JPS6142858A - Nonaqueous electrolyte battery - Google Patents
Nonaqueous electrolyte batteryInfo
- Publication number
- JPS6142858A JPS6142858A JP59162547A JP16254784A JPS6142858A JP S6142858 A JPS6142858 A JP S6142858A JP 59162547 A JP59162547 A JP 59162547A JP 16254784 A JP16254784 A JP 16254784A JP S6142858 A JPS6142858 A JP S6142858A
- Authority
- JP
- Japan
- Prior art keywords
- iron
- negative electrode
- positive electrode
- battery
- iron sulfide
- 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
- H01M4/06—Electrodes for primary cells
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【発明の詳細な説明】
（イ）産業上の利用分野
本発明は二硫化鉄を正極活物質とする非水電解液電池の
改良に関するものである。DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application The present invention relates to improvement of a non-aqueous electrolyte battery using iron disulfide as a positive electrode active material.
（ロ） 従来の技術
負極活物質にリチウム、正極活物質に金属の酸化物、塩
化物、ハロゲンの炭素化合物など及び電解液としてプロ
ピレンカーボネート、ｒ−ブチロラフ！・ン、１．２ジ
メトキシエタンなどの有機溶媒に過塩素酸リチウム、ホ
ウフッ化リチウムなどの無機塩を溶解させたものを用い
る非水電解液電池は高エネルギー密度を有し、且自己放
電が少いなどの利点を備えるため注目されており、現在
までに二酸化マンガン、フッ化炭素などを正極活物質と
する３ｖ系の非水電解液電池が実用化きれている。(b) Conventional technology The negative electrode active material is lithium, the positive electrode active material is metal oxide, chloride, halogen carbon compound, etc., and the electrolyte is propylene carbonate, r-butyrorough!・Non-aqueous electrolyte batteries that use inorganic salts such as lithium perchlorate and lithium borofluoride dissolved in organic solvents such as 1.2 dimethoxyethane have high energy density and low self-discharge. It has attracted attention due to its advantages such as low energy consumption, and to date, 3V type non-aqueous electrolyte batteries using manganese dioxide, carbon fluoride, etc. as positive electrode active materials have been put into practical use.
そして近年になると、１．５ｖ系の非水電解液電池や二
次電池系の非水電解液電池にも大きな興味がもたれ研究
きれている。特に小型電子機器の電源電池として既存電
池との互換性を有する１、５ｖ系の非水電解液電池が注
目されている。In recent years, 1.5V type non-aqueous electrolyte batteries and secondary battery type non-aqueous electrolyte batteries have attracted great interest and research has been completed. In particular, 1.5V type non-aqueous electrolyte batteries, which are compatible with existing batteries, are attracting attention as power batteries for small electronic devices.
１．５ｖ系の非水電解液電池に用いる正極活物質として
は例えば特開昭５８〜５７２６２号公報に開示きれてい
るように二硫化鉄が知られているが、二硫化鉄（Ｆｌ！
Ｓ２ ）を正極活物質とした場合、初期放電電圧は高い
ものの放電の進行に伴いＦｅ５ｚ→ＬｉｘＦｅＳｇ二Ｆ
ｅ＋ＬｉｚＳの反応により放電電圧が２段階の特性を示
すという問題がある。Iron disulfide is known as a positive electrode active material used in 1.5V non-aqueous electrolyte batteries, as disclosed in, for example, JP-A-58-57262, but iron disulfide (Fl!
When S2) is used as the positive electrode active material, although the initial discharge voltage is high, as the discharge progresses, Fe5z→LixFeSg2F
There is a problem in that the discharge voltage exhibits two-step characteristics due to the reaction of e+LizS.
又、硫化鉄（ＦｅＳ）を正極活物質とした場合には平均
放電電圧が低く、且単位体積当りの充填容量が低いため
放電時間も短かいという問題がある。Furthermore, when iron sulfide (FeS) is used as the positive electrode active material, there are problems in that the average discharge voltage is low and the filling capacity per unit volume is low, resulting in a short discharge time.
（ハ） 発明が解決しようとする問題点本発明は二硫化
鉄を正極活物質として用いた場合における２段階の放電
電圧特性を改善することにある。(c) Problems to be Solved by the Invention The present invention aims to improve two-step discharge voltage characteristics when iron disulfide is used as a positive electrode active material.
（ニ） 問題点を解決するための手段本発明は正極と
して二硫化鉄を主体とする成型体と、該成型体の少くと
も負極と対向する表面に配置せる硫化鉄を主体とする層
とで構成したものを用いることを特徴とする。(d) Means for Solving the Problems The present invention comprises a molded body mainly composed of iron disulfide as a positive electrode, and a layer mainly composed of iron sulfide disposed on at least the surface of the molded body facing the negative electrode. It is characterized by using the configured one.
（ホ）作用
本発明電池によれば、正極表面の硫化鉄が負極のリチウ
ムと反応して活性な鉄を生成し、この鉄が二硫化鉄と反
応して硫化鉄を生成し、そしてこの生成硫化鉄がリチウ
ムと反応するという反応機構が、二硫化鉄とリチウムと
の反応機構と併行して進行する。(E) Function According to the battery of the present invention, iron sulfide on the surface of the positive electrode reacts with lithium on the negative electrode to produce active iron, which reacts with iron disulfide to produce iron sulfide, and this production The reaction mechanism in which iron sulfide reacts with lithium proceeds in parallel with the reaction mechanism between iron disulfide and lithium.
（へ） 実施例 以下本発明の実施例につき図面に基づき詳述する。(f) Examples Embodiments of the present invention will be described in detail below with reference to the drawings.
正極の作成；
市販の二硫化鉄（ＦｅＳ２）８５重量％に導電剤として
の黒鉛１０重量％及び結着剤としてのフッ素樹脂粉末５
重量％を加えて充分混合した後、約２トン／ｅｌＴ１２
の圧力で加圧成型して径１５．０ｍ／ｍ、厚み０．９ｍ
／ｍの成型体（２）を得る。Preparation of positive electrode: 85% by weight of commercially available iron disulfide (FeS2), 10% by weight of graphite as a conductive agent, and 5% by weight of fluororesin powder as a binder.
After adding weight% and mixing thoroughly, about 2 tons/elT12
Pressure molded at a pressure of 15.0 m/m in diameter and 0.9 m in thickness.
/m molded body (2) is obtained.
次いでこの成型体（２）の表面に、市販の硫化鉄（Ｆｅ
Ｓ）８５１ｉ量％と黒鉛１０重量％とフッ素樹脂粉末５
重量％とを混合した合剤を充填し、これらを再度約２ト
ン／口２の圧力で加圧成型して成型体（２）の表面に硫
化鉄を主体とする層（３）を配置し、ついで２００〜３
００℃の温度で焼成して正！（１）とする、尚、正極（
１）の寸法は径１５．０ｎ／＋、厚み１．１ｍ／ａ＋で
ある。Next, commercially available iron sulfide (Fe
S) 851i amount%, graphite 10% by weight, and fluororesin powder 5
% by weight, and pressure molded again at a pressure of about 2 tons/mouth 2 to place a layer (3) mainly composed of iron sulfide on the surface of the molded body (2). , then 200-3
Baking at a temperature of 00℃ is positive! (1), and the positive electrode (
The dimensions of 1) are diameter 15.0n/+ and thickness 1.1m/a+.
電池の作成：
厚み約０．６ｔａ／−のリチウム圧延板を径１５．０ｍ
／ｍに打抜いた負極（４）を周縁に絶縁バッキング（５
）を配置せる負極毎（６）の内底面に負極集電体（７）
を介して圧着すると共に、負極（４）上にプロピレンカ
ーボネートと１，２ジメトキシエタンとの混合溶媒にホ
ウフッ化リチウムを１モル／Ｑ溶解した電解液を含浸せ
るセパレータ（８）及び負極（４）と対向する面倒に硫
化鉄を主体とする層（３）が位置する如く正極（１〉を
載置し、ついで内底面に正極集電体（９〉を固設せる正
極缶（１０）を被せて後、正極缶（１０〉の開口縁を絶
縁バッキング（５）に締着して完成電池とする。この電
池を（Ａ）とする。Making the battery: A rolled lithium plate with a thickness of about 0.6 ta/- is 15.0 m in diameter.
The negative electrode (4) punched out to a diameter of /m is surrounded by an insulating backing (5
) on the inner bottom surface of each negative electrode (6) where a negative electrode current collector (7) is placed.
A separator (8) and a negative electrode (4) are impregnated with an electrolytic solution in which 1 mol/Q of lithium borofluoride is dissolved in a mixed solvent of propylene carbonate and 1,2 dimethoxyethane on the negative electrode (4). The positive electrode (1) is placed so that the layer (3) mainly composed of iron sulfide is located on the opposite side, and then the positive electrode can (10) with the positive electrode current collector (9) fixed on the inner bottom is covered. After that, the opening edge of the positive electrode can (10) is fastened to the insulating backing (5) to form a completed battery.This battery is designated as (A).
又、比較のために二硫化鉄（ＦｅＳ２）を主体とする成
型体のみで構成した正極を用いた第１の比較電池（Ｂ）
と、−硫化鉄（ＦｅＳ）を主体とする成型体のみで構成
した正極を用いた第２の比較電池（Ｃ）とを作成した。In addition, for comparison, a first comparison battery (B) using a positive electrode composed only of a molded body mainly composed of iron disulfide (FeS2) was prepared.
and a second comparative battery (C) using a positive electrode composed only of a molded body mainly composed of iron sulfide (FeS).
尚、第１、第２の比較電池は正極を除いて他は本発明電
池と同様である。Note that the first and second comparison batteries were the same as the battery of the present invention except for the positive electrode.
第３図はこれらの電池□を２０°Ｃにおいて５．６にΩ
定負荷で放電した時の放電特性を示し、図より本発明電
池（Ａ）は比較電池（Ｂ）（Ｃ）に比して高０放電電圧
を有し、且平坦性に優れた放電特性を示すことがわかる
。Figure 3 shows the resistance of these batteries □ to 5.6Ω at 20°C.
The figure shows the discharge characteristics when discharged under a constant load, and the figure shows that the battery of the present invention (A) has a higher zero discharge voltage than the comparative batteries (B) and (C), and has discharge characteristics with excellent flatness. I understand what is shown.
この理由を考察するに、本発明電池の場合番こけ、正極
が二硫化鉄を主体とする成型体と、該成型体の少くとも
負極と対向する表面に配置せる硫化鉄を主体とする層と
で構成されているため、放電時には正極表面の硫化鉄と
負極活物質としてのリチウムとが下記０式に基づき反応
して活性な鉄を生じる。Considering the reason for this, in the case of the battery of the present invention, the positive electrode has a molded body mainly composed of iron disulfide, and a layer mainly composed of iron sulfide disposed on at least the surface facing the negative electrode of the molded body. During discharge, iron sulfide on the surface of the positive electrode and lithium as the negative electrode active material react based on the following formula 0 to produce active iron.
２ Ｌｉ＋ Ｆｅ５−＋Ｆｅ＋Ｌｉ２ Ｓ −・−・
■モして、この活性な鉄が二硫化鉄と下記０式に基づ
き反応して硫化鉄を生成する。2 Li+ Fe5−+Fe+Li2 S −・−・
(2) Then, this active iron reacts with iron disulfide based on the following formula 0 to produce iron sulfide.
Ｆｅ＋Ｆｌ！Ｓ２４２ ＦｅＳ −＝■この■式で得
られた硫化鉄が更に０式に基づきリチウムと反応する。Fe+Fl! S242 FeS -=■ The iron sulfide obtained by this formula (■) further reacts with lithium based on the formula 0.
このような■、■式の反応機構が、二硫化鉄とリチウム
との反応機構と併行して円滑に進むため電池特性が改善
きれると考えられる。It is thought that the battery characteristics can be improved because the reaction mechanism of formulas (1) and (2) proceeds smoothly in parallel with the reaction mechanism of iron disulfide and lithium.
（ト）発明の効果 。(g) Effects of the invention.
上述した如く゛、本発明によれば２段階の放電電圧特性
を示すことなく、且高電圧の１．５■系非丞電解液電池
を得ることができるものであり、その工業的価値は極め
て大である。As mentioned above, according to the present invention, it is possible to obtain a high voltage 1.5-inch non-electrolyte battery without exhibiting two-stage discharge voltage characteristics, and its industrial value is extremely high. It's large.
第１図乃至第２図は本発明に係り、第１図は正極の断面
図、第２図は電池の断面図を示す、第３図は本発明電池
と比較電池との放電特性比較図である。
（１）・・・正極、（２）・・・二硫化鉄を主体とする
成型体、（３）・・・硫化鉄を主体とする層、（４〉・
・・負極、（５）・・・絶縁バッキング、（６）・・・
負極毎、（８）・・・セパレータ、（１０〉・・・正極
缶、（Ａ）・・・本発明電池、（Ｂ）（Ｃ）・・・比較
電池。Figures 1 and 2 relate to the present invention; Figure 1 is a cross-sectional view of the positive electrode, Figure 2 is a cross-sectional view of the battery, and Figure 3 is a comparison diagram of the discharge characteristics of the battery of the present invention and a comparative battery. be. (1)...Positive electrode, (2)...Molded body mainly composed of iron disulfide, (3)...Layer mainly composed of iron sulfide, (4>...
... Negative electrode, (5) ... Insulating backing, (6) ...
Each negative electrode, (8) Separator, (10> Positive electrode can, (A) Invention battery, (B) (C) Comparative battery.
Claims (1)
くとも負極と対向する表面に配置せる硫化鉄を主体とす
る層とで構成される正極を用いたことを特徴とする非水
電解液電池。(1) A non-aqueous product characterized by using a positive electrode composed of a molded body mainly composed of iron disulfide and a layer mainly composed of iron sulfide disposed on at least the surface of the molded body facing the negative electrode. electrolyte battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59162547A JPS6142858A (en) | 1984-08-01 | 1984-08-01 | Nonaqueous electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59162547A JPS6142858A (en) | 1984-08-01 | 1984-08-01 | Nonaqueous electrolyte battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6142858A true JPS6142858A (en) | 1986-03-01 |
Family
ID=15756666
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59162547A Pending JPS6142858A (en) | 1984-08-01 | 1984-08-01 | Nonaqueous electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6142858A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4829224B2 (en) * | 2004-05-28 | 2011-12-07 | インターナショナル レクティフィアー コーポレイション | Front contact formation for surface mounting |
-
1984
- 1984-08-01 JP JP59162547A patent/JPS6142858A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4829224B2 (en) * | 2004-05-28 | 2011-12-07 | インターナショナル レクティフィアー コーポレイション | Front contact formation for surface mounting |
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