JPH0560232B2 - - Google Patents
Info
- Publication number
- JPH0560232B2 JPH0560232B2 JP59259672A JP25967284A JPH0560232B2 JP H0560232 B2 JPH0560232 B2 JP H0560232B2 JP 59259672 A JP59259672 A JP 59259672A JP 25967284 A JP25967284 A JP 25967284A JP H0560232 B2 JPH0560232 B2 JP H0560232B2
- Authority
- JP
- Japan
- Prior art keywords
- battery
- raw material
- static electricity
- electrolyte
- organic solvent
- 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 - Lifetime
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
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
-
- 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
-
- 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
- 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)
Description
【発明の詳細な説明】
産業上の利用分野
本発明は粉末状の溶融塩電解質原料を取り扱う
電池の製造法に関するもので、乾燥雰囲気におけ
る静電気の影響のない電池の製造法を提供するも
のである。[Detailed Description of the Invention] Industrial Application Field The present invention relates to a method for manufacturing a battery that uses a powdered molten salt electrolyte raw material, and provides a method for manufacturing a battery that is free from the influence of static electricity in a dry atmosphere. .
従来の技術
高エネルギー密度の電池として、負極にアルカ
リ金属やアルカリ土金属、もしくはこれらの合金
を用いた溶融塩電池は高エネルギー密度の電池と
して開発が進められている。一次電池として代表
的なものに熱電池がある。熱電池の詳細は次の文
献に述べられている。（Development of ａ
Lithium Alloy Iron Disulfide 60−MInute
Primary Thermal Battery、SAND 79−0814、
Sandia Laboratories、April 1979）。ここに述
べられている熱電池は、正極に二硫化鉄FeS2を、
負極にリチウム合金を、電解質に溶融塩のLiCl−
KCl共晶塩を、セパレータとして酸化マグネシウ
ムMgOを使用している。BACKGROUND OF THE INVENTION Molten salt batteries using alkali metals, alkaline earth metals, or alloys thereof for negative electrodes are being developed as high energy density batteries. A typical primary battery is a thermal battery. Details of thermal batteries are described in the following documents: （Development of a
Lithium Alloy Iron Disulfide 60−M Inute
Primary Thermal Battery, SAND 79−0814,
Sandia Laboratories, April 1979). The thermal cell described here has iron disulfide FeS 2 as the positive electrode,
Lithium alloy is used as the negative electrode, and molten salt LiCl− is used as the electrolyte.
KCl eutectic salt is used, and magnesium oxide MgO is used as a separator.
また充電可能な二次電池として特開昭51−
66448には、溶融塩電解質を使用した高温電池が
述べられている。 Also, as a rechargeable secondary battery, JP-A-51-
66448 describes a high temperature battery using a molten salt electrolyte.
これらの電池はいずれも粉末状の電解質原料を
用いて製造されている。 All of these batteries are manufactured using powdered electrolyte raw materials.
発明が解決しようとする問題点
溶融塩を電解質に使用した電池は、低温では出
力を取り出すことができないが、高温では溶融し
て電導性を示すようになり、高出力、高エネルギ
ー密度が可能である。正極と負極を分離するセパ
レータは、溶融した電解質を保持するために絶縁
性のセラミツク粉末が使用されている。このよう
なセラミツク粉末と溶融塩との混合物からなる電
解質原料は、低温では固体であるために、プレス
成形することが可能であり、平板状に成形したも
のが正極と負極の間に挟まれて使用される。高温
では電解質が溶融するが、混合されたセラミツク
粉末により、電解質の流動性が抑えられた電極間
の短絡を防止している。Problems to be solved by the invention Batteries that use molten salt as an electrolyte cannot produce output at low temperatures, but at high temperatures they melt and become conductive, making it possible to achieve high output and high energy density. be. The separator that separates the positive and negative electrodes uses insulating ceramic powder to hold the molten electrolyte. The electrolyte raw material, which is a mixture of ceramic powder and molten salt, is solid at low temperatures, so it can be press-molded, and the plate-shaped material is sandwiched between the positive and negative electrodes. used. Although the electrolyte melts at high temperatures, the mixed ceramic powder suppresses the fluidity of the electrolyte and prevents short circuits between the electrodes.
負極に用いるアルカリ金属やアルカリ土金属、
もしくはこれらの合金は極めて活性が高く、空気
中の水分と反応し易く、また電解質も吸湿しやす
いものが多いために、電池の製造は乾燥した空気
のドライルームや不活性雰囲気のグローブボツク
ス中で行われている。このような低水分の雰囲気
では静電気が発生しやすく、電池の製造を困難に
していた。すなわち、製造装置や測定装置等に静
電気が発ししやすいだけでなく、原料粉末の流動
や振動でも静電気が発生し、人体やグローブボツ
クスのアクリル板やグローブ等に原料粉末が付着
し、作業環境を汚染したり、静電気の放電による
発火の危険性やノイズの発生による電子機器の誤
差や故障の原因となつたりした。 Alkali metals and alkaline earth metals used in negative electrodes,
Alternatively, since these alloys are extremely active and easily react with moisture in the air, and many electrolytes also tend to absorb moisture, batteries are manufactured in dry rooms with dry air or glove boxes with inert atmosphere. It is being done. Static electricity is likely to occur in such a low-moisture atmosphere, making it difficult to manufacture batteries. In other words, not only is static electricity easily generated in manufacturing equipment and measuring equipment, but also static electricity is generated due to the flow and vibration of the raw material powder, and the raw powder adheres to the human body, the acrylic plate of the glove box, gloves, etc., and pollutes the work environment. This could cause contamination, the risk of fire due to static electricity discharge, and the generation of noise that could cause errors or malfunctions in electronic equipment.
問題点を解決するための手段
本発明は低水分の乾燥雰囲気で、粉末状の溶融
塩電解質原料を取り扱う電池の製造法において、
比誘電率30以上の有機溶媒を添加した粉末状の電
解質原料を使用することを特徴とするものであ
る。Means for Solving the Problems The present invention is a battery manufacturing method that handles powdered molten salt electrolyte raw materials in a dry atmosphere with low moisture content.
It is characterized by using a powdered electrolyte raw material to which an organic solvent with a dielectric constant of 30 or more is added.
作 用
本発明によれば、電解質原料粉末に比誘導率30
以上の有機溶媒を添加することにより、静電気の
発生がなくなり、また静電気の影響を受けなくな
つた。比誘電率30以上の有機溶媒は電解質原料粉
末に吸着されて、常温での絶縁性を低下させるた
めに静電気が発生しにくくなるものと考えられ
る。有機溶媒の添加量は極めてわずかであり、数
十ppm〜数千ppmで効果が認められた。Effect According to the present invention, the electrolyte raw material powder has a specific inductivity of 30
By adding the above-mentioned organic solvent, the generation of static electricity was eliminated and the product was no longer affected by static electricity. It is thought that an organic solvent with a dielectric constant of 30 or more is adsorbed by the electrolyte raw material powder and reduces the insulation properties at room temperature, making it difficult to generate static electricity. The amount of organic solvent added was extremely small, and the effect was observed at tens of ppm to several thousand ppm.
実施例
１ 電解質原料粉末50ｇに種々の有機溶媒を添加
し、添加量と静電気の関係を調べた。電解質原
料粉末はLiCl−KCl共晶塩と酸化マグネシウム
との混合物で、100メツシユ〜325メツシユの粉
末である。Example 1 Various organic solvents were added to 50 g of electrolyte raw material powder, and the relationship between the amount added and static electricity was investigated. The electrolyte raw material powder is a mixture of LiCl-KCl eutectic salt and magnesium oxide, and is a powder of 100 mesh to 325 mesh.
種々の有機溶媒を添加した電解質原料粉末約
0.5ｇをステンレス製のスプーンに取りグロー
ブボツクス中のアクリル板の上に置いた時、静
電気により飛散するかどうかを調べた。比誘電
率30以上のプロピレンカーボネート（比誘電率
64.4）、γ−ブチロラクトン（同39.1）、アセト
ニトリル（同38）、ジメチルホルムアミド（同
36.7）、プロピレングリコール（同32）等は3μ
／50ｇ以上の添加により静電気の影響がなく
なり、粉末の飛散が認められなくなつた。比誘
電率30以下のテトラヒドロフラン（同6.2）、ジ
メトキシエタン（同7.2）、ピリジン（同12.0）
等は、100μ／50ｇ以上添加しても添加の効
果がなく、静電気によりスプーン上からアクリ
ル板への粉末の飛散が認められた。 Electrolyte raw material powder containing various organic solvents
When 0.5g was taken into a stainless steel spoon and placed on an acrylic plate in a glove box, it was investigated whether it would scatter due to static electricity. Propylene carbonate with a relative permittivity of 30 or more (relative permittivity
64.4), γ-butyrolactone (39.1), acetonitrile (38), dimethylformamide (38)
36.7), 3μ for propylene glycol (32), etc.
By adding more than /50g, the effect of static electricity disappeared and powder scattering was no longer observed. Tetrahydrofuran (6.2), dimethoxyethane (7.2), pyridine (12.0) with dielectric constant of 30 or less
Even if 100μ/50g or more of the above was added, there was no effect, and the powder was observed to scatter from the top of the spoon onto the acrylic plate due to static electricity.
電解質原料粉末に添加する有機溶媒は負極に
悪影響を与えないために非プロトン性のものが
好ましく、また有機溶媒の蒸気による作業環境
の悪化を防ぐため、その蒸気圧は低いものが好
ましい。特にプロピレンカーボネートとγ−ブ
チロラクトンはこれらの条件を満足するもので
あり、最適なものである。比誘電率30以上の有
機溶媒を添加した電解質原料粉末は静電気が発
生しにくいだけでなく、周縁部に帯電した静電
気も放電しやすくするために、乾燥雰囲気中に
おける静電気の悪影響の防止が可能となつた。 The organic solvent added to the electrolyte raw material powder is preferably aprotic in order not to adversely affect the negative electrode, and preferably has a low vapor pressure in order to prevent deterioration of the working environment due to the vapor of the organic solvent. In particular, propylene carbonate and γ-butyrolactone satisfy these conditions and are optimal. The electrolyte raw material powder containing an organic solvent with a dielectric constant of 30 or more is not only less likely to generate static electricity, but also makes it easier to discharge static electricity charged at the periphery, making it possible to prevent the negative effects of static electricity in a dry atmosphere. Summer.
２ 電解質原料粉末50ｇ当り30μのプロピレン
カーボネートを添加した電解質層を用いて熱電
池を構成した。熱電池として、負極層にリチウ
ム−アルミニウム合金0.7ｇ、正極層に二硫化
鉄64％、LiCl−KCl共晶塩34％、二酸化ケイ素
２％からなる混合物1.5ｇを使用した。電解質
層はLiCl−KCl共晶塩60％とMgO粉末40％か
らなるプロピレンカーボネートを添加した混合
物2.0ｇを使用した。素電池は負極層、電解質
層、正極層の各層が三層一体に加圧成形されて
おり、直径54mm、厚さ1.05mmの円板状である。
これらの素電池15枚と、FeとKClO4との混合
物よりなる発熱剤とを交互に積層して熱電池を
構成し、電池を活性化して6.6Aの電流で放電
した。その結果、正極にプロピレンカーボネー
トを添加しない従来電池と全く同じ放電特性を
示し、添加による悪影響はみられなかつた。本
発明実施電池は素電池の製造工程において、電
解質原料粉末の静電気による飛散は全く認めら
れず、作業環境の汚染がなく、製造が容易であ
つた。2. A thermal battery was constructed using an electrolyte layer to which 30μ of propylene carbonate was added per 50g of electrolyte raw material powder. As a thermal battery, 0.7 g of a lithium-aluminum alloy was used for the negative electrode layer, and 1.5 g of a mixture consisting of 64% iron disulfide, 34% LiCl-KCl eutectic salt, and 2% silicon dioxide was used for the positive electrode layer. For the electrolyte layer, 2.0 g of a mixture of 60% LiCl-KCl eutectic salt and 40% MgO powder to which propylene carbonate was added was used. The unit cell has a negative electrode layer, an electrolyte layer, and a positive electrode layer that are pressure-molded as a three-layer unit, and has a disk shape with a diameter of 54 mm and a thickness of 1.05 mm.
A thermal battery was constructed by alternately stacking 15 of these unit cells and a heating agent made of a mixture of Fe and KClO 4 , and the battery was activated and discharged with a current of 6.6 A. As a result, the battery exhibited exactly the same discharge characteristics as a conventional battery without the addition of propylene carbonate to the positive electrode, and no adverse effects were observed due to the addition. In the battery according to the present invention, no scattering of the electrolyte raw material powder due to static electricity was observed during the manufacturing process of the unit cell, and the work environment was not contaminated and the manufacturing process was easy.
発明の効果
以上のように、本発明は粉末状の電解質原料を
用いる電池の製造法において、静電気の防止に効
果があるものであり、静電気の発生にともなう
種々の悪影響を防止するものである。電解質原料
に添加する有機溶媒は比誘電率30以上のものを主
剤とする混合物でもよく、またイオン性の溶質を
溶解したものを用いてもよい。なお、正極と負極
と負極が別の工程で成形される場合においては、
プロトン性の有機溶媒も使用可能である。負極が
電池特性に悪影響を及ぼす有機溶媒は、電池組立
途中において、加熱乾燥により容易に取り除くこ
とが可能である。Effects of the Invention As described above, the present invention is effective in preventing static electricity in a battery manufacturing method using powdered electrolyte raw materials, and prevents various adverse effects associated with the generation of static electricity. The organic solvent added to the electrolyte raw material may be a mixture whose main ingredient is one having a dielectric constant of 30 or more, or may be a mixture containing an ionic solute dissolved therein. In addition, if the positive electrode, negative electrode, and negative electrode are molded in separate processes,
Protic organic solvents can also be used. The organic solvent in the negative electrode that adversely affects battery characteristics can be easily removed by heating and drying during battery assembly.
Claims (1)
質原料を取り扱う電池の製造法において、比誘電
率30以上の有機溶媒を添加した粉末状の電解質原
料を使用することを特徴とする電池の製造法。 ２ 有機溶媒としてプロピレンカーボネートを使
用することを特徴とする特許請求の範囲第１項記
載の電池の製造法。 ３ 有機溶媒としてγ−ブチロラクトンを使用す
ることを特徴とする特許請求の範囲第１項記載の
電池の製造法。[Scope of Claims] 1. In a battery manufacturing method that handles a powdery molten salt electrolyte raw material in a dry atmosphere with low moisture, it is possible to use a powdery electrolyte raw material to which an organic solvent with a dielectric constant of 30 or more is added. Characteristic battery manufacturing method. 2. The method for manufacturing a battery according to claim 1, characterized in that propylene carbonate is used as the organic solvent. 3. The method for manufacturing a battery according to claim 1, characterized in that γ-butyrolactone is used as the organic solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59259672A JPS61138462A (en) | 1984-12-07 | 1984-12-07 | Manufacture of cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59259672A JPS61138462A (en) | 1984-12-07 | 1984-12-07 | Manufacture of cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61138462A JPS61138462A (en) | 1986-06-25 |
| JPH0560232B2 true JPH0560232B2 (en) | 1993-09-01 |
Family
ID=17337294
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59259672A Granted JPS61138462A (en) | 1984-12-07 | 1984-12-07 | Manufacture of cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61138462A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2697676B1 (en) * | 1992-10-29 | 1994-12-09 | Accumulateurs Fixes | Lithium thermal battery. |
-
1984
- 1984-12-07 JP JP59259672A patent/JPS61138462A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61138462A (en) | 1986-06-25 |
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