JPH0815072B2 - Method for manufacturing thermal battery electrodes - Google Patents
Method for manufacturing thermal battery electrodesInfo
- Publication number
- JPH0815072B2 JPH0815072B2 JP59254608A JP25460884A JPH0815072B2 JP H0815072 B2 JPH0815072 B2 JP H0815072B2 JP 59254608 A JP59254608 A JP 59254608A JP 25460884 A JP25460884 A JP 25460884A JP H0815072 B2 JPH0815072 B2 JP H0815072B2
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- thermal battery
- negative electrode
- organic solvent
- raw material
- 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 12
- 238000000034 method Methods 0.000 title claims description 3
- 239000002994 raw material Substances 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 14
- 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
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- 239000000956 alloy Substances 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 2
- 230000005611 electricity Effects 0.000 description 17
- 230000003068 static effect Effects 0.000 description 17
- 229910000838 Al alloy Inorganic materials 0.000 description 6
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-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
- 239000000203 mixture Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 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
- 230000002411 adverse Effects 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 229910013618 LiCl—KCl Inorganic materials 0.000 description 1
- 241000321453 Paranthias colonus Species 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- NFMAZVUSKIJEIH-UHFFFAOYSA-N bis(sulfanylidene)iron Chemical compound S=[Fe]=S NFMAZVUSKIJEIH-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910000339 iron disulfide Inorganic materials 0.000 description 1
- 230000007257 malfunction Effects 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
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide 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
- 238000005303 weighing Methods 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 本発明は粉末状の負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 negative electrode raw material is pressure-molded into an electrode, and in particular, it is a heat-free electrode 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 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 Litum Alloy Iron Disuifid
e 60−Minute Primary Thermal Battery,SAND 79−081
4,Sandia Laboratories,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 Batteries using an alkali metal, an alkaline earth metal, or an alloy thereof for the negative electrode are being developed as a high energy density battery. A thermal battery is a typical primary battery. The details of this battery are described in (Development of a Litum Alloy Iron Disuifid
e 60−Minute Primary Thermal Battery, SAND 79−081
4, Sandia Laboratories, 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。特に負極原料粉末は静電気により
飛散しやすく秤量誤差の原因となっていた。Problems to be Solved by the Invention Alkali metals and alkaline earth metals used for the negative electrode, or alloys thereof are extremely highly active and easily react with moisture in the air, so that the electrode is manufactured in a dry air dry room or It is held in an inert 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. In particular, the negative electrode raw material powder was easily scattered by static electricity, which caused a weighing error.
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、アルカリ金属やアルカリ
土類金属、もしくはこれらを含む合金からなる粉末状の
負極原料に比誘電率30以上の非プロトン性有機溶媒を添
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 Problems The present invention relates to a powdery negative electrode raw material made of an alkali metal, an alkaline earth metal, or an alloy containing them in a dry room of dry air or a glove box in an inert atmosphere. An aprotic organic solvent having a rate of 30 or more is added, followed by pressure molding to provide an electrode for a thermal battery, which is used as an electrode.
作用 本発明によれば、負極原料粉末に比誘電率30以上の非
プロトン性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以上の有機溶媒は負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 aprotic organic solvent having a relative dielectric constant of 30 or more to the negative electrode raw material powder, the generation of static electricity is eliminated and the influence of static electricity is eliminated. An organic solvent having a relative dielectric constant of 30 or more is adsorbed on the negative electrode raw material powder,
It is considered that static electricity is less likely to be generated because the insulating property between particles is lowered. 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.粒度を100メッシュ〜325メッシュとしたリチウム−ア
ルミニウム合金粉末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。有機溶媒を添加したリチ
ウム−アルミニウム合金約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、静電気によりリチウム−アルミニウム合金が飛散す
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3
9.1），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５μ
l/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以下のエチル
アルコール（同25.0），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、リチウム−アルミニウ
ム合金粉末は静電気によりスプーン上からアクリル板へ
と飛散した。Example 1 Various organic solvents were added to 50 g of a lithium-aluminum alloy powder having a particle size of 100 mesh to 325 mesh, and the relationship between the added amount and static electricity was investigated. When about 0.5 g of a lithium-aluminum alloy containing an organic solvent was placed in a stainless steel spoon and placed on an acrylic plate in a glove box, it was examined whether or not the lithium-aluminum alloy was scattered by static electricity. Propylene carbonate with a dielectric constant of 30 or more (relative permittivity 64.4), γ-butyrolactone (3
9.1), acetonitrile (38), dimethylformamide (36.7), propylene glycol (32), etc. 5μ
By adding more than 1 / 50g, the influence of static electricity disappeared and no scattering of powder was observed. Ethyl alcohol with a dielectric constant of 30 or less (25.0), tetrahydrofuran (6.
2), dimethoxyethane (7.2), pyridine (12.0)
Even when 100 μl / 50 g or more of these substances were added, the lithium-aluminum alloy powder was scattered from the spoon onto the acrylic plate by static electricity.
負極原料粉末に添加する有機溶媒は負極との反応を防
ぐため、非プロトン製であることが必要であり、また有
機溶媒の蒸気による作業環境の悪化を防ぐため、蒸気圧
が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 negative electrode raw material powder needs to be aprotic in order to prevent reaction with the negative electrode, and preferably has a low vapor pressure in order to prevent deterioration of the working environment due to vapor of the organic solvent. In particular, propylene carbonate and γ-butyrolactone satisfy these conditions and are optimal.
2.リチウム−アルミニウム合金粉末50g当り50μｌのプ
ロピレンカーボネートを添加した負極を用いて熱電池を
構成した。熱電池として、負極層にプロピレンカーボネ
ート添加リチウム−アルミニウム合金0.7g,電解質層にL
iCl−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、負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負
極原料粉末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
段がなくなった。2. A thermal battery was constructed using a negative electrode to which 50 μl of propylene carbonate was added per 50 g of lithium-aluminum alloy powder. As a thermal battery, 0.7g of lithium-aluminum alloy with propylene carbonate added to the negative electrode layer and L to the electrolyte layer
A 2.0 g mixture of iCl-KCl eutectic salt and MgO powder was used. As the positive electrode layer, 1.5 g of a mixture composed of 64% iron disulfide, 34% LiCl-KCl eutectic salt and 2% silicon dioxide was used. Dew point −50
In a low-humidity dry room at ℃ or below, sequentially fill the mold with the powdered positive electrode raw material, powdered electrolyte raw material, and powdered negative electrode raw material in layers, and add three layers integrally with a pressing machine. Press formed. 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. The unit cell has a negative electrode layer, an electrolyte layer, and a positive electrode layer, which are integrally pressure-molded, and has a disk shape with a diameter of 54 mm and a thickness of 1.05 mm. A thermal battery is constructed by alternately stacking 15 of these unit cells and an exothermic agent made of a mixture of Fe and KClO 4, and activating the battery.6.
It was discharged at a current of 6A. As a result, it showed exactly the same discharge characteristics as the conventional battery in which propylene carbonate was not added to the negative electrode. By the practice of the present invention, in the manufacturing process of the electrode no scattering of the negative electrode raw material powder due to static electricity is observed,
The work environment is not polluted and manufacturing is easy. Also,
There is no malfunction of the scale due to static electricity, and the middle stage of manufacturing work is gone.
発明の効果 以上のように、本発明は粉末状の負極原料を加圧成形
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、負極原料粉末に添
加する有機溶媒は少量であるために電池特性に悪影響は
及ぼさないが、好ましくない場合は、電極成形後に加熱
乾燥して取り除いてもよい。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 negative 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. Since the amount of the organic solvent added to the negative electrode raw material powder is small, it does not adversely affect the battery characteristics, but if it is not preferable, it may be removed by heating and drying after molding the electrode.
Claims (3)
グローブボックス内において、アルカリ金属やアルカリ
土類金属、もしくはこれらを含む合金からなる粉末状の
負極原料に比誘電率30以上の非プロトン性有機溶媒を添
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 powder of negative electrode raw material made of an alkali metal, an alkaline earth metal, or an alloy containing them in a dry room of dry air or in a glove box in an inert atmosphere, and an aprotic substance having a relative dielectric constant of 30 or more. A method for manufacturing an electrode for a thermal battery, in which an organic solvent is added and then pressure-molded into an electrode.
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 aprotic organic solvent.
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
項記載の熱電池用電極の製造法。3. A γ-butyrolactone is used as the aprotic organic solvent.
A method for producing an electrode for a thermal battery according to the item.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59254608A JPH0815072B2 (en) | 1984-11-30 | 1984-11-30 | Method for manufacturing thermal battery electrodes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59254608A JPH0815072B2 (en) | 1984-11-30 | 1984-11-30 | Method for manufacturing thermal battery electrodes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61133558A JPS61133558A (en) | 1986-06-20 |
| JPH0815072B2 true JPH0815072B2 (en) | 1996-02-14 |
Family
ID=17267394
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59254608A Expired - Lifetime JPH0815072B2 (en) | 1984-11-30 | 1984-11-30 | Method for manufacturing thermal battery electrodes |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0815072B2 (en) |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5539132A (en) * | 1978-09-11 | 1980-03-18 | Matsushita Electric Ind Co Ltd | Thermal battery |
| JPS55136465A (en) * | 1979-04-10 | 1980-10-24 | Japan Storage Battery Co Ltd | Manufacturing method of negative electrode plate for alkaline storage 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 JP59254608A patent/JPH0815072B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61133558A (en) | 1986-06-20 |
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