0014]
【発明の実施の形態】（実施例１）図１は本発明に係る
ＮａＳ電池の第１の実施例であり、袋管状の固体電解質
１の長手方向（軸方向）に対して直角に切断した横断面
である。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS (Embodiment 1) FIG. 1 is a first embodiment of a NaS battery according to the present invention, which is cut at a right angle to the longitudinal direction (axial direction) of a tubular solid electrolyte 1. It is a cross section.
【００１５】該図の如く、正極容器４内に固体電解質１
が装着され、固体電解質１の内部がナトリウム極（負
極）６となりナトリウム７が充填されている。固体電解
質１の外周には絶縁物を用いた高抵抗層１３を設ける。
この高抵抗層１３の一例としては、アルミナやガラス等
絶縁物を多孔体やメッシュに加工し、シート状に整形し
た物、または、粒子状や粉末状態の物を用いる。高抵抗
層１３の外周には電子伝導性のある補助導電体１４を設
ける。補助導電体１４の一例としてはグラファイトやカ
ーボン、その他金属を多孔体やメッシュに加工し、シー
ト状に整形した物、または、粒子状や粉末状態の物を用
いる。さらに、その外周には充放電反応の電流を流すた
めの集電極１０を設ける。集電極１０は正極容器４と電
気的に接続されている。集電極１０の外周にはさらに、
正極活物質の吸上げ供給パス１５を設ける。正極活物質
の吸上げ供給パス１５の一例としては毛細管力を利用
し、多硫化ナトリウムを供給したい場合には、多硫化ナ
トリウムに優先的に濡れ易い材料、すなわち、優先浸透
性がある材料を、硫黄を供給したい場合には硫黄に優先
浸透性がある材料を選定し、多孔体やメッシュに加工し
て用いるのが良い。多硫化ナトリウムに優先浸透性のあ
る材料としては、アルミナやガラス，ステンレス鋼等が
考えられる。一方、硫黄に優先浸透性のある材料として
は、グラファイトやカーボン等が考えられる。無論、多
孔体やメッシュではなく、集電極１０の外表面にウイッ
クや溝を形成して同一の機能を果たさせることも可能で
ある。As shown in the figure, the solid electrolyte 1 is placed in the positive electrode container 4.
Is attached, and the inside of the solid electrolyte 1 becomes a sodium electrode (negative electrode) 6 and is filled with sodium 7. A high resistance layer 13 using an insulator is provided on the outer periphery of the solid electrolyte 1.
As an example of the high resistance layer 13, a material obtained by processing an insulating material such as alumina or glass into a porous body or a mesh and shaping it into a sheet, or a material in a particle or powder state is used. An auxiliary conductor 14 having electron conductivity is provided on the outer periphery of the high resistance layer 13. As an example of the auxiliary conductor 14, graphite, carbon, or other metal processed into a porous body or a mesh and shaped into a sheet, or a particle or powder is used. Further, a collector electrode 10 for passing a current for charge / discharge reaction is provided on the outer periphery thereof. The collector electrode 10 is electrically connected to the positive electrode container 4. Further on the outer periphery of the collecting electrode 10,
A suction supply path 15 for the positive electrode active material is provided. As an example of the suction supply path 15 for the positive electrode active material, if capillary force is used and sodium polysulfide is to be supplied, a material that is preferentially wetted by sodium polysulfide, that is, a material that has preferential permeability, When supplying sulfur, it is preferable to select a material having a preferential permeability to sulfur and process it into a porous body or mesh before use. Alumina, glass, stainless steel, etc. are considered as the material having preferential permeability to sodium polysulfide. On the other hand, as a material having preferential permeability to sulfur, graphite, carbon, or the like can be considered. Of course, it is also possible to form a wick or a groove on the outer surface of the collecting electrode 10 instead of the porous body or the mesh so that the same function can be achieved.
【００１６】次に、固体電解質１の径方向に向かう活物
質の流路パスについて説明する。径方向に向かう硫黄の
流路パス１６を集電極１０から固体電解質１に向かって
装着する。この時、硫黄の流路パス１６は集電極１０並
びに、正極活物質の吸上げ供給パス１５を貫通してバル
ク１８まで到達するように形成する。一方、多硫化ナト
リウムの半径方向に向かう流路パス１７は、正極活物質
の吸上げ供給パス１５から、集電極１０，補助導電体１
４を貫通して高抵抗層１３に向かい装着する。一方、ナ
トリウムイオンの径方向に向かう流路パス１９も、集電
極１０から補助導電体１４を貫通して高抵抗層１３に向
かい装着する。ナトリウムイオンは多硫化ナトリウムを
伝導パスとするため、ナトリウムイオンの流路パス１９
は、多硫化ナトリウムの流路パス１７と共用も可能であ
る。図１では共用した場合を表示した。活物質の液面２
０と液面上部の空間は硫黄蒸気とカバーガス２１で覆わ
れている。Next, the flow path of the active material in the radial direction of the solid electrolyte 1 will be described. A flow path path 16 for sulfur that goes in the radial direction is attached from the collecting electrode 10 toward the solid electrolyte 1. At this time, the sulfur flow path 16 is formed so as to reach the bulk 18 through the collector electrode 10 and the suction supply path 15 for the positive electrode active material. On the other hand, the flow path path 17 of the sodium polysulfide in the radial direction extends from the suction supply path 15 of the positive electrode active material to the collector electrode 10 and the auxiliary conductor 1.
It penetrates 4 and faces the high resistance layer 13, and attaches it. On the other hand, the flow path path 19 extending in the radial direction of sodium ions is also attached from the collecting electrode 10 through the auxiliary conductor 14 toward the high resistance layer 13. Since sodium ion uses sodium polysulfide as a conduction path, sodium ion flow path path 19
Can be shared with the sodium polysulfide flow path 17. In FIG. 1, the shared case is displayed. Liquid level 2 of active material
0 and the space above the liquid surface are covered with sulfur vapor and cover gas 21.
【００１７】以下、充放電に伴う電池内の活物質挙動を
説明する。電池はナトリウムや硫黄等電池活物質が液体
状態となる３００℃に加熱して運転した。放電運転で
は、補助導電体１４に含浸された硫黄がナトリウム極
（負極）６から固体電解質１を透過したナトリウム７と
反応して、多硫化ナトリウム１２を生成する。生成した
多硫化ナトリウム１２は多硫化ナトリウムの流路パス１
７あるいは、高抵抗層１３を流路パスとしてバルク１８
へと流下する。不足する硫黄はバルク１８の硫黄１１か
ら硫黄の流路パス１６を経て補助導電体１４へと補給さ
れる。The behavior of the active material in the battery due to charge / discharge will be described below. The battery was operated by heating it to 300 ° C. at which the battery active material such as sodium and sulfur becomes liquid. In the discharge operation, the sulfur impregnated in the auxiliary conductor 14 reacts with the sodium 7 that has permeated the solid electrolyte 1 from the sodium electrode (negative electrode) 6 to generate sodium polysulfide 12. The generated sodium polysulfide 12 is a sodium polysulfide flow path 1
7 or bulk 18 using the high resistance layer 13 as a flow path.
Run down to. The lacking sulfur is replenished from the sulfur 11 in the bulk 18 to the auxiliary conductor 14 via the sulfur flow path 16.
【００１８】一方充電では、補助導電体１４内の多硫化
ナトリウムをナトリウムと硫黄に解離し、ナトリウムは
ナトリウムイオンの流路パス１９を通って高抵抗層１３
へ向かい、さらに固体電解質１を透過してナトリウム極
（負極）６にもどる。硫黄は硫黄の流路パス１６を経て
バルクの硫黄１１へと流出する。無論、バルクでは硫黄
と五硫化ナトリウムは二層に分離する。充電反応で不足
した多硫化ナトリウムは多硫化ナトリウムの流路パス１
７あるいは、高抵抗層１３を流路パスとしてバルク１８
から補給される。さらに充電が進んでも多硫化ナトリウ
ムの流路パス１７によって電池容器の底部に存在する多
硫化ナトリウムが吸上げられ、正極活物質（多硫化ナト
リウム）の吸上げ供給パス１５を通って、補助導電体１
４の上部まで供給されるので正極容器４内に存在する殆
どの多硫化ナトリウムが充電可能である。On the other hand, during charging, sodium polysulfide in the auxiliary conductor 14 is dissociated into sodium and sulfur, and the sodium passes through the sodium ion flow path 19 to form the high resistance layer 13.
To the sodium electrode (negative electrode) 6 through the solid electrolyte 1. Sulfur flows out to bulk sulfur 11 via the sulfur flow path 16. Of course, in the bulk, sulfur and sodium pentasulfide separate into two layers. Sodium polysulfide that was insufficient due to the charging reaction is sodium polysulfide flow path 1
7 or bulk 18 using the high resistance layer 13 as a flow path.
Will be supplied from. Even if the charging is further advanced, sodium polysulfide existing at the bottom of the battery container is sucked up by the sodium polysulfide flow path 17, and passes through the suction supply path 15 for the positive electrode active material (sodium polysulfide), and then the auxiliary conductor. 1
Since most of the sodium polysulfide existing in the positive electrode container 4 can be charged because it is supplied up to the upper part of 4.
【００１９】なお、上記の硫黄の流路パス１６，多硫化
ナトリウムの流路パス１７，ナトリウムイオンの流路パ
ス１９は固体電解質１の径方向に流路を形成するが、こ
れらのパスは固体電解質１の軸方向にも連続する構造と
する。また、硫黄の流路パス１６，多硫化ナトリウムの
流路パス１７，ナトリウムイオンの流路パス１９は含浸
する電池活物質を除き、構成部材は必ずしも導電性部材
である必要はない。The sulfur flow path 16, sodium polysulfide flow path 17 and sodium ion flow path 19 described above form a flow path in the radial direction of the solid electrolyte 1, but these paths are solid. The structure is also continuous in the axial direction of the electrolyte 1. In addition, the sulfur flow passage path 16, the sodium polysulfide flow passage path 17, and the sodium ion flow passage path 19 do not necessarily have to be conductive members except for the battery active material to be impregnated.
【００２０】バルク１８の活物質液面高さ２２は、集電
極１０全体が液面下になるように配置した。正極容器に
ついては図１では矩形としたが円形，楕円形等任意の形
状であっても何ら機能を損ねるものではない。The active material liquid level height 22 of the bulk 18 was arranged so that the entire collecting electrode 10 was below the liquid level. Although the positive electrode container has a rectangular shape in FIG. 1, it does not impair the function even if it has an arbitrary shape such as a circular shape or an elliptical shape.
【００２１】（実施例２）図４は本発明の第２の実施例
を示す図である。図１の正極活物質（多硫化ナトリウ
ム）の吸上げ供給パス１５を除去し、かつ、硫黄の流路
パス１６を除去して補助導電体１４が直接バルクの電池
活物質とコンタクトできるように集電極１０に開口部２
３を設けたものである。無論、ナトリウムイオンの流路
パス１９を兼ねた多硫化ナトリウムの流路パス１７が存
在し、電池反応に必要なナトリウムイオンと多硫化ナト
リウムを補助導電体１４に供給する。(Embodiment 2) FIG. 4 is a diagram showing a second embodiment of the present invention. The suction supply path 15 for the positive electrode active material (sodium polysulfide) of FIG. 1 is removed, and the flow path path 16 for sulfur is removed so that the auxiliary conductor 14 can directly contact the bulk battery active material. Opening 2 in electrode 10
3 is provided. Of course, there is a sodium polysulfide flow path 17 that also serves as a sodium ion flow path 19, and supplies sodium ions and sodium polysulfide necessary for the battery reaction to the auxiliary conductor 14.
【００２２】（実施例３）図５は本発明の第３の実施例
を示す図である。図１の正極活物質（多硫化ナトリウ
ム）の吸上げ供給パス１５を除去し、かつ、多硫化ナト
リウムの流路パス１７を除去して補助導電体１４が直接
バルクの電池活物質とコンタクトできるように集電極１
０に開口部２３を設けたものである。無論、硫黄の流路
パス１６が存在し、電池反応に必要な硫黄を補助導電体
１４に供給する。(Embodiment 3) FIG. 5 is a diagram showing a third embodiment of the present invention. By removing the suction supply path 15 of the positive electrode active material (sodium polysulfide) shown in FIG. 1 and the flow path path 17 of sodium polysulfide, the auxiliary conductor 14 can directly contact the bulk battery active material. Collector electrode 1
0 is provided with the opening 23. Of course, the sulfur flow path 16 is provided to supply the auxiliary conductor 14 with sulfur required for the cell reaction.
【００２３】（実施例４）図６は本発明の第４の実施例
を示す図である。図１の正極活物質（多硫化ナトリウ
ム）の吸上げ供給パス１５を除去したが、ナトリウムイ
オンの流路パス１９を兼ねた多硫化ナトリウムの流路パ
ス１７と硫黄の流路パス１６が装備され、電池反応に必
要な硫黄と多硫化ナトリウムは補助導電体１４に供給さ
れる。(Embodiment 4) FIG. 6 is a diagram showing a fourth embodiment of the present invention. The suction supply path 15 for the positive electrode active material (sodium polysulfide) shown in FIG. 1 is removed, but a sodium polysulfide flow path 17 and a sulfur flow path 16 which also function as sodium ion flow paths 19 are provided. The sulfur and sodium polysulfide necessary for the battery reaction are supplied to the auxiliary conductor 14.
【００２４】（実施例５）図７は本発明の第５の実施例
を示す図である。図１の正極活物質（多硫化ナトリウ
ム）の吸上げ供給パス１５を正極容器４の内周に沿わせ
て構成し、ナトリウムイオンの流路パス１９を兼ねた多
硫化ナトリウムの流路パス１７を接触することにより、
電池反応に必要なナトリウムイオンと多硫化ナトリウム
を補助導電体１４に供給する。(Embodiment 5) FIG. 7 is a diagram showing a fifth embodiment of the present invention. The suction supply path 15 for the positive electrode active material (sodium polysulfide) of FIG. 1 is configured along the inner circumference of the positive electrode container 4, and the sodium polysulfide flow path 17 also serves as the sodium ion flow path 19. By touching,
Sodium ions and sodium polysulfide necessary for the battery reaction are supplied to the auxiliary conductor 14.
【００２５】（実施例６）図８は本発明の第６の実施例
を示す図である。図１に示した正極容器４内の電池活物
質の液面２２（実質的には硫黄１１の液面）を下げて、
補助導電体１４をカバーガス及び硫黄蒸気２１に露出さ
せ、充放電運転した例である。この場合は、正極容器４
内を硫黄蒸気で満たす程度に減圧すると、さらに、特性
が改善される。理由は硫黄蒸気によって補助導電体１４
に硫黄を供給することが可能となるためである。(Sixth Embodiment) FIG. 8 is a diagram showing a sixth embodiment of the present invention. By lowering the liquid surface 22 (substantially the liquid surface of sulfur 11) of the battery active material in the positive electrode container 4 shown in FIG.
In this example, the auxiliary conductor 14 is exposed to the cover gas and the sulfur vapor 21 and the charging / discharging operation is performed. In this case, the positive electrode container 4
The characteristics are further improved by reducing the pressure so that the inside is filled with sulfur vapor. The reason is that the sulfur vapor causes the auxiliary conductor 14
This is because it becomes possible to supply sulfur to the.
【００２６】なお、図１で正極活物質（多硫化ナトリウ
ム）の吸上げ供給パス１５は硫黄吸上げ流路パスとする
事が可能である。また、上記二種の流路パスを固体電解
質の軸方向に交互に設けることも可能である。また、軸
方向ではなく、周方向に半分ずつ等設けることも有効で
ある。上記実施例は、固体電解質として、円筒管を用い
た。電池の性能を最大限引き出すには、固体電解質管を
水平に設置することが好ましい。The suction supply path 15 for the positive electrode active material (sodium polysulfide) in FIG. 1 can be a sulfur suction passage path. It is also possible to alternately provide the two types of flow path in the axial direction of the solid electrolyte. It is also effective to provide half or the like in the circumferential direction instead of the axial direction. In the above example, a cylindrical tube was used as the solid electrolyte. In order to maximize the battery performance, it is preferable to install the solid electrolyte tube horizontally.
【００２７】[0027]
【発明の効果】以上説明したように本発明によれば、従
来のナトリウム硫黄電池を２倍出力、かつ、２倍容量以
上の優れた電池特性で運転できる電池を提供できる。As described above, according to the present invention, it is possible to provide a battery which can double the output of the conventional sodium-sulfur battery and can be operated with excellent battery characteristics of double the capacity or more.
【図１】本発明の第１の実施例の横断面を示す図。FIG. 1 is a diagram showing a cross section of a first embodiment of the present invention.
【図２】従来例の構造を示す図。FIG. 2 is a diagram showing a structure of a conventional example.
【図３】集電極を用いた電池の構造を示す図。FIG. 3 is a diagram showing a structure of a battery using a collecting electrode.
【図４】本発明の第２の実施例の横断面を示す図。FIG. 4 is a diagram showing a cross section of a second embodiment of the present invention.
【図５】本発明の第３の実施例の横断面を示す図。FIG. 5 is a diagram showing a cross section of a third embodiment of the present invention.
【図６】本発明の第４の実施例の横断面を示す図。FIG. 6 is a diagram showing a cross section of a fourth embodiment of the present invention.
【図７】本発明の第５の実施例の横断面を示す図。FIG. 7 is a diagram showing a cross section of a fifth embodiment of the present invention.
【図８】本発明の第６の実施例の横断面を示す図。FIG. 8 is a diagram showing a cross section of a sixth embodiment of the present invention.
１…固体電解質、２…安全容器、３…硫黄極、４…正極
容器、５…負極容器、６…ナトリウム極（負極）、７…
ナトリウム、８…多硫化ナトリウム極、９…硫黄極、１
０…集電極、１１…硫黄、１２…多硫化ナトリウム、１
３…高抵抗層、１４…補助導電体、１５，２４…正極活
物質（多硫化ナトリウム）の吸上げ供給パス、１６…硫
黄の流路パス、１７…多硫化ナトリウムの流路パス、１
８…バルク、１９…ナトリウムイオンの流路パス、２０
…活物質液面、２１…カバーガス及び硫黄蒸気、２２…
活物質液面高さ、２３…集電極の開口部。1 ... Solid electrolyte, 2 ... Safety container, 3 ... Sulfur electrode, 4 ... Positive electrode container, 5 ... Negative electrode container, 6 ... Sodium electrode (negative electrode), 7 ...
Sodium, 8 ... Sodium polysulfide electrode, 9 ... Sulfur electrode, 1
0 ... Collection electrode, 11 ... Sulfur, 12 ... Sodium polysulfide, 1
3 ... High resistance layer, 14 ... Auxiliary conductor, 15, 24 ... Suction supply path of positive electrode active material (sodium polysulfide), 16 ... Sulfur flow path path, 17 ... Sodium polysulfide flow path path, 1
8 ... Bulk, 19 ... Sodium ion flow path, 20
… Active material liquid level, 21… Cover gas and sulfur vapor, 22…
Liquid level of active material, 23 ... Opening of collector electrode.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 斎藤 義則 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・電機開発研究所内 Ｆターム(参考） 5H029 AJ02 AJ03 AK05 AL13 AM15 BJ02 BJ16 DJ05 DJ07 DJ09 EJ07 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Yoshinori Saito 2-12-1 Omika-cho, Hitachi-shi, Ibaraki Prefecture Ceremony Company Hitachi, Ltd. F-term (reference) 5H029 AJ02 AJ03 AK05 AL13 AM15 BJ02 BJ16 DJ05 DJ07 DJ09 EJ07
Claims (8)
硫黄または多硫化ナトリウム溶融塩を主成分とする正極
活物質と、前記負極活物質と正極活物質間に介在され、
ナトリウムイオンが通過できる固体電解質と、正極電流
を流す集電極とを備えたナトリウム硫黄電池において、
前記固体電解質と集電極間に補助導電体を装着して電池
反応領域を形成し、この電池反応領域に前記集電極から
固体電解質に向かうナトリウムイオンの流路パスを設け
たことを特徴とするナトリウム硫黄電池。1. A negative electrode active material containing sodium as a main component,
A positive electrode active material containing sulfur or sodium polysulfide molten salt as a main component, and interposed between the negative electrode active material and the positive electrode active material,
In a sodium-sulfur battery provided with a solid electrolyte through which sodium ions can pass, and a collector electrode for passing a positive electrode current,
An auxiliary conductor is mounted between the solid electrolyte and the collecting electrode to form a battery reaction region, and a sodium ion flow path from the collecting electrode to the solid electrolyte is provided in the battery reaction region. Sulfur battery.
硫黄または多硫化ナトリウム溶融塩を主成分とする正極
活物質と、前記負極活物質と正極活物質間に介在され、
ナトリウムイオンが通過できる固体電解質と、正極電流
を流す集電極とを備えたナトリウム硫黄電池において、
前記固体電解質と集電極間に補助導電体を装着して電池
反応領域を形成し、この電池反応領域に多硫化ナトリウ
ムの流路パスを設けたことを特徴とするナトリウム硫黄
電池。2. A negative electrode active material containing sodium as a main component,
A positive electrode active material containing sulfur or sodium polysulfide molten salt as a main component, and interposed between the negative electrode active material and the positive electrode active material,
In a sodium-sulfur battery provided with a solid electrolyte through which sodium ions can pass, and a collector electrode for passing a positive electrode current,
A sodium-sulfur battery, wherein an auxiliary conductor is attached between the solid electrolyte and the collector electrode to form a battery reaction region, and a flow path of sodium polysulfide is provided in the battery reaction region.
黄または多硫化ナトリウム溶融塩を主成分とする正極活
物質、前記負極活物質と正極活物質間に介在し、ナトリ
ウムイオンが通過できる固体電解質ならびに、正極電流
を流す集電極を主たる構成要素とするナトリウム硫黄電
池において、前記固体電解質と集電極間に補助導電体を
装着すると共に、この補助導電体の内側層に高抵抗層を
設けて電池反応領域を形成し、この電池反応領域に硫黄
の流路パスを設けたことを特徴とするナトリウム硫黄電
池。3. A negative electrode active material containing sodium as a main component, a positive electrode active material containing sulfur or sodium polysulfide molten salt as a main component, and a solid which is interposed between the negative electrode active material and the positive electrode active material and through which sodium ions can pass. In an electrolyte and a sodium-sulfur battery whose main component is a collecting electrode for passing a positive electrode current, an auxiliary conductor is attached between the solid electrolyte and the collecting electrode, and a high resistance layer is provided on the inner layer of the auxiliary conductor. A sodium-sulfur battery characterized in that a battery reaction region is formed and a sulfur flow path is provided in this battery reaction region.
リウム硫黄電池において、前記流路パスを円筒状固体電
解質の半径方向並びに軸方向に設けたことを特徴とした
ナトリウム硫黄電池。4. The sodium-sulfur battery according to any one of claims 1 to 3, wherein the flow path is provided in a radial direction and an axial direction of the cylindrical solid electrolyte.
リウム硫黄電池において、前記流路パスを形成する構造
材として電気導電性のない材料を用いることを特徴とす
るナトリウム硫黄電池。5. The sodium-sulfur battery according to any one of claims 1 to 3, wherein a material having no electrical conductivity is used as a structural material forming the flow path.
硫黄または多硫化ナトリウム溶融塩を主成分とする正極
活物質と、前記負極活物質と正極活物質間に介在され、
ナトリウムイオンが通過できる固体電解質と、正極電流
を流す集電極とを備えたナトリウム硫黄電池において、
前記固体電解質と集電極間に補助導電体を装着すると共
に、その補助導電体の内側層に高抵抗層を装着して電池
反応領域を形成し、この電池反応領域にナトリウムイオ
ンの流路パスと、多硫化ナトリウムの流路パスと、硫黄
の流路パスをそれぞれ１乃至複数個設けたことを特徴と
したナトリウム硫黄電池。6. A negative electrode active material containing sodium as a main component,
A positive electrode active material containing sulfur or sodium polysulfide molten salt as a main component, and interposed between the negative electrode active material and the positive electrode active material,
In a sodium-sulfur battery provided with a solid electrolyte through which sodium ions can pass, and a collector electrode for passing a positive electrode current,
An auxiliary conductor is mounted between the solid electrolyte and the collector electrode, and a high resistance layer is mounted on the inner layer of the auxiliary conductor to form a battery reaction region, and a sodium ion flow path is formed in the battery reaction region. A sodium-sulfur battery characterized in that one or more sodium polysulfide flow paths and one or more sulfur flow paths are provided.
硫黄または多硫化ナトリウム溶融塩を主成分とする正極
活物質と、前記負極活物質と正極活物質間に介在され、
ナトリウムイオンが通過できる固体電解質と、正極電流
を流す集電極とを備えたナトリウム硫黄電池において、
前記固体電解質と集電極間に補助導電体を装着すると共
に、その補助導電体の内側層に高抵抗層を装着して電池
反応領域を形成し、この電池反応領域にナトリウムイオ
ンの流路パスと、多硫化ナトリウムの流路パスと、硫黄
の流路パスの少なくとも一つを設け、かつ、硫黄吸上げ
流路パスと多硫化ナトリウム吸上げ流路パスを固体電解
質の軸方向並びに周方向に交互に設置したことを特徴と
したナトリウム硫黄電池。7. A negative electrode active material containing sodium as a main component,
A positive electrode active material containing sulfur or sodium polysulfide molten salt as a main component, and interposed between the negative electrode active material and the positive electrode active material,
In a sodium-sulfur battery provided with a solid electrolyte through which sodium ions can pass, and a collector electrode for passing a positive electrode current,
An auxiliary conductor is mounted between the solid electrolyte and the collector electrode, and a high resistance layer is mounted on the inner layer of the auxiliary conductor to form a battery reaction region, and a sodium ion flow path is formed in the battery reaction region. , At least one of a sodium polysulfide flow path and a sulfur flow path is provided, and the sulfur suction flow path and the sodium polysulfide suction flow path are alternated in the axial and circumferential directions of the solid electrolyte. A sodium-sulfur battery characterized by being installed in.
リウム硫黄電池において、前記固体電解質を水平に設置
したことを特徴としたナトリウム硫黄電池。8. The sodium-sulfur battery according to any one of claims 1 to 7, wherein the solid electrolyte is installed horizontally.
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|---|---|---|---|
| JP2002020874A JP2003223929A (en) | 2002-01-30 | 2002-01-30 | Sodium-sulfur battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002020874A JP2003223929A (en) | 2002-01-30 | 2002-01-30 | Sodium-sulfur battery |
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| Publication Number | Publication Date |
|---|---|
| JP2003223929A true JP2003223929A (en) | 2003-08-08 |
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ID=27744253
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|---|---|---|---|
| JP2002020874A Pending JP2003223929A (en) | 2002-01-30 | 2002-01-30 | Sodium-sulfur battery |
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| JP (1) | JP2003223929A (en) |
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2002
- 2002-01-30 JP JP2002020874A patent/JP2003223929A/en active Pending
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