JPS59191269A - High temperature cell - Google Patents
High temperature cellInfo
- Publication number
- JPS59191269A JPS59191269A JP6740683A JP6740683A JPS59191269A JP S59191269 A JPS59191269 A JP S59191269A JP 6740683 A JP6740683 A JP 6740683A JP 6740683 A JP6740683 A JP 6740683A JP S59191269 A JPS59191269 A JP S59191269A
- Authority
- JP
- Japan
- Prior art keywords
- magnesia
- battery
- porous
- separator
- particles
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/30—Deferred-action cells
- H01M6/36—Deferred-action cells containing electrolyte and made operational by physical means, e.g. thermal cells
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Primary Cells (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、負極にリチウムあるいはリチウム合金を、正
極に硫化鉄、二硫化鉄などを用い、セパレータにマグネ
シアの枠体に充填した多孔質のマグネシア粒子を用いる
溶融塩電池に関りるものである。Detailed Description of the Invention The present invention provides a molten salt battery using lithium or a lithium alloy for the negative electrode, iron sulfide, iron disulfide, etc. for the positive electrode, and porous magnesia particles filled in a magnesia frame for the separator. It is related to.
従来、溶融塩を用いる高温形の電池においては、セパレ
ータ材質として、電池の作動温度である５ｏｏ′ｃ７）
η後での安定性、溶〜；塩中での耐蝕性、活物質に対す
る反応性等の面から窒化ホウ素とマグネシアが検討され
ている。窒化ホウ素を素材としたセパレータは、窒化ホ
ウ素をフェルト化することにＪこり多孔質に１ノで用い
ている。このフ、Ｌルトセパレータは多孔度も９０％弱
の大さな値を示し、電気的絶縁性などの電池のセバレー
、夕に要求される特性を充分に満足しＣいるものの、セ
パレータを多孔質とする７ｊめのフェルト化の価格が非
常に高い上、活物質の保持が不充分であるという問題が
あった。また窒化ホウ素はそのＪよでは溶融塩に濡れな
いため、窒化ホウ素をフェルト化した後、熱分解により
マグネシアを生成１する硝酸マグネシウムなどを用いて
繊維の表面（こングネシアを析出させて、溶融塩への濡
れ性を改ｉｊＸりるといった処理の工程を要した。Conventionally, in high-temperature batteries using molten salt, the separator material is 5oo'c7), which is the operating temperature of the battery.
Boron nitride and magnesia have been studied from the viewpoints of stability after η, corrosion resistance in salt, reactivity with active materials, etc. A separator made of boron nitride is used in a porous manner in which boron nitride is made into felt. Although this flat separator has a large porosity of just under 90% and fully satisfies the characteristics required for battery separators such as electrical insulation, it is difficult to make the separator porous. There was a problem in that the price of making the 7jth felt was very high, and the retention of the active material was insufficient. In addition, since boron nitride does not get wet with molten salt in its J shape, after felting boron nitride, magnesium nitrate, which produces magnesia by thermal decomposition, is used to deposit the molten salt on the surface of the fiber (to precipitate magnesia). It required a processing step to improve the wettability of the material.
ざらに狐、窒化ホウ素フェル［−を用いたしパレータは
、極板の充放電による変形につれて、厚ざが変化してし
まい、電池の寿命をり勘゛くづるどいっｔ、：欠点があ
った。The pallet made of boron nitride fer [-] has a drawback: the thickness changes as the electrode plate deforms due to charging and discharging, making it difficult to consider the life of the battery. .
マグネシアは現１ｉ′Ｊ：でのところ、繊組１ヒが行わ
れていないため、マグネシア粉末をセパレータに用いる
試みが行われている。しかし粉末を用いるセパレータは
、多孔度が５０％Ｍｒｒ ｍと小さく、そのために電池
での活物質利用率も低い値にとど４ってしまう。それに
電池組立て時においても、粉末のため取扱いが不便で、
電解質粉末と共に加圧成形して板状にするなどの処理を
必要とするといった欠点があった。At present, magnesia has not been subjected to fiber assembly, so attempts are being made to use magnesia powder in separators. However, a separator using powder has a small porosity of 50% Mrrm, and therefore the utilization rate of active material in a battery remains at a low value. Also, when assembling the battery, it is inconvenient to handle because it is a powder.
It has the disadvantage that it requires processing such as pressure molding together with electrolyte powder to form a plate shape.
本発明は、これらの欠点を改良し、安価で取扱いが容易
な上、溶融塩への濡れも良く、充分な多孔度を有し、電
池作動中、常に均一な厚みを有するセパレータを使用し
た電池を提供するものでｊうる。The present invention improves these drawbacks and provides a battery using a separator that is inexpensive, easy to handle, has good wettability to molten salt, has sufficient porosity, and has a constant thickness during battery operation. I can benefit from something that provides.
以下その実施例について詳述する。Examples thereof will be described in detail below.
多孔質のマグネシア粒子は、平均粒径０．３μのＮ貿マ
グネシアと、硝酸マグネシウムを原料にして製造したａ
まず苗質マグネシアに対して、硝酸マグネシウム水溶液
をマグネシアに挽Ｄ’；” シて ２重量％添加し、押
し出し造粒法により顆粒状とした後、この顆粒を１００
０℃で焼成して、多孔質でかつ取扱いに充分耐える強度
を有する粒子を得た。The porous magnesia particles were manufactured using N-trade magnesia with an average particle size of 0.3μ and magnesium nitrate as raw materials.
First, 2% by weight of an aqueous magnesium nitrate solution was added to the magnesia seedling, and the granules were made into granules by extrusion granulation.
By firing at 0°C, particles were obtained that were porous and strong enough to withstand handling.
次にこの多孔質粒子の１００〜１５０μの粒度のもの及
び上部が開放となったくし形の枠体を用いて、第１図に
示すような本発明になるリチウム−）ｆｌｉ化鉄電鉄電
池み、充放電試ｊ倹を行った１、電′池の組立ば、それ
ぞれ加圧成形’ ｋｎｇ 、 ｆＱ ｊ＋ｑ板の間に、
上部が開放となったマグネシアの（し形の枠体をはさみ
、それらを電槽に１車人後、くし形の枠体のくしの歯の
間に、多孔質のマグネシア粒子を充ｌ）νすることによ
り行った。Next, using these porous particles with a particle size of 100 to 150 μm and a comb-shaped frame with an open top, a lithium-)fli iron electric railway battery according to the present invention as shown in FIG. After carrying out the charging and discharging test 1, when assembling the battery, between the pressure molding and fQ j+q plates,
Magnesia with an open top (sandwich the diamond-shaped frame, place them in a battery container, and then fill in porous magnesia particles between the teeth of the comb-shaped frame) ν It was done by doing.
図にＪ′３いて（１）は硫化３久を・活物質ど覆る正１
（ｌよで、硫化鉄の粉末の５０μから３００μの粒良の
ものに、電解質の塩化リブラム−塩（ヒカリウムの５０
μから１５０μの粒度のものを１５重ｈ）％添７１■Ｌ
、ハニカム形’Ａｔ＜の集電体に充填した１好、等ｚ湿
にて １ （１０ＭＰａで加圧成形し、板状とし）ζも
ので゛ある１、なお、イル板表面には活物質保持のため
の２０（ｌメッシコのステンレス鋼製の網を右する。＜
２＞４Ｊ本発明による上部が開放となったく（〕形のマ
グネシアの枠体に多孔質のマグネシア粒子を充填するこ
と（・二より形成したけパレータで、（３）はりチウム
−アルミニウム合金を活物質とする負極である。、負（
・５も正極と同・様に、ハニカム形状の集電体中に、５
０μから３００μ斗での粒度のリヂウムーアルミニウム
合金粉末と５０μから １００μまでの粒度の電解質粉
末１５重■％を充填し、室温にて ｉｏｏＭｐｌで加圧
成形した板状体である。負極においても活物質保持のた
めの２００メツシユのステンレスｆｆ４Ｍの網を有する
。電解質には５４重量％塩化リチウム−塩化ｈリウ１１
の溶融塩を用いた。電池の作動湿度は４７０℃とした。In the figure, J'3 (1) is a positive 1 covering the sulfide 3 and the active material.
(In this case, iron sulfide powder with a grain size of 50 to 300 μ is mixed with the electrolyte Lybram chloride salt (hypotassium 50 μ
Added 15% of particle size from μ to 150μ 71■L
, a honeycomb-shaped current collector is filled with 1, at equal humidity 1 (press-formed at 10 MPa and made into a plate shape). 20(l mesh) stainless steel mesh for retention.
2>4J According to the present invention, porous magnesia particles are filled into a magnesia frame with an open upper part. It is the negative electrode of the substance., negative (
・Similarly to the positive electrode, 5 is placed in the honeycomb-shaped current collector.
It is a plate-shaped body filled with 15% by weight of lithium aluminum alloy powder with a particle size of 0μ to 300μ and an electrolyte powder with a particle size of 50μ to 100μ, and press-formed with iooMpl at room temperature. The negative electrode also has a 200-mesh stainless steel FF4M net for holding the active material. The electrolyte contains 54% by weight lithium chloride-h chloride 11
molten salt was used. The operating humidity of the battery was 470°C.
なお、正極の容量は２５ＡｔＴ及び１００△１）とし、
負極容量は正極の１．３倍とした。In addition, the capacity of the positive electrode is 25AtT and 100△1),
The negative electrode capacity was 1.3 times that of the positive electrode.
本発明による多孔質のマグネシア粒子をマグネシアの枠
体の間に流し込むことにより形成した粒子層の多孔度は
８５％と大ぎな幀を示し、水銀圧入法により測定したそ
の細孔分布は、３０μと１μに大きなピークを示した。The particle layer formed by pouring the porous magnesia particles according to the present invention between the magnesia frames has a large porosity of 85%, and the pore distribution measured by mercury intrusion method is 30μ. A large peak was observed at 1μ.
前者の細孔は粒子間の間隙によるしのであり、後者の微
小な細孔は粒子の内部に分布するもので必るが、粒子間
の間隙は活物質の粒径より小さく、レバレータ層で充分
に活物質が保持できることがわかる。The former pores are caused by gaps between particles, while the latter micro pores are distributed inside the particles and are necessary, but the gaps between particles are smaller than the particle size of the active material, and the lever layer is sufficient. It can be seen that the active material can be retained.
容量２５Ａ１１の電池による電池試験においては、本発
明による多孔質のマグネシア粒子を用いた電池の２．５
Ａ充放電時の正極活物質利用率が８３％と高い値を示し
た。同様の構成？１″′多孔度４６％のマグネシア粉末
セパレータを用いた電池では、品物ｊｊｊ利用率は６４
％にとどまり、多孔度８９％の窒化ホウ素フェルトはパ
１ノー夕を用いたものも８（５％と、本発明によるセパ
レータと同等の値となった。In a battery test using a battery with a capacity of 25A11, it was found that the battery using porous magnesia particles according to the present invention had a capacity of 2.5A.
A: The utilization rate of the positive electrode active material during charging and discharging was as high as 83%. Similar configuration? In a battery using a magnesia powder separator with a porosity of 46%, the product jjj utilization rate is 64
Boron nitride felt with a porosity of 89% had a porosity of 8 (5%), which is equivalent to that of the separator according to the present invention.
さらに、極（反面偵４４ｆＳの１００Δ１１電池を組み
、゛電池の充放電による極板の変形の影響をみた。窒化
ホウ素フェルト−セパ１ノータを用いた電池の８１侍間
率充放電で１００サイクル後の０１板厚ざは、正極で１
，２倍に、負極は゛電池のふくれが極板の中火にか〕こ
より、最高部では１．５倍に達した。そのためセパレー
タ厚さは、電池中央部ｌ゛は初１！Ｉ］の１／３以下に
なってしまった。本発明によるマグネシアの枠体及び多
孔質のマグネシア粒子をセパレータに用いた電池では、
同様の条件下でもセパ１ノータ層の厚みの変化はなく、
極板の形イノ（変化も緩和きれ、窒化ホウ素フェル１−
セパレータを用いた電池よりも、長寿命化が期待される
。また本発明にょる１００Ａ ｈ電池の活物質利用率は
、２５△ｈ電池と同様高い値を示した。Furthermore, a 100Δ11 battery with a polarity of 44fS was assembled to examine the effect of deformation of the polar plate due to charging and discharging of the battery. After 100 cycles at a rate of 81% charging and discharging of a battery using a boron nitride felt-separator. The 01 plate thickness is 1 at the positive electrode.
, 2 times, and the negative electrode reached 1.5 times at the highest point due to the bulging of the battery causing the middle heat of the electrode plate. Therefore, the thickness of the separator at the center of the battery is 1! I] has become less than 1/3. In a battery using a magnesia frame and porous magnesia particles as a separator according to the present invention,
Even under similar conditions, there was no change in the thickness of the Sepa 1 Nota layer,
The shape of the electrode plate (changes can be relaxed, boron nitride fer 1-
It is expected to have a longer lifespan than batteries using separators. Further, the active material utilization rate of the 100A h battery according to the present invention showed a high value similar to that of the 25Δh battery.
以上の説明及び実施例から明らかなように、本発明は、
従来のセパレータの欠点を改良し、安価なマグネシウム
化合物を原料として、多孔質で、溶融塩への濡れも良好
な上、充分に活物質が保持され、厚さの変することのな
いセパレータを用いた溶融塩電池を提供するものである
。As is clear from the above description and examples, the present invention
We have improved the shortcomings of conventional separators by using a separator made from an inexpensive magnesium compound that is porous, has good wettability to molten salt, retains the active material sufficiently, and does not change in thickness. The present invention provides a molten salt battery.
第１図は本発明になる電池の一実施例を示″ｃＪＩ１７
ｉ面図である。
１・・・・・・正極、２・・・・・・マグネシアの枠体
に多孔質のマグネシア粒子を充１眞してなるセパレータ
、３・・・・・・負極
図 １Figure 1 shows an embodiment of the battery according to the present invention.
It is an i-side view. 1... Positive electrode, 2... Separator made of a magnesia frame filled with porous magnesia particles, 3... Negative electrode Figure 1
Claims (1)
化物を用い、極間にセパレータとして多孔質のマグネシ
ア粒子を充填したマグネシアの枠体を介在させることを
特徴とする高温形電池。A high-temperature battery characterized by using lithium or a lithium alloy for the negative electrode, metal sulfide for the positive electrode, and interposing a magnesia frame filled with porous magnesia particles as a separator between the electrodes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6740683A JPS59191269A (en) | 1983-04-15 | 1983-04-15 | High temperature cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6740683A JPS59191269A (en) | 1983-04-15 | 1983-04-15 | High temperature cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS59191269A true JPS59191269A (en) | 1984-10-30 |
Family
ID=13344019
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6740683A Pending JPS59191269A (en) | 1983-04-15 | 1983-04-15 | High temperature cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59191269A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101014626B1 (en) | 2009-01-30 | 2011-02-16 | 국방과학연구소 | Electrolyte separator for thermal battery, method for fablicatign the same, and thermal battery having the same |
-
1983
- 1983-04-15 JP JP6740683A patent/JPS59191269A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101014626B1 (en) | 2009-01-30 | 2011-02-16 | 국방과학연구소 | Electrolyte separator for thermal battery, method for fablicatign the same, and thermal battery having the same |
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