JPS5987764A - Manufacture of positive active material for organic electrolyte battery - Google Patents
Manufacture of positive active material for organic electrolyte batteryInfo
- Publication number
- JPS5987764A JPS5987764A JP57199219A JP19921982A JPS5987764A JP S5987764 A JPS5987764 A JP S5987764A JP 57199219 A JP57199219 A JP 57199219A JP 19921982 A JP19921982 A JP 19921982A JP S5987764 A JPS5987764 A JP S5987764A
- Authority
- JP
- Japan
- Prior art keywords
- active material
- battery
- organic electrolyte
- cufes2
- electrolyte battery
- 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.)
- Granted
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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
-
- 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)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Primary Cells (AREA)
Abstract
Description
【発明の詳細な説明】
並業上の利用分野
本発明は、有機電解質電池の正ｊｔｆｉ、活’ｉｔ／Ｊ
Ｓにに用いるＣｕＦｅＳ２の製造法に関する。DETAILED DESCRIPTION OF THE INVENTION Field of Application The present invention relates to positive jtfi, active/j
The present invention relates to a method for manufacturing CuFeS2 used for S.
従来例の構成とその問題点
酸化銅（Ｃｕｂ）や硫化鉄（Ｆ’、ｅ Ｓ ２ ） を
ｉＥ極活物濁とする有機電解質電池は、それら活物ａの
単位わせたときの放電電圧が約１．６■で、従来の酸化
銀電池などと互換性があるなどの特長を有している。し
たがって、電子ウォッチをはじめ各種の小形電子機器用
電源として注目されている。Structure of conventional examples and their problems In an organic electrolyte battery that uses copper oxide (Cub) or iron sulfide (F', e S 2 ) as the iE active material, the discharge voltage when the units of these active materials a are combined is It has the advantage of being compatible with conventional silver oxide batteries, etc., with a battery life of approximately 1.6 square meters. Therefore, it is attracting attention as a power source for various small electronic devices including electronic watches.
′１￥１５子ウォッチは、使用される電池電圧の変動カ
ニその精度に大きな影響を力える。このため、放電々Ｂ
の変化がより少ない電池が必要となる。しかし、ＣｕＯ
やＦ ｅ Ｓ ２を正極活物７１７として用いると、放
電々圧の安定性に問題がある。'1￥15 The fluctuation of the battery voltage used in a child's watch has a great effect on its accuracy. For this reason, the discharge B
A battery with less change in temperature is needed. However, CuO
If F e S 2 or F e S 2 is used as the positive electrode active material 717, there is a problem in the stability of discharge pressure.
すなわち、正極活物質がＣｕＯの場合は、放電を開始し
てから電圧が安定化する捷でに電圧が落ち込む現象があ
る。一方、Ｆ ｅ Ｓ ２の場合は、このノｉ（電機槽
がＦｅＳ２＋Ｌｉ→ＬｉｘＦｅＳ２→Ｆｅ十Ｌｉ２Ｓで
二段の放電曲線となる。したがって、前述の、しうなウ
ォソグーの精度面での間：須を有していた。That is, when the positive electrode active material is CuO, there is a phenomenon in which the voltage drops before the voltage stabilizes after starting discharge. On the other hand, in the case of F e S 2, this noi (electrical tank becomes a two-stage discharge curve with FeS2 + Li → LixFeS2 → Fe + Li2S. Therefore, the above-mentioned interval in terms of accuracy of the had.
これらの改良策として、ＣｕＯおよびＦ ｅ Ｓ ２に
天然の黄銅鉱（Ｃｕ’Ｆ’ｅ Ｓ ２ ）を混合して用
いることにより、前述のような欠点を除去する提案があ
る。As a measure to improve these, there is a proposal to eliminate the above-mentioned drawbacks by using a mixture of CuO and Fe S 2 with natural chalcopyrite (Cu'F'e S 2 ).
ところが、天然の黄銅鉱を用いた場合は、特に６０℃で
３０日間程度の高温保存で容量劣化が大きいという問題
がある。この容量劣化の原因は、混合した黄銅鉱の不純
物によるものと考えられる。However, when natural chalcopyrite is used, there is a problem in that capacity deterioration is large, especially when stored at a high temperature of 60° C. for about 30 days. The cause of this capacity deterioration is thought to be due to impurities in the mixed chalcopyrite.
発明の目的
本発明は、以上のような不都合を除去し、保存特性の良
好な有機電解質電池を与える正極活物質Ｃｕ Ｆ ｅ
Ｓ ２ を得る方法を提供することを目的とする。Object of the Invention The present invention eliminates the above-mentioned disadvantages and provides an organic electrolyte battery with good storage characteristics using a positive electrode active material CuFe.
The purpose is to provide a method for obtaining S 2 .
発明の構成
本発明は、Ｃｕ ２ ＳとＦ ｅ Ｓ ２とを１：２の
モル比で混合し、この混合物を６００〜７００℃の不活
性雰囲気中で熱処理することを特徴とする。Structure of the Invention The present invention is characterized in that Cu 2 S and Fe S 2 are mixed at a molar ratio of 1:2, and this mixture is heat-treated in an inert atmosphere at 600 to 700°C.
Ｃｕ Ｓ、Ｆ’ｅＳ２の融点はそれぞれ１１３０℃。The melting points of Cu S and F'eS2 are each 1130°C.
６４２℃であり、このように融点が犬きく異なる物ａを
加熱して１つの物質を合成するのは一般的でないが、本
発明者らは、上記のような’Ａ（’ｌで熱処理すること
により、ＣｕＦｅＳ２を合成することに成功した。642°C, and it is not common to synthesize a single substance by heating substances a with such vastly different melting points. By doing so, we succeeded in synthesizing CuFeS2.
本発明による反応式は次式で表さ１′しる。The reaction formula according to the present invention is expressed by the following formula.
Ｃｕ Ｓ＋２ＦｅＳ２−＋２ＣｕＦｅＳ２＋Ｓ↑ここ
で熱処理温度が６００℃以下では、上記反応が進行しに
〈〈長時間を要する。寸だ、７００℃以」二になるとＦ
ｅ Ｓ ２の分解などにより、非化学昂論的化合物を
形成しやすい。まだ、合成時の雰囲気は、酸素あるいは
空気中では前記硫化物が酸化されるため、アルゴンガス
などの不活性ガスを使用する必要がある。Cu S+2FeS2-+2CuFeS2+S↑Here, if the heat treatment temperature is 600°C or lower, it takes a long time for the above reaction to proceed. It's over 700 degrees F.
e It is easy to form non-chemical compounds due to decomposition of S2, etc. However, since the sulfide is oxidized in oxygen or air during synthesis, it is necessary to use an inert gas such as argon gas.
実施例の説明
Ｃｕ ＳとＦｅＳ とを１：２のモル比で混合し、
２ ２
これをアルゴン雰囲気中において、６２０’Ｃの温度で
５時間熱処理した後、冷却し、粉砕した。得られた試料
は、Ｘ線回折によってＣｕ Ｆ ｅ Ｓ ２である（二
とが確認された。Description of Examples CuS and FeS are mixed in a molar ratio of 1:2,
2 2 This was heat treated at a temperature of 620'C for 5 hours in an argon atmosphere, then cooled and pulverized. The obtained sample was confirmed to be CuFeS2 by X-ray diffraction.
得られだＣｕ Ｆ ｅ Ｓ ２を用いて以下に示すよう
な電池をを試作し、従来品との比較試験をした。Using the obtained Cu Fe S 2, a battery as shown below was prototyped, and a comparison test with a conventional product was conducted.
表のような組成からなる正極混合物をニッケル製のエキ
スパンデッドメタル集電体に加圧、充填し、厚み０．３
５瀧のシート状電極を作シ、直径５．８ｔｎｍに打ち抜
いて正極とする。A positive electrode mixture having the composition shown in the table was pressurized and filled into a nickel expanded metal current collector to a thickness of 0.3.
A sheet-like electrode with a diameter of 5.5 mm was made and punched out to a diameter of 5.8 tnm to serve as a positive electrode.
以 １ 余 白
これらの■−極を用いて第１図に示すボタン形電池を絹
み立てた。第１図において、１はニッケルメッキを施［
７だ厚さ０．１５ ａｍのステンレス鋼からなど、外径
８．５ ＋ｎｍ、高さ０．６０ｍｎ＋ の封口板で、
その粗面化した内面には直径６゜５＋＋ｕｉ 、 ）阜
さ０．２５ｍｍの金属リチウムからなる負極２を圧着し
ている。３はポリプロピレン製不織布からなるセパレー
タで、炭酸プロピレンと１，２−ジメトギシエタンとを
体積比で１：１の割合で混合した溶媒に過塩素酸リチウ
ムを１モル１を溶解させた電解液を含浸している。４は
前記の正極で、その片面には集電体としての前記フーキ
スパンデソドメタル５を有する。1 Margin Using these ■-poles, a button-shaped battery as shown in FIG. 1 was fabricated. In Figure 1, 1 is nickel plated [
A sealing plate made of stainless steel with a thickness of 0.15 am and an outer diameter of 8.5 nm and a height of 0.60 mm.
A negative electrode 2 made of metallic lithium and having a diameter of 6°5++ ui and a height of 0.25 mm is bonded to the roughened inner surface. 3 is a separator made of polypropylene nonwoven fabric, impregnated with an electrolytic solution in which 1 mol 1 of lithium perchlorate is dissolved in a solvent that is a mixture of propylene carbonate and 1,2-dimethoxyethane in a volume ratio of 1:1. ing. 4 is the above-mentioned positive electrode, and one side thereof has the above-mentioned Fukispande metal 5 as a current collector.
６はニッケルメッキを施した厚さ０．１６ ｍｍのステ
ンレス鋼よりなる外径９．５＋ｎｍ、高さ１．２咽のケ
ース、７はポリプロピレン製ガスクノトである。6 is a case made of nickel-plated stainless steel with a thickness of 0.16 mm and has an outer diameter of 9.5+ nm and a height of 1.2 mm, and 7 is a polypropylene gasket.
前記の各トド正極を用いて作製した電池を試作直後およ
び６０℃で３０日間保存後に、２０℃において３ｏＫＱ
の定抵抗放電をしたときの放電曲線を第２図に示す。Immediately after trial production and after storage at 60°C for 30 days, batteries manufactured using each of the above-mentioned Todo positive electrodes had a temperature of 3oKQ at 20°C.
Figure 2 shows the discharge curve when constant resistance discharge is performed.
図から明らかなように、従来のＣｕ Ｆ ｅ Ｓ ２
を混合した電池は高温保存における容量劣化が太きｂの
に対し、本発明のＣｕＦｅ２を用いた電／ｌ１２１１−
ｊきわめて保存性にすぐれていることがわかる。As is clear from the figure, the conventional Cu Fe S 2
The battery containing CuFe2 of the present invention has a large capacity deterioration during high-temperature storage, whereas the battery containing CuFe2 of the present invention
It can be seen that it has extremely good storage stability.
発明のダ１果
以−１このように、本発明は、有機電解質電池の高ンＨ
，保存による容量劣化の少ない正極活物質を与えるもの
で、電子ウォッチなどに適（７た電池を得ることができ
る。ADVANTAGES OF THE INVENTION-1 As described above, the present invention provides an organic electrolyte battery with high
, it provides a positive electrode active material with little capacity deterioration due to storage, making it possible to obtain batteries suitable for electronic watches and the like.
第１図は本発明の実施例に用いた電池の一部を断面にし
た正面図、第２図は放電特性の比軸を示す。
２・川・・負４Ｌ−３・・・・・・セパレータ、４・・
・・・・正極。
代理人の氏名 弁理士 中 尾 敏 男 ほか１名＠１
図FIG. 1 is a partially sectional front view of a battery used in an example of the present invention, and FIG. 2 shows a specific axis of discharge characteristics. 2. River... Negative 4L-3...Separator, 4...
...Positive electrode. Name of agent: Patent attorney Toshio Nakao and 1 other person @1
figure
Claims (1)
合で混合したイｊイ、合物を、６００〜７００℃の不活
性雰囲気中で熱処理することによりＣｕＦｅＳ２を得る
ことを特徴とする有機電角イ賃′／Ｊｍ池用正極活物１
ｊ４の製ｊ告ａ、。CuFeS2 is obtained by heat-treating a compound obtained by mixing Cu2S and leS2 at a molar ratio of 1:2 in an inert atmosphere at 600 to 700°C. Organic electrode active material 1 for positive electrode /Jm pond
J4's production a.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57199219A JPS5987764A (en) | 1982-11-12 | 1982-11-12 | Manufacture of positive active material for organic electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57199219A JPS5987764A (en) | 1982-11-12 | 1982-11-12 | Manufacture of positive active material for organic electrolyte battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5987764A true JPS5987764A (en) | 1984-05-21 |
| JPH0326503B2 JPH0326503B2 (en) | 1991-04-11 |
Family
ID=16404115
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57199219A Granted JPS5987764A (en) | 1982-11-12 | 1982-11-12 | Manufacture of positive active material for organic electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5987764A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60243970A (en) * | 1984-05-17 | 1985-12-03 | Matsushita Electric Ind Co Ltd | Manufacture of positive active material for organic electrolyte battery |
-
1982
- 1982-11-12 JP JP57199219A patent/JPS5987764A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60243970A (en) * | 1984-05-17 | 1985-12-03 | Matsushita Electric Ind Co Ltd | Manufacture of positive active material for organic electrolyte battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0326503B2 (en) | 1991-04-11 |
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