JPH0815073B2 - Method for manufacturing thermal battery electrodes - Google Patents
Method for manufacturing thermal battery electrodesInfo
- Publication number
- JPH0815073B2 JPH0815073B2 JP59254609A JP25460984A JPH0815073B2 JP H0815073 B2 JPH0815073 B2 JP H0815073B2 JP 59254609 A JP59254609 A JP 59254609A JP 25460984 A JP25460984 A JP 25460984A JP H0815073 B2 JPH0815073 B2 JP H0815073B2
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- thermal battery
- raw material
- positive electrode
- static electricity
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 238000000034 method Methods 0.000 title description 3
- 239000002994 raw material Substances 0.000 claims description 18
- 239000003960 organic solvent Substances 0.000 claims description 12
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 6
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 6
- 230000005611 electricity Effects 0.000 description 16
- 230000003068 static effect Effects 0.000 description 16
- 239000000843 powder Substances 0.000 description 14
- 230000000694 effects Effects 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- NFMAZVUSKIJEIH-UHFFFAOYSA-N bis(sulfanylidene)iron Chemical compound S=[Fe]=S NFMAZVUSKIJEIH-UHFFFAOYSA-N 0.000 description 3
- 230000005496 eutectics Effects 0.000 description 3
- 229910000339 iron disulfide Inorganic materials 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910013618 LiCl—KCl Inorganic materials 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 241000321453 Paranthias colonus Species 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0416—Methods of deposition of the material involving impregnation with a solution, dispersion, paste or dry powder
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/043—Processes of manufacture in general involving compressing or compaction
- H01M4/0433—Molding
-
- 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
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は粉末状の正極原料を加圧成形して電極とする
熱電池用電極の製造法に関するもので、特に乾燥雰囲気
における静電気の影響のない熱電池用電極の製造法を提
供するものである。Description: TECHNICAL FIELD The present invention relates to a method for producing an electrode for a thermal battery, in which a powdery positive electrode raw material is pressure-molded to form an electrode, and in particular, it is a heat-free battery that is not affected by static electricity in a dry atmosphere. A method for manufacturing a battery electrode is provided.
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
やアルカリ土類金属、もしくはこれらの合金を用いた電
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。この
電池の詳細は次の文献に述べられている（Development
of a Litium Alloy Iron Disulfide 60−Minute Primar
y Thermal Battery,SAND 79−0814,Sandia Laboratorie
s,April 1979）。また二次電池として高温電池が研究さ
れている（特開昭57−61271）。2. Description of the Related Art As a high energy density battery, a battery using an alkali metal, an alkaline earth metal, or an alloy thereof for a negative electrode is under development as a high energy density battery. A thermal battery is a typical primary battery. Details of this battery are described in the following document (Development
of a Litium Alloy Iron Disulfide 60−Minute Primar
y Thermal Battery, SAND 79-0814, Sandia Laboratorie
s, April 1979). A high temperature battery has been studied as a secondary battery (Japanese Patent Laid-Open No. 57-61271).
これらの電池はいずれも粉末状の負極原料を加圧成形
して電極としている。In each of these batteries, a powdery negative electrode raw material is pressure-molded to form an electrode.
発明が解決しようとする問題点 負極に用いるアルカリ金属やアルカリ土類金属、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
反応しやすく、また電解質も吸湿しやすいものが多いた
めに、電極の製造は乾燥空気のドライルームや不活性雰
囲気のグローブボックス中で行なわれている。このよう
な低水分の雰囲気では静電気が発生しやすく、電極の製
造を困難にしていた。すなわち、製造装置や測定装置等
に静電気が発生しやすいだけでなく、原料粉末の流動や
振動等でも静電気が発生し、人体やグローブボックスの
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ったり
した。Problems to be Solved by the Invention Alkali metals and alkaline earth metals used for the negative electrode, or alloys thereof are extremely high in activity, easily react with moisture in the air, and since many electrolytes also easily absorb moisture, The electrodes are manufactured in a dry air dry room or in an inert atmosphere glove box. In such an atmosphere of low water content, static electricity is easily generated, which makes it difficult to manufacture the electrode. That is, not only static electricity is easily generated in the 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 material powder adheres to the acrylic plate and gloves of the human body and glove box. Could cause the risk of ignition due to the discharge of static electricity, or the error or failure of electronic equipment due to the generation of noise.
問題点を解決するための手段 本発明は、乾燥空気のドライルームや不活性雰囲気の
グローブボックス内において、粉末状の正極原料に比誘
電率30以上の有機溶媒を添加したのち、加圧成形して電
極とする熱電池用電極の製造法を提供するものである。Means for solving the problem The present invention, in a dry room of dry air or a glove box of an inert atmosphere, after adding an organic solvent having a relative dielectric constant of 30 or more to the powdery positive electrode raw material, pressure molding The present invention provides a method for manufacturing an electrode for a thermal battery, which is used as an electrode.
作用 本発明によれば、正極原料粉末に比誘電率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った。比誘電率30以
上の有機溶媒は正極原料粉末に吸着されて、粒子間の絶
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, by adding an organic solvent having a relative dielectric constant of 30 or more to the positive electrode raw material powder, the generation of static electricity is eliminated and the influence of static electricity is eliminated. It is considered that an organic solvent having a relative permittivity of 30 or more is adsorbed by the positive electrode raw material powder and reduces the insulating property between particles, so that static electricity is less likely to be generated. The amount of the organic solvent added was extremely small, and the effect was recognized at several tens ppm to several thousands ppm.
実施例 1.正極原料粉末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。正極原料粉末は二硫化鉄とLi
Cl−KCl共晶塩と二酸化ケイ素との混合物で、100メッシ
ュ〜325メッシュの粉末である。Example 1. Various organic solvents were added to 50 g of the positive electrode raw material powder, and the relationship between the added amount and static electricity was investigated. Positive electrode raw material powder is iron disulfide and Li
It is a mixture of Cl-KCl eutectic salt and silicon dioxide, and is a powder of 100 mesh to 325 mesh.
種々の有機溶媒を添加した正極原料粉末約0.5gをステ
ンレス製のスプーンに取りグローブボックス中のアクリ
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。非誘電率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５μl/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
れなくなった。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100μl/50g以上添加しても添加の効果がな
く、静電気によりスピーン上からアクリル板への粉末の
飛散が認められた。Approximately 0.5 g of the positive electrode raw material powder to which various organic solvents were added was placed in a stainless steel spoon and placed on an acrylic plate in a glove box, and it was examined whether or not it would be scattered by static electricity. Propylene carbonate with a dielectric constant of 30 or more (relative permittivity 64.4), γ-butyrolactone (39.1), acetonitrile (38), dimethylformamide (36.7),
Addition of 5 μl / 50 g or more of propylene glycol (same as 32) eliminated the influence of static electricity, and no scattering of powder was observed. Tetrahydrofuran with a relative dielectric constant of 30 or less (same as 6.2), dimethoxyethane (same as 7.2), pyridine (same as above)
12.0) and the like had no effect even when added in an amount of 100 μl / 50 g or more, and the scattering of powder from the spine to the acrylic plate was observed due to static electricity.
正極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
溶媒の上記による作業環境の悪化を防ぐため、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。The organic solvent added to the positive electrode raw material powder is preferably an aprotic one because it does not adversely affect the negative electrode, and a low vapor pressure is preferable in order to prevent the working environment from being deteriorated by the above. Especially propylene carbonate and γ
-Butyrolactone satisfies these conditions and is optimal.
2.正極原料粉末50g当り30μｌのプロピレンカーボネー
トを添加した正極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,電解
質層にLiCl−KCl共晶塩とMgO粉末の混合物2.0gを使用し
た。正極層として、二硫化鉄64％,LiCl−KCl共晶塩34
％，二酸化ケイ素２％からなるプロピレンカーボネート
を添加した混合物1.5gを使用した。露点−50℃以下の低
湿度ドライルーム内で、成形型に順次、前述の粉末状の
正極原料、粉末状の電解質原料、粉末状の負極原料をそ
れぞれ層状に充填し、プレス機で３層を一体に加圧成形
した。正極と電解質層と負極はそれぞれ単独に成形した
のち、組み合わせてもよい。正極と電解質層と負極から
なる単位を素電池と呼んでいる。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1
5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た。本
発明の実施により、電極の製造工程において正極原料粉
末の静電気による飛散は全く認められなくなり、作業環
境の汚染がなくなり製造が容易となった。また、静電気
による秤量計の誤動作もなくなり、製造作業の中断がな
くなった。2. A thermal battery was constructed using a positive electrode to which 30 μl of propylene carbonate was added per 50 g of the positive electrode raw material powder. As a thermal battery, 0.7 g of a lithium-aluminum alloy was used for the negative electrode layer, and 2.0 g of a mixture of a LiCl-KCl eutectic salt and MgO powder was used for the electrolyte layer. As the positive electrode layer, iron disulfide 64%, LiCl-KCl eutectic salt 34
%, A mixture of 1.5 g of propylene carbonate consisting of 2% of silicon dioxide was used. In a low-humidity dry room with a dew point of -50 ° C or lower, the above-mentioned powdery positive electrode raw material, powdery electrolyte raw material, and powdery negative electrode raw material are filled in layers in order in a molding die, and three layers are formed by a pressing machine. It was integrally pressure-molded. The positive electrode, the electrolyte layer, and the negative electrode may be molded separately and then combined. A unit composed of a positive electrode, an electrolyte layer and a negative electrode is called a unit cell. In the unit cell, each layer of the negative electrode layer, the electrolyte layer, and the positive electrode layer is pressure-molded into three layers,
It is a disc with a diameter of 54 mm and a thickness of 1.05 mm. These unit cells 1
A thermal battery was constructed by alternately stacking 5 sheets and an exothermic agent made of a mixture of Fe and KClO 4, and the battery was activated and discharged at a current of 6.6A. As a result, it showed exactly the same discharge characteristics as the conventional battery in which propylene carbonate was not added to the positive electrode. By carrying out the present invention, scattering of the positive electrode raw material powder due to static electricity was not observed at all in the manufacturing process of the electrode, and the work environment was eliminated and the manufacturing was facilitated. In addition, the malfunction of the scale due to static electricity disappeared, and the interruption of manufacturing work was eliminated.
発明の効果 以上のように、本発明は粉末状の正極原料を加圧成形
して電極とする電極の製造法において、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。なお、正極と負極が別の
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。電池特性に悪影響を及ぼす有機溶
媒は、電極成形後に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 method of manufacturing an electrode in which a powdery positive electrode raw material is pressure-molded to form an electrode, and various adverse effects associated with the generation of static electricity are exerted. Is to prevent. In addition, when the positive electrode and the negative electrode are molded in separate steps, a protic organic solvent can also be used. The organic solvent that adversely affects the battery characteristics can be easily removed by heating and drying after forming the electrode.
Claims (3)
グローブボックス内において、粉末状の正極原料に比誘
電率30以上の有機溶媒を添加したのち、加圧成形して電
極とする熱電池用電極の製造法。1. A thermal battery for forming an electrode by adding an organic solvent having a relative permittivity of 30 or more to a powdery positive electrode raw material in a dry room of dry air or a glove box in an inert atmosphere, and then forming the electrode. Electrode manufacturing method.
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
熱電池用電極の製造法。2. The method for producing a thermal battery electrode according to claim 1, wherein propylene carbonate is used as the organic solvent.
することを特徴とする特許請求の範囲第１項記載の熱電
池用電極の製造法。3. The method for producing a thermal battery electrode according to claim 1, wherein γ-butyrolactone is used as the organic solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59254609A JPH0815073B2 (en) | 1984-11-30 | 1984-11-30 | Method for manufacturing thermal battery electrodes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59254609A JPH0815073B2 (en) | 1984-11-30 | 1984-11-30 | Method for manufacturing thermal battery electrodes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61133559A JPS61133559A (en) | 1986-06-20 |
| JPH0815073B2 true JPH0815073B2 (en) | 1996-02-14 |
Family
ID=17267409
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59254609A Expired - Lifetime JPH0815073B2 (en) | 1984-11-30 | 1984-11-30 | Method for manufacturing thermal battery electrodes |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0815073B2 (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5539132A (en) * | 1978-09-11 | 1980-03-18 | Matsushita Electric Ind Co Ltd | Thermal battery |
| JPS6057185B2 (en) * | 1980-05-14 | 1985-12-13 | 松下電器産業株式会社 | thermal battery |
| JPS5780666A (en) * | 1980-11-06 | 1982-05-20 | Nec Corp | Lithium battery and its manufacture |
| JPS57176669A (en) * | 1981-04-23 | 1982-10-30 | Toshiba Battery Co Ltd | Manufacture of organic solvent battery |
| JPS59169074A (en) * | 1983-03-16 | 1984-09-22 | Japan Storage Battery Co Ltd | Thermal cell |
-
1984
- 1984-11-30 JP JP59254609A patent/JPH0815073B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61133559A (en) | 1986-06-20 |
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