JPS61279055A - Organic solvent battery - Google Patents
Organic solvent batteryInfo
- Publication number
- JPS61279055A JPS61279055A JP60120628A JP12062885A JPS61279055A JP S61279055 A JPS61279055 A JP S61279055A JP 60120628 A JP60120628 A JP 60120628A JP 12062885 A JP12062885 A JP 12062885A JP S61279055 A JPS61279055 A JP S61279055A
- Authority
- JP
- Japan
- Prior art keywords
- ceramic powder
- organic solvent
- conductive ceramic
- metal container
- 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
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/664—Ceramic materials
-
- 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
Abstract
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は有機溶媒電池に関し、更に詳しくは。[Detailed description of the invention] [Industrial application field] The present invention relates to organic solvent batteries, and more particularly.
正極合剤と正極端子を兼ねる金属容器との間の接触抵抗
が小さく、かつ、貯蔵昨においても内部抵抗が上昇する
ことのない有機溶媒ＴＬ池に関する。The present invention relates to an organic solvent TL cell in which the contact resistance between a positive electrode mixture and a metal container that also serves as a positive electrode terminal is low, and the internal resistance does not increase even during storage.
［従来の技術］
炭酸フロピレン、１．２−ジメトキシエタンのような有
機溶媒に電解質を溶解せしめた溶液を電解液とする有機
溶媒電池は、概ね次のような構造になっている。すなわ
ち、正極端子を兼ねる導電性の金属容器（例えばステン
レス鋼製の缶）の中に、ペレットに成形した正極合剤を
充填し、この上に有機溶媒と電解質とから成る電解液を
含浸せしめたセパレータを介して負極を載置し、更にこ
こに負極端子を兼ねる導電性の金属蓋（例えばステンレ
ス鋼製のキャップ）を冠着せしめ、容器と蓋の間を絶縁
バッキングで絶縁しかつ間隙を密着した気密構造体であ
る。[Prior Art] An organic solvent battery whose electrolyte is a solution of an electrolyte dissolved in an organic solvent such as phlopylene carbonate or 1,2-dimethoxyethane generally has the following structure. That is, a conductive metal container (for example, a stainless steel can) that also serves as a positive electrode terminal is filled with a positive electrode mixture formed into pellets, and an electrolytic solution consisting of an organic solvent and an electrolyte is impregnated on top of the positive electrode mixture. A negative electrode is placed through a separator, and a conductive metal lid (for example, a stainless steel cap) that also serves as a negative electrode terminal is placed on top of the separator.The container and lid are insulated with an insulating backing and the gap is tightly sealed. It is an airtight structure.
このような構造の有機溶媒電池において、正極合剤の成
形ペレットを正極端子も兼ねる金属容器に充ｌＮする際
には、従来から金属容器の側に微粉末黒鉛のペーストを
塗布してここに成形ベレットを充填することが行なわれ
ている。これは、両者間の接触抵抗を低減せしめ、電池
全体の内部電気抵抗を小たらしめるだめの処置である。In an organic solvent battery with such a structure, when filling a metal container that also serves as a positive electrode terminal with molded pellets of positive electrode mixture, conventionally, a paste of finely powdered graphite is applied to the side of the metal container and molded there. Filling of pellets is carried out. This is a measure to reduce the contact resistance between the two and to reduce the internal electrical resistance of the entire battery.
［発明が解決しようとする問題点］
しかしながら、上記した処置を施した電池は、たしかに
その製作初期において内部抵抗は低い値を示しているが
、しかし貯蔵過程でその内部抵抗が徐々に上昇する。こ
のような現象は、大電流放電を必要とするような使用時
にしばしば問題になることである。[Problems to be Solved by the Invention] However, although the battery subjected to the above-described treatment does exhibit a low internal resistance at the initial stage of manufacture, the internal resistance gradually increases during storage. Such a phenomenon often becomes a problem in applications that require large current discharge.
本発明は、上記した問題を解消して、貯蔵中においても
内部抵抗の上昇が少ない有機溶媒電池の提供を目的とす
る。The present invention aims to solve the above-mentioned problems and provide an organic solvent battery in which the internal resistance does not increase much even during storage.
［問題点を解決するための手段］
本発明者らは、金属容器に微粉末黒鉛のペーストを塗布
した場合の上記問題点の原因につき鋭意追究した結果、
以下の知見を得るに到った。すなわち、上記ペーストの
主成分は微粉末黒鉛であり、これ自体は電気抵抗が低い
ので金属容器と正極合剤間の接触抵抗を低減せしめるに
有効であるが、しかし一方では、この黒鉛には微隘では
あれ鉄、カルシウムなどの不純物が含有されていて、貯
蔵過程でこれら不純物が電解液に溶解しそれが負極の表
面に析出するという事態を招くということである。その
結果、電池の内部抵抗が上昇するのである。[Means for Solving the Problems] As a result of intensive investigation into the causes of the above-mentioned problems when a paste of finely powdered graphite is applied to a metal container, the present inventors have found that:
We have obtained the following knowledge. In other words, the main component of the paste is finely powdered graphite, which itself has low electrical resistance and is therefore effective in reducing the contact resistance between the metal container and the positive electrode mixture. Impurities such as iron and calcium are contained in the electrolyte, and during storage, these impurities dissolve in the electrolyte and precipitate on the surface of the negative electrode. As a result, the internal resistance of the battery increases.
したがって、本発明者らは、電解液に溶解する不純物を
含有しない導電性粉末を用いれば上記不都合は解消しう
るとの着想を抱き、その導電性粉末を探索した結果、後
述の導電性セラミックス粉末は好適であるとの事実を見
出し本発明の有機溶媒電池を開発するに到った。Therefore, the present inventors had the idea that the above-mentioned disadvantages could be solved by using a conductive powder that does not contain impurities that dissolve in the electrolytic solution, and as a result of searching for such a conductive powder, the conductive ceramic powder described below It was discovered that the organic solvent battery of the present invention is suitable.
すなわち、本発明の有機溶媒電池は、正極合剤と正極端
子を兼ねる金属容器とが導電性セラミックス粉末を介し
て接触していることを特徴とする。That is, the organic solvent battery of the present invention is characterized in that a positive electrode mixture and a metal container that also serves as a positive electrode terminal are in contact with each other via a conductive ceramic powder.
本発明電池に用いる導電性セラミックス粉末としては、
↑ａＮ、 ＺｒＮ、ＴｉＮ、 ＮｂＮ、 ＶＮなどの窒
化物の粉末； ＴｉＣ，’ｖＪｃ、 ＴａＣなとの炭化
物の粉末をあげることができる。これらはそれぞれ単独
で又は２種以上を適宜に混合して用いることができる。The conductive ceramic powder used in the battery of the present invention includes:
↑Nitride powders such as aN, ZrN, TiN, NbN, and VN; Carbide powders such as TiC, 'vJc, and TaC can be mentioned. These can be used alone or in an appropriate mixture of two or more.
これらセラミックスの粉末は、例えば気相反応法によっ
て容易に製造することができる。例えば、ＴｉＮ粉末は
、二塩化チタン、窒素、水素から次の反応： Ｔｉ（
Ｉ；Ｌ２＋繕Ｎ２＋２Ｈ２→ＴｉＮ＋ ４ＨＣ文に基づ
いて製造することができる。この気相反応法においては
、反応圧２反応温度等の条件によって粒子径が変化する
ので、これら条件を適宜選定すれば所望する粒径の粉末
を得ることができる。These ceramic powders can be easily produced, for example, by a gas phase reaction method. For example, TiN powder is made from titanium dichloride, nitrogen, and hydrogen by the following reaction: Ti(
I; L2+Touch N2+2H2→TiN+ It can be manufactured based on the 4HC statement. In this gas phase reaction method, the particle size changes depending on conditions such as reaction pressure and reaction temperature, so if these conditions are appropriately selected, a powder with a desired particle size can be obtained.
この導電性セラミックス粉末は、その所定量を水；メタ
ノール、エタノールのようなアルコールに分散させてペ
ーストにし、このペーストを金属容器の正極合剤との接
触面に一様に塗布して使用に供される。なお、ペースト
の調製時には、ポリアクリル酸ソーダのような増粘剤を
添加してより粘稠性のペーストにすると、塗布後乾燥し
ても正極合剤のベレットが正極容器から剥落することを
完全に防止できて有効である。This conductive ceramic powder is prepared by dispersing a predetermined amount in water or alcohol such as methanol or ethanol to make a paste, and uniformly applying this paste to the surface of the metal container that will come in contact with the positive electrode mixture. be done. When preparing the paste, adding a thickener such as sodium polyacrylate to make the paste more viscous will completely prevent the positive electrode mixture pellet from falling off from the positive electrode container even if it dries after application. It is effective in preventing this.
ペーストの調製時、用いる導電性セラミックス粉末の粒
径は １−以下であることが好ましい。粒径が１μより
大きい場合には、水、アルコールに分散させたとき自重
で沈降する傾向が増大し、その結果、塗布時の均一塗布
が困難となるからである。When preparing the paste, the particle size of the conductive ceramic powder used is preferably 1 or less. This is because if the particle size is larger than 1 μm, there is an increased tendency for the particles to settle under their own weight when dispersed in water or alcohol, and as a result, uniform application during application becomes difficult.
［発明の実施例］
実施例１〜８
常用の気相成長法で平均粒径が１−以下である各種の導
電性セラミックス粉末を合成した。これら各粉末２５重
量部を水７５重量部に分散せしめてペーストとした。[Examples of the Invention] Examples 1 to 8 Various conductive ceramic powders having an average particle size of 1 or less were synthesized by a commonly used vapor phase growth method. 25 parts by weight of each of these powders were dispersed in 75 parts by weight of water to form a paste.
各ペーストを正極端子も兼ねるステンレス鋼製容器の内
面に均一に塗布したのち室温で充分に乾燥した。Each paste was uniformly applied to the inner surface of a stainless steel container that also served as a positive electrode terminal, and then thoroughly dried at room temperature.
ついで、ここに、正極活物質が３５０℃焼成の二酸化マ
ンガン、導電剤が黒鉛、結着剤がＰＴＦＥである正極合
剤の成形ペレットを置き、この−ヒに、炭酸プロピレン
と１．２−ジメトキシエタンとから成る混合溶媒（容積
混合比、１：１）に過塩酸リチウム １モル相当量が溶
解せしめられた電解液を保持するボロピレン製不織布の
セパレータを載せたのち。Next, a molded pellet of a positive electrode mixture in which the positive electrode active material is manganese dioxide fired at 350°C, the conductive agent is graphite, and the binder is PTFE is placed, and propylene carbonate and 1,2-dimethoxy After placing a separator made of boropyrene nonwoven fabric holding an electrolytic solution in which an amount equivalent to 1 mole of lithium perchlorate was dissolved in a mixed solvent consisting of ethane (volume mixing ratio, 1:1).
更にこの」二には負極である金属リチウム板を圧着した
ステンレス鋼製の金属蓋を冠着し、ポリプロピレン製バ
ッキングを介して全体をｖ：！してＣＲ２０１８型電池
各１００個を製作した。Furthermore, a stainless steel metal lid with a metal lithium plate, which is the negative electrode, is crimped onto this second, and the whole is covered with a polypropylene backing. Then, 100 CR2018 type batteries were manufactured.
これら各電池につき、内部抵抗の影響が最も顕著に現わ
れる重負荷放電を、初度及び６０℃で２０日間貯蔵後に
測定した。その平均値を一括して表に示した。測定方法
は、 −１０℃の温度で電池に １０にΩの定抵抗を接
続し、この状態で放電して放電深度がそれぞれ２％、４
０％、８０％になった時点で抵抗を ３００Ωに切換え
て３秒間放電した時の端子電圧を測定するという方法で
あった。For each of these batteries, heavy load discharge, where the influence of internal resistance is most apparent, was measured initially and after storage at 60° C. for 20 days. The average values are collectively shown in the table. The measurement method is to connect a constant resistor of 10Ω to the battery at a temperature of -10°C, and discharge it in this state to reach a depth of discharge of 2% and 4%, respectively.
The method was to switch the resistance to 300Ω when the voltage reached 0% and 80%, and measure the terminal voltage after discharging for 3 seconds.
［発明の効果］
以上の説明で明らかなように、本発明の有機溶媒電池は
、正極合剤と金属容器間に例えば気相成長法で合成され
電解液に溶解する不純物を含まない導電性セラミックス
粉末が介在しているので、貯蔵中の内部抵抗が上昇する
ことがなく長期に安定して使用することができる。[Effects of the Invention] As is clear from the above explanation, the organic solvent battery of the present invention has a conductive ceramic material synthesized by, for example, a vapor phase growth method and containing no impurities that dissolves in the electrolytic solution, between the positive electrode mixture and the metal container. Since the powder is present, internal resistance does not increase during storage and it can be used stably for a long period of time.
Claims (1)
ラミックス粉末を介して接触していることを特徴とする
有機溶媒電池。 ２、該導電性セラミックス粉末が、窒化タンタル、窒化
ジルコニウム、窒化チタン、窒化ニオブ、窒化バナジウ
ム、炭化チタン、炭化タングステン、炭化タンタルの群
から選ばれる少なくとも１種のセラミックスの粉末であ
る特許請求の範囲第１項記載の有機溶媒電池。 ３、該導電性セラミックス粉末の平均粒径が１μｍ以下
である特許請求の範囲第１項又は第２項記載の有機溶媒
電池。[Scope of Claims] 1. An organic solvent battery characterized in that a positive electrode mixture and a metal container that also serves as a positive electrode terminal are in contact with each other via conductive ceramic powder. 2. Claims in which the conductive ceramic powder is at least one ceramic powder selected from the group of tantalum nitride, zirconium nitride, titanium nitride, niobium nitride, vanadium nitride, titanium carbide, tungsten carbide, and tantalum carbide. The organic solvent battery according to item 1. 3. The organic solvent battery according to claim 1 or 2, wherein the conductive ceramic powder has an average particle size of 1 μm or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60120628A JPS61279055A (en) | 1985-06-05 | 1985-06-05 | Organic solvent battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60120628A JPS61279055A (en) | 1985-06-05 | 1985-06-05 | Organic solvent battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS61279055A true JPS61279055A (en) | 1986-12-09 |
Family
ID=14790926
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60120628A Pending JPS61279055A (en) | 1985-06-05 | 1985-06-05 | Organic solvent battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61279055A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160149217A1 (en) * | 2013-06-27 | 2016-05-26 | Toyota Jidosha Kabushiki Kaisha | Electrode for non-aqueous secondary battery |
-
1985
- 1985-06-05 JP JP60120628A patent/JPS61279055A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160149217A1 (en) * | 2013-06-27 | 2016-05-26 | Toyota Jidosha Kabushiki Kaisha | Electrode for non-aqueous secondary battery |
| US9819025B2 (en) * | 2013-06-27 | 2017-11-14 | Toyota Jidosha Kabushiki Kaisha | Electrode for non-aqueous secondary battery |
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