JPH11273719A - Manufacture of sodium-sulfur battery - Google Patents
Manufacture of sodium-sulfur batteryInfo
- Publication number
- JPH11273719A JPH11273719A JP10072633A JP7263398A JPH11273719A JP H11273719 A JPH11273719 A JP H11273719A JP 10072633 A JP10072633 A JP 10072633A JP 7263398 A JP7263398 A JP 7263398A JP H11273719 A JPH11273719 A JP H11273719A
- Authority
- JP
- Japan
- Prior art keywords
- active material
- electrode active
- sodium
- negative electrode
- positive electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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)
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
電池の製造方法に係り、特に、容量低下等の不都合を生
じることのないナトリウム−硫黄電池の製造方法に関す
るものである。[0001] The present invention relates to a method for manufacturing a sodium-sulfur battery, and more particularly to a method for manufacturing a sodium-sulfur battery which does not cause a disadvantage such as a decrease in capacity.
【０００２】[0002]
【従来の技術】まず、ナトリウム−硫黄電池を図面を参
照して説明する。図５（ａ）及び図５（ｂ）に示す円筒
形のナトリウム−硫黄電池１には、ナトリウムからなる
負極活物質２と、硫黄からなる正極活物質３と、負極活
物質２と正極活物質３との間に配置された固体電解質４
と、正極活物質３を含浸して正極活物質３の電子伝導を
補助するための炭素繊維布からなる導電助材５と、正極
活物質３及び導電助材５と外部回路とを電気的に接続す
る正極集電体６とが備えられている。2. Description of the Related Art First, a sodium-sulfur battery will be described with reference to the drawings. The cylindrical sodium-sulfur battery 1 shown in FIGS. 5A and 5B has a negative electrode active material 2 made of sodium, a positive electrode active material 3 made of sulfur, a negative electrode active material 2 and a positive electrode active material. 3 and a solid electrolyte 4 disposed between
A conductive auxiliary material 5 made of carbon fiber cloth for impregnating the positive electrode active material 3 to assist electron conduction of the positive electrode active material 3, and electrically connecting the positive electrode active material 3, the conductive auxiliary material 5, and an external circuit to each other. A positive electrode current collector 6 to be connected is provided.
【０００３】図５（ａ）及び図５（ｂ）においては、固
体電解質４は有底の円筒管４′であり、その材質はナト
リウムイオンに対して伝導性を有するセラミックスまた
はガラス等からなるものであって、例えばβ−アルミナ
（Ｎａ2Ｏ・１１Ａｌ2Ｏ3）や、安定化剤としてＭｇ
Ｏ、Ｌｉ2Ｏ等が添加されたβ”−アルミナ（３Ｎａ2Ｏ
・１６Ａｌ2Ｏ3）等が用いられる。また、図５（ａ）及
び図５（ｂ）においては、正極集電体６は円筒缶６′で
あり、その材質は例えばステンレス、Ｎｉ合金等が用い
られる。In FIGS. 5 (a) and 5 (b), the solid electrolyte 4 is a bottomed cylindrical tube 4 'made of ceramics or glass having conductivity to sodium ions. For example, β-alumina (Na 2 O · 11Al 2 O 3 ) or Mg as a stabilizer
Β ″ -alumina (3Na 2 O) to which O, Li 2 O, etc. are added
.16Al 2 O 3 ). 5 (a) and 5 (b), the positive electrode current collector 6 is a cylindrical can 6 ', and its material is, for example, stainless steel, Ni alloy, or the like.
【０００４】ナトリウム−硫黄電池１においては、負極
活物質２は、固体電解質４の円筒管４′に収納されてい
る。また、固体電解質４の円筒管４′は、正極集電体６
である円筒缶６′に収納されている。更に、正極活物質
３（硫黄）が含浸された炭素繊維布からなる導電助材５
は、円筒缶６′と固体電解質４の円筒管４′との間に配
置されている。このようにして、固体電解質４は、負極
活物質２と正極活物質３との間に配置されて、負極活物
質２と正極活物質３とを隔離している。つまり、負極活
物質２は、固体電解質４からなる円筒管４′内の負極活
物質収納部Ａ内に収納され、また、正極活物質３は、円
筒管４′の外周側における正極集電体６からなる円筒缶
６′内の正極活物質収納部Ｂ内に収納されている。[0004] In the sodium-sulfur battery 1, the negative electrode active material 2 is contained in a cylindrical tube 4 ′ of a solid electrolyte 4. The cylindrical tube 4 ′ of the solid electrolyte 4 is connected to the positive electrode current collector 6.
In a cylindrical can 6 '. Further, a conductive auxiliary material 5 made of carbon fiber cloth impregnated with the positive electrode active material 3 (sulfur)
Is disposed between the cylindrical can 6 ′ and the cylindrical tube 4 ′ of the solid electrolyte 4. In this manner, the solid electrolyte 4 is disposed between the negative electrode active material 2 and the positive electrode active material 3, and separates the negative electrode active material 2 from the positive electrode active material 3. That is, the negative electrode active material 2 is stored in the negative electrode active material storage portion A in the cylindrical tube 4 ′ made of the solid electrolyte 4, and the positive electrode active material 3 is stored in the positive electrode current collector on the outer peripheral side of the cylindrical tube 4 ′. 6 is housed in a positive electrode active material housing B in a cylindrical can 6 ′.
【０００５】更に、固体電解質４の円筒管４′の上部に
は、ガラス半田等の接合材によりα−アルミナ等からな
る絶縁リング７が接合されている。絶縁リング７は円筒
缶６′に接合されて負極活物質２及び正極活物質３を密
封している。封口体８は、絶縁リング７に接合されてお
り、負極端子の役割を果たす。また、封口体８には、負
極集電体９が接続されている。負極集電体９は、負極活
物質２と負極端子である封口体８とを電気的に接続して
いる。Further, an insulating ring 7 made of α-alumina or the like is joined to the upper portion of the cylindrical tube 4 ′ of the solid electrolyte 4 by a joining material such as glass solder. The insulating ring 7 is joined to the cylindrical can 6 ′ to seal the negative electrode active material 2 and the positive electrode active material 3. The sealing body 8 is joined to the insulating ring 7 and serves as a negative electrode terminal. Further, a negative electrode current collector 9 is connected to the sealing body 8. The negative electrode current collector 9 electrically connects the negative electrode active material 2 and the sealing member 8 as a negative electrode terminal.
【０００６】このナトリウム−硫黄電池１の負極におけ
る放電反応は、式（１）に示す通りである。即ち、負極
活物質２であるナトリウム（Ｎａ）がナトリウムイオン
（Ｎａ+）と電子（ｅ-）とに分かれ、ナトリウムイオン
（Ｎａ+）は固体電解質４内を伝導して正極活物質３中
に侵入し、電子（ｅ-）は負極集電体９及び封口体８を
介して外部回路に流れる。正極における放電反応は、式
（２）に示す通りであり、正極活物質３中に侵入したナ
トリウムイオン（Ｎａ+）が硫黄（Ｓ）と反応して、多
硫化ナトリウム（Ｎａ2Ｓx）を生成する。The discharge reaction at the negative electrode of the sodium-sulfur battery 1 is as shown in equation (1). That is, sodium (Na), which is the negative electrode active material 2, is divided into sodium ions (Na + ) and electrons (e − ), and the sodium ions (Na + ) conduct in the solid electrolyte 4 and enter the positive electrode active material 3. invading electrons (e -) flows in the external circuit via the negative electrode current collector 9 and the sealing member 8. The discharge reaction at the positive electrode is as shown in equation (2). Sodium ions (Na + ) that have entered the positive electrode active material 3 react with sulfur (S) to convert sodium polysulfide (Na 2 S x ). Generate.
【０００７】ナトリウム−硫黄電池１の充電時には、放
電反応と逆の反応が起こり、ナトリウム（Ｎａ）および
硫黄（Ｓ）が生成する。通常は、多硫化ナトリウム（Ｎ
ａ2Ｓx）の一部が残留する程度まで充電する。これは、
硫黄（Ｓ）よりも多硫化ナトリウム（Ｎａ2Ｓx）の固有
抵抗が低いために、多硫化ナトリウム（Ｎａ2Ｓx）を残
存させておけば正極活物質の抵抗の上昇を抑えることが
できるからである。[0007] When charging the sodium-sulfur battery 1, a reaction reverse to the discharge reaction occurs, and sodium (Na) and sulfur (S) are generated. Usually, sodium polysulfide (N
a 2 S x ) is charged to the extent that a portion thereof remains. this is,
Since the specific resistance of sodium polysulfide (Na 2 S x ) is lower than that of sulfur (S), an increase in the resistance of the positive electrode active material can be suppressed by leaving sodium polysulfide (Na 2 S x ). Because.
【０００８】[0008]
【数１】 (Equation 1)
【０００９】[0009]
【数２】 (Equation 2)
【００１０】[0010]
【発明が解決しようとする課題】ところで、上記ナトリ
ウム−硫黄電池１の製造工程において、負極活物質２及
び正極活物質３がそれぞれ収納される負極活物質収納部
Ａ及び正極活物質収納部Ｂ内に酸素が混入していると、
これら負極活物質２及び正極活物質３が酸化してしま
い、特に、負極活物質２であるナトリウムが酸化して酸
化ナトリウムが生成されると、容量低下などの原因とな
ってしまう。このため、これら負極活物質２及び正極活
物質３を各収納部Ａ、Ｂへ収納する際には、アルゴンガ
ス等の不活性ガスによって収納部Ａ、Ｂ内をパージしな
ければならず、その作業に多大な手間を要してしまい、
電池の製造期間の長期化及びコストアップを招いてしま
うという問題があった。By the way, in the manufacturing process of the above-mentioned sodium-sulfur battery 1, in the negative electrode active material storage portion A and the positive electrode active material storage portion B in which the negative electrode active material 2 and the positive electrode active material 3 are stored, respectively. If oxygen is mixed in
The negative electrode active material 2 and the positive electrode active material 3 are oxidized. In particular, when sodium as the negative electrode active material 2 is oxidized to generate sodium oxide, it causes a decrease in capacity and the like. For this reason, when storing the negative electrode active material 2 and the positive electrode active material 3 in the storage sections A and B, the storage sections A and B must be purged with an inert gas such as argon gas. It takes a lot of time to work,
There has been a problem that the production period of the battery is lengthened and the cost is increased.
【００１１】この発明は、上記事情に鑑みてなされたも
ので、極めて容易に優れた性能のナトリウム−硫黄電池
を短期間にてかつ低コストにて製造することが可能なナ
トリウム−硫黄電池の製造方法を提供することを目的と
している。The present invention has been made in view of the above circumstances, and is a method for manufacturing a sodium-sulfur battery capable of extremely easily manufacturing a high-performance sodium-sulfur battery in a short period of time and at low cost. It is intended to provide a way.
【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、請求項１記載のナトリウム−硫黄電池の製造方法
は、少なくともナトリウムを含む負極活物質と、少なく
とも硫黄を含む正極活物質と、前記負極活物質と前記正
極活物質との間に位置してナトリウムイオンに対して伝
導性を有する固体電解質とを有するナトリウム−硫黄電
池の製造方法であって、前記負極活物質及び前記正極活
物質を収納する際に、これら負極活物質及び正極活物質
が収納される収納部の両方あるいは少なくともいずれか
一方に、酸素を吸着する酸素吸着材を投入することを特
徴としている。つまり、収納部へ負極活物質及び正極活
物質を収納する際に、収納部の両方あるいは少なくとも
いずれか一方に、酸素を吸着する酸素吸着材を投入する
ので、この酸素吸着材が投入された収納部内の酸素が確
実に除去される。According to a first aspect of the present invention, there is provided a method for manufacturing a sodium-sulfur battery, comprising: a negative electrode active material containing at least sodium; a positive electrode active material containing at least sulfur; A method for producing a sodium-sulfur battery having a solid electrolyte having conductivity for sodium ions located between a negative electrode active material and the positive electrode active material, wherein the negative electrode active material and the positive electrode active material are At the time of storage, an oxygen adsorbent that adsorbs oxygen is introduced into both or at least one of the storage sections in which the negative electrode active material and the positive electrode active material are stored. In other words, when the negative electrode active material and the positive electrode active material are stored in the storage section, an oxygen adsorbent for adsorbing oxygen is charged into both or at least one of the storage sections. Oxygen in the section is reliably removed.
【００１３】[0013]
【発明の実施の形態】以下、本発明のナトリウム−硫黄
電池の製造方法を図によって説明する。図１において、
符号１１は、本実施の形態のナトリウム−硫黄電池であ
る。このナトリウム−硫黄電池１１は、円筒管４′内の
負極活物質収納部Ａに設けられた負極集電体９が、有底
円筒状に形成された負極円筒体９′とされており、その
上端が前記封口体８に接続されている。この有底円筒状
に形成された負極円筒体９′の底板部分には、その中心
に孔部１２が形成されており、これにより、この負極円
筒体９′の内部と固体電解質４からなる円筒管４′内と
が連通されている。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS A method for manufacturing a sodium-sulfur battery according to the present invention will be described below with reference to the drawings. In FIG.
Reference numeral 11 denotes a sodium-sulfur battery of the present embodiment. In this sodium-sulfur battery 11, the negative electrode current collector 9 provided in the negative electrode active material storage section A in the cylindrical tube 4 'is a negative electrode cylindrical body 9' formed in a bottomed cylindrical shape. The upper end is connected to the sealing body 8. A hole 12 is formed at the center of the bottom plate portion of the negative electrode cylindrical body 9 ′ formed in a bottomed cylindrical shape, whereby a cylinder composed of the inside of the negative electrode cylindrical body 9 ′ and the solid electrolyte 4 is formed. The inside of the pipe 4 'is communicated.
【００１４】そして、この負極円筒体９′の内部及び負
極円筒体９′と円筒管４′との隙間、つまり、負極活物
質収納部Ａに、ナトリウムからなる負極活物質２が充填
されて収納されている。また、封口体８には、その中心
に、前記負極円筒体９′の内径と略同一径の開口部１３
が形成されており、この開口部１３は、封口体８の上部
から固定された蓋体１４によって封鎖されている。The inside of the negative electrode cylinder 9 'and the gap between the negative electrode cylinder 9' and the cylindrical tube 4 ', that is, the negative electrode active material storage portion A is filled with the negative electrode active material 2 made of sodium and stored. Have been. The sealing member 8 has, at its center, an opening 13 having substantially the same diameter as the inner diameter of the negative electrode cylinder 9 ′.
The opening 13 is closed by a lid 14 fixed from above the sealing body 8.
【００１５】次に、上記構成のナトリウム−硫黄電池１
１の製造方法をその手順に沿って説明する。 （１）まず、液状の硫黄からなる正極活物質３を含浸さ
せた後正極活物質３を固化させた導電助材５を円筒缶
６′内に収納し、この導電助材５内へ円筒管４′を挿入
し、円筒管４′内へ負極円筒体９′を挿入するととも
に、円筒管４′の上端外周に固定した絶縁リング７と円
筒缶６′の上端及び絶縁リング７と封口体８とを、ガラ
ス半田等の接合材を用いて熱圧接合する。このようにす
ると、正極活物質３が含浸された導電助材５が収納され
た円筒管４′の外周側における円筒缶６′内の正極活物
質収納部Ｂが封鎖され、また、円筒管４′内の所定位置
に、負極円筒体９′が配置された状態に封口体８が取り
付けられて、図２に示す状態とされる。ここで、導電助
材５に含浸された正極活物質３が収納される正極活物質
収納部Ｂには、この正極活物質収納部Ｂを封鎖する直前
に、酸素吸着材１７を投入する。この酸素吸着材１７
は、周囲の酸素と結合することによりその周囲における
酸素を除去する、例えば、酸素と結合して酸化物となる
チタンあるいはジルコニウム等の粉末である。Next, the sodium-sulfur battery 1 having the above structure
The first manufacturing method will be described along the procedure. (1) First, a conductive auxiliary material 5 in which a positive electrode active material 3 made of liquid sulfur is impregnated and then solidified is stored in a cylindrical can 6 ′, and a cylindrical tube is inserted into the conductive auxiliary material 5. 4 ', the negative electrode cylinder 9' is inserted into the cylindrical tube 4 ', and the insulating ring 7 fixed to the outer periphery of the upper end of the cylindrical tube 4', the upper end of the cylindrical can 6 ', the insulating ring 7 and the sealing member 8 Are thermally and pressure-bonded using a bonding material such as glass solder. In this way, the positive electrode active material storage portion B in the cylindrical can 6 'on the outer peripheral side of the cylindrical tube 4' in which the conductive auxiliary material 5 impregnated with the positive electrode active material 3 is stored is closed. The sealing body 8 is attached in a state where the negative electrode cylindrical body 9 'is arranged at a predetermined position in the space shown in FIG. Here, the oxygen adsorbent 17 is charged into the positive electrode active material storage section B in which the positive electrode active material 3 impregnated in the conductive auxiliary material 5 is stored, just before the positive electrode active material storage section B is closed. This oxygen adsorbent 17
Is a powder such as titanium or zirconium, which combines with oxygen in the surroundings to remove the oxygen in the surroundings, for example, becomes an oxide by combining with oxygen.
【００１６】（２）次いで、図３に示すように、封口体
８の開口部１３に、ナトリウム容器１５の吐出口１６を
接続する。このナトリウム容器１５は、その吐出口１６
が、封口体８の開口部１３と略同一径とされており、そ
の内部には、固形ナトリウム２′が収納されている。 （３）封口体８の開口部１３へナトリウム容器１５の吐
出口１６を接続した状態にて、ナトリウム容器１５内の
固形ナトリウム２′を吐出口１６から押し出す。このよ
うにすると、図４に示すように、ナトリウム容器１５の
吐出口１６から押し出された固形ナトリウム２′が封口
体８の開口部１３を介して負極活物質収納部Ａに配置さ
れた負極円筒体９′の内部へ入り込む。(2) Next, as shown in FIG. 3, the discharge port 16 of the sodium container 15 is connected to the opening 13 of the sealing body 8. This sodium container 15 has an outlet 16
Has a diameter substantially the same as that of the opening 13 of the sealing body 8, and contains therein solid sodium 2 ′. (3) With the discharge port 16 of the sodium container 15 connected to the opening 13 of the sealing body 8, the solid sodium 2 ′ in the sodium container 15 is pushed out from the discharge port 16. In this manner, as shown in FIG. 4, the solid sodium 2 ′ extruded from the discharge port 16 of the sodium container 15 is placed in the negative electrode active material accommodating section A through the opening 13 of the sealing body 8. It gets inside the body 9 '.
【００１７】（４）所定量の固形ナトリウム２′を負極
活物質収納部Ａ内の負極円筒体９′内へ充填して収納し
たら、封口体８の開口部１３に蓋体１４を取り付け、負
極活物質収納部Ａを封鎖する（図４参照）。ここで、固
形ナトリウム２′が収納される負極活物質収納部Ａに
は、負極活物質Ａを蓋体１４によって封鎖する直前に、
前述したように、酸素吸着材１７を投入する。この酸素
吸着材１７としては、前記同様、周囲の酸素と結合す
る、例えば、酸素と結合して酸化物となるチタンあるい
はジルコニウム等の粉末が用いられる。なお、この負極
活物質収納部Ａへの酸素吸着材１７の投入量としては、
負極活物質収納部Ａ内の酸素を十分に吸着することがで
き、しかも収納されるナトリウムの容量低下等の不都合
を生じることのない量（負極活物質収納部Ａ内に充填さ
れるナトリウム量の約５〜１５％程度）が好ましい。(4) After a predetermined amount of solid sodium 2 'is filled and stored in the negative electrode cylindrical body 9' in the negative electrode active material storage section A, the lid 14 is attached to the opening 13 of the sealing body 8, The active material storage section A is closed (see FIG. 4). Here, in the negative electrode active material storage section A in which the solid sodium 2 ′ is stored, immediately before the negative electrode active material A is closed by the lid 14,
As described above, the oxygen adsorbent 17 is charged. As described above, as the oxygen adsorbing material 17, a powder such as titanium or zirconium which binds to the surrounding oxygen, for example, becomes an oxide by binding to oxygen is used. The amount of the oxygen adsorbent 17 charged into the negative electrode active material storage section A is as follows.
An amount capable of sufficiently adsorbing oxygen in the negative electrode active material storage part A and causing no inconvenience such as a decrease in the capacity of the stored sodium (the amount of sodium filled in the negative electrode active material storage part A). About 5 to 15%) is preferable.
【００１８】（５）次に、ナトリウムの融点（約８０
℃）以上に加熱するとともに、蓋体１４に設けられた調
整孔から加圧する。このようにすると、負極円筒体９′
内の固形ナトリウム２′が液状化して負極円筒体９′の
底板部分の孔部１２から負極円筒体９′の外部へ流出
し、この負極円筒体９′と円筒管４′との隙間へ入り込
み、負極活物質収納部Ａへのナトリウムの充填が完了す
る（図１参照）。ここで、負極活物質収納部Ａ及び正極
活物質収納部Ｂへ投入した酸素吸着材１７は、それぞれ
負極活物質２及び正極活物質３に拡散し、これにより、
負極活物質収納部Ａ及び正極活物質収納部Ｂ内の酸素が
除去され、酸素による容量低下等の不都合が確実に取り
除かれる。(5) Next, the melting point of sodium (about 80
(° C.) or more, and pressurize through an adjustment hole provided in the lid 14. In this way, the negative electrode cylinder 9 '
The solid sodium 2 'in the inside liquefies and flows out of the hole 12 in the bottom plate portion of the negative electrode cylinder 9' to the outside of the negative electrode cylinder 9 'and enters the gap between the negative electrode cylinder 9' and the cylindrical tube 4 '. Then, the filling of the negative electrode active material container A with sodium is completed (see FIG. 1). Here, the oxygen adsorbent 17 charged into the negative electrode active material storage part A and the positive electrode active material storage part B diffuses into the negative electrode active material 2 and the positive electrode active material 3, respectively.
Oxygen in the negative electrode active material storage section A and the positive electrode active material storage section B is removed, and disadvantages such as a decrease in capacity due to oxygen are reliably removed.
【００１９】このように、本実施の形態のナトリウム−
硫黄電池の製造方法によれば、負極活物質収納部Ａ及び
正極活物質収納部Ｂへ負極活物質２及び正極活物質３を
収納する際に、負極活物質収納部Ａ及び正極活物質収納
部Ｂへ、周囲の酸素と結合することによりその周囲にお
ける酸素を除去する、例えば、チタンあるいはジルコニ
ウム等の粉末からなる酸素吸着材１７を投入するので、
前述したように、負極活物質収納部Ａ及び正極活物質収
納部Ｂ内の酸素を確実に除去することができる。これに
より、負極活物質収納部Ａ及び正極活物質収納部Ｂ内に
混入した酸素による負極活物質２及び正極活物質３の酸
化を確実に防止することができ、特に、負極活物質２で
あるナトリウムが酸化して酸化ナトリウムが生成される
ことによる容量低下が確実に防止されて安定した充放電
性能が得られた電池を製造することができる。As described above, the sodium-
According to the method for manufacturing a sulfur battery, when the negative electrode active material 2 and the positive electrode active material 3 are stored in the negative electrode active material storage A and the positive electrode active material storage B, the negative electrode active material storage A and the positive electrode active material storage B, the oxygen adsorbent 17 made of a powder such as titanium or zirconium, for example, is added to remove oxygen in the surroundings by combining with the surrounding oxygen.
As described above, oxygen in the negative electrode active material storage section A and the positive electrode active material storage section B can be reliably removed. Thereby, the oxidation of the negative electrode active material 2 and the positive electrode active material 3 by the oxygen mixed in the negative electrode active material storage part A and the positive electrode active material storage part B can be reliably prevented. It is possible to manufacture a battery in which a reduction in capacity due to oxidation of sodium to generate sodium oxide is reliably prevented, and stable charge / discharge performance is obtained.
【００２０】また、単に、負極活物質収納部Ａ及び正極
活物質収納部Ｂへ酸素吸着材１７を投入する作業を行う
だけで良いので、従来のように、アルゴンガス等の不活
性ガスによって負極活物質収納部Ａ及び正極活物質収納
部Ｂ内をパージするような煩雑な作業を不要とすること
ができ、これにより、電池の製造期間の短縮及び製造コ
ストの低減を図ることができる。Further, since it is only necessary to simply perform the operation of charging the oxygen adsorbing material 17 into the negative electrode active material storage section A and the positive electrode active material storage section B, as in the conventional case, the negative electrode is inert gas such as argon gas. Complicated work such as purging the active material storage section A and the positive electrode active material storage section B can be eliminated, thereby shortening the manufacturing period of the battery and reducing the manufacturing cost.
【００２１】なお、上記実施の形態のナトリウム−硫黄
電池の製造方法は、上記構造のナトリウム−硫黄電池１
１に限らず、例えば、円筒管４′の外周側の空間が、負
極活物質２が収納される負極活物質収納部Ａとされ、円
筒管４′の内部が、正極活物質３が収納される正極活物
質収納部Ｂとされた構造のナトリウム−硫黄電池を製造
する場合にも適応することができるのは勿論である。ま
た、負極活物質収納部Ａ及び正極活物質収納部Ｂへ投入
する酸素吸着材１７としては、粉末に限らず棒状であっ
ても良い。なおまた、各収納部Ａ、Ｂへの負極活物質
２、正極活物質３の充填の仕方としては、上記の例に限
定されることはなく、例えば、液状のナトリウムを負極
収納部Ａへ充填するような充填方法であっても良い。ま
た、酸素吸着材１７は、負極活物質収納部Ａ及び正極活
物質収納部Ｂへそれぞれ負極活物質２及び正極活物質３
を収納させる前に投入しても良い。The method for manufacturing the sodium-sulfur battery according to the above-described embodiment uses the sodium-sulfur battery 1 having the above structure.
For example, the space on the outer peripheral side of the cylindrical tube 4 ′ is a negative electrode active material storage portion A in which the negative electrode active material 2 is stored, and the inside of the cylindrical tube 4 ′ stores the positive electrode active material 3. Needless to say, the present invention can be applied to the case of manufacturing a sodium-sulfur battery having a structure in which the positive electrode active material storage portion B is used. Further, the oxygen adsorbing material 17 to be charged into the negative electrode active material storage part A and the positive electrode active material storage part B is not limited to powder, but may be rod-shaped. In addition, the method of filling the negative electrode active material 2 and the positive electrode active material 3 into each of the storage sections A and B is not limited to the above example. For example, liquid sodium is charged into the negative electrode storage section A. The filling method may be as follows. Further, the oxygen adsorbing material 17 transfers the negative electrode active material 2 and the positive electrode active material 3 to the negative electrode active material storage portion A and the positive electrode active material
May be put in before storing.
【００２２】[0022]
【発明の効果】以上、説明したように、本発明のナトリ
ウム−硫黄電池の製造方法によれば、下記の効果を得る
ことができる。請求項１記載のナトリウム−硫黄電池の
製造方法によれば、収納部へ負極活物質及び正極活物質
を収納する際に、収納部の両方あるいは少なくともいず
れか一方に、酸素を吸着する酸素吸着材を投入するの
で、この酸素吸着材が投入された収納部内の酸素を確実
に除去することができる。これにより、収納部内に混入
した酸素による活物質の酸化を確実に防止することがで
き活物質の酸化による容量低下が確実に防止されて安定
した充放電性能が得られた電池を製造することができ
る。また、単に、収納部へ酸素吸着材を投入する作業を
行うだけで良いので、従来のように、アルゴンガス等の
不活性ガスによって収納部内をパージするような煩雑な
作業を不要とすることができ、これにより、電池の製造
期間の短縮及び製造コストの低減を図ることができる。As described above, according to the method for manufacturing a sodium-sulfur battery of the present invention, the following effects can be obtained. According to the method for manufacturing a sodium-sulfur battery according to claim 1, when storing the negative electrode active material and the positive electrode active material in the storage section, an oxygen adsorbent that adsorbs oxygen to both or at least one of the storage sections. , The oxygen in the storage section into which the oxygen adsorbent has been charged can be reliably removed. This makes it possible to reliably prevent the oxidation of the active material due to the oxygen mixed in the storage portion, and to reliably manufacture the battery in which the capacity reduction due to the oxidation of the active material is prevented and stable charge / discharge performance is obtained. it can. In addition, since it is sufficient to simply perform the operation of charging the oxygen adsorbent into the storage unit, it is not necessary to perform a complicated operation of purging the storage unit with an inert gas such as argon gas as in the related art. As a result, the manufacturing period of the battery and the manufacturing cost can be reduced.
【図１】 本発明の実施の形態のナトリウム−硫黄電池
の製造方法を説明するナトリウム−硫黄電池の縦断面図
である。FIG. 1 is a longitudinal sectional view of a sodium-sulfur battery explaining a method for manufacturing a sodium-sulfur battery according to an embodiment of the present invention.
【図２】 本発明の実施の形態のナトリウム−硫黄電池
の製造方法を説明する固形ナトリウムの充填前のナトリ
ウム−硫黄電池の縦断面図である。FIG. 2 is a longitudinal sectional view of a sodium-sulfur battery before filling with solid sodium, illustrating a method for manufacturing a sodium-sulfur battery according to an embodiment of the present invention.
【図３】 本発明の実施の形態のナトリウム−硫黄電池
の製造方法を説明する固形ナトリウムの充填作業中のナ
トリウム−硫黄電池の縦断面図である。FIG. 3 is a vertical cross-sectional view of the sodium-sulfur battery during a filling operation of solid sodium for explaining the method of manufacturing the sodium-sulfur battery according to the embodiment of the present invention.
【図４】 本発明の実施の形態のナトリウム−硫黄電池
の製造方法を説明する固形ナトリウムが充填されたナト
リウム−硫黄電池の縦断面図である。FIG. 4 is a longitudinal sectional view of a sodium-sulfur battery filled with solid sodium, illustrating a method for manufacturing a sodium-sulfur battery according to an embodiment of the present invention.
【図５】 ナトリウム−硫黄電池の構成及び構造を示す
図であって、（ａ）はナトリウム−硫黄電池の縦断面図
であり、（ｂ）はナトリウム−硫黄電池の横断面図であ
る。5A and 5B are diagrams showing a configuration and a structure of a sodium-sulfur battery, wherein FIG. 5A is a longitudinal sectional view of the sodium-sulfur battery, and FIG. 5B is a transverse sectional view of the sodium-sulfur battery.
２ 負極活物質（ナトリウム） ３ 正極活物質 ４ 固体電解質 １１ ナトリウム−硫黄電池 １７ 酸素吸着材 Ａ 負極活物質収納部（収納部） Ｂ 正極活物質収納部（収納部） 2 negative electrode active material (sodium) 3 positive electrode active material 4 solid electrolyte 11 sodium-sulfur battery 17 oxygen adsorbent A negative electrode active material storage section (storage section) B positive electrode active material storage section (storage section)
Claims (1)
と、少なくとも硫黄を含む正極活物質と、前記負極活物
質と前記正極活物質との間に位置してナトリウムイオン
に対して伝導性を有する固体電解質とを有するナトリウ
ム−硫黄電池の製造方法であって、 前記負極活物質及び前記正極活物質を収納する際に、こ
れら負極活物質及び正極活物質が収納される収納部の両
方あるいは少なくともいずれか一方に、酸素を吸着する
酸素吸着材を投入することを特徴とするナトリウム−硫
黄電池の製造方法。1. A negative electrode active material containing at least sodium, a positive electrode active material containing at least sulfur, and a solid electrolyte located between the negative electrode active material and the positive electrode active material and having conductivity for sodium ions. A method for manufacturing a sodium-sulfur battery having: wherein, when the negative electrode active material and the positive electrode active material are stored, both or at least one of the storage units in which the negative electrode active material and the positive electrode active material are stored A method for producing a sodium-sulfur battery, characterized in that an oxygen adsorbent for adsorbing oxygen is introduced into the device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10072633A JPH11273719A (en) | 1998-03-20 | 1998-03-20 | Manufacture of sodium-sulfur battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10072633A JPH11273719A (en) | 1998-03-20 | 1998-03-20 | Manufacture of sodium-sulfur battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11273719A true JPH11273719A (en) | 1999-10-08 |
Family
ID=13494998
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10072633A Pending JPH11273719A (en) | 1998-03-20 | 1998-03-20 | Manufacture of sodium-sulfur battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11273719A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010092856A (en) * | 2008-10-07 | 2010-04-22 | General Electric Co <Ge> | Energy storage device and associated method |
| JP2014239025A (en) * | 2013-05-07 | 2014-12-18 | 株式会社神戸製鋼所 | Positive electrode container for sodium-sulfur battery |
-
1998
- 1998-03-20 JP JP10072633A patent/JPH11273719A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010092856A (en) * | 2008-10-07 | 2010-04-22 | General Electric Co <Ge> | Energy storage device and associated method |
| JP2014239025A (en) * | 2013-05-07 | 2014-12-18 | 株式会社神戸製鋼所 | Positive electrode container for sodium-sulfur battery |
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