JPH10199544A - Lithium primary battery - Google Patents
Lithium primary batteryInfo
- Publication number
- JPH10199544A JPH10199544A JP9002895A JP289597A JPH10199544A JP H10199544 A JPH10199544 A JP H10199544A JP 9002895 A JP9002895 A JP 9002895A JP 289597 A JP289597 A JP 289597A JP H10199544 A JPH10199544 A JP H10199544A
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- positive electrode
- iron
- battery
- sulfur compound
- 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
-
- Y02E60/12—
Landscapes
- Primary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、鉄の硫黄化合物を
電極材料に用いるリチウム一次電池に関するものであっ
て、詳しくは、一般式、Ｆｅ1-x Ｓ（０＜ｘ＜１）で表
される鉄の硫黄化合物を正極又は負極に用いるリチウム
一次電池に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithium primary battery using a sulfur compound of iron as an electrode material. More specifically, the present invention relates to a general formula, Fe.sub.1 -xS (0 <x <1). The present invention relates to a lithium primary battery using a sulfur compound of iron for a positive electrode or a negative electrode.
【０００２】リチウム一次電池は、水溶液系一次電池に
比べて、高いエネルギー密度の電池として注目されてい
る電池である。[0002] A lithium primary battery has attracted attention as a battery having a higher energy density than an aqueous primary battery.
【０００３】[0003]
【従来の技術】鉄化合物は、原料の鉄が資源的にも豊富
で且つ安価であることから、電極活物質への適用が試み
られてきた。2. Description of the Related Art An iron compound has been attempted to be applied to an electrode active material because iron as a raw material is abundant in resources and inexpensive.
【０００４】特に、二硫化鉄（ＦｅＳ2 ）や硫化鉄（Ｆ
ｅＳ）は、他のリチウム一次電池の正極材料に比べて、
単位重量当たりの理論放電容量が大きいことや、水溶液
系一次電池の電池電圧と互換性があることから、実用化
に向けた検討が実施され、ＦｅＳ2 に関してはリチウム
一次電池用正極として実用化されている。In particular, iron disulfide (FeS 2 ) and iron sulfide (F
eS) is higher than the cathode material of other lithium primary batteries,
Because of its large theoretical discharge capacity per unit weight and compatibility with the battery voltage of aqueous primary batteries, studies have been conducted toward its practical use, and FeS 2 has been commercialized as a positive electrode for lithium primary batteries. ing.
【０００５】しかし、ＦｅＳに関しては、ＦｅＳ2 に比
べて腐食性が強いことや、十分な性能が引き出せないこ
とから、これまで具体的な実用化の提案は成されていな
かった。However, since FeS is more corrosive than FeS 2 and cannot exhibit sufficient performance, no specific practical application has been proposed so far.
【０００６】一方、リチウム電池は、軽量・小型でエネ
ルギー密度の高い高性能電池として、最近その重要性が
増している電池である。[0006] On the other hand, lithium batteries are recently increasing in importance as high performance batteries that are lightweight, small and have high energy density.
【０００７】[0007]
【発明が解決しようとする課題】本発明の目的は、鉄化
合物を用いた新規なリチウム一次電池を提供することに
ある。An object of the present invention is to provide a novel lithium primary battery using an iron compound.
【０００８】[0008]
【課題を解決するための手段】本発明者は、鉄化合物を
用いた新規なリチウム電池を提案するために鋭意検討を
行った結果、一般式、Ｆｅ1-X Ｓ（０＜ｘ＜１）で表さ
れる鉄の硫黄化合物が、リチウム一次電池の正極又は負
極に適用可能であり、正極または負極に用いることで、
従来にはない新しいリチウム一次電池が構成可能である
ことを見出し、本発明を完成するに至った。Means for Solving the Problems The present inventors have conducted intensive studies to propose a new lithium battery using an iron compound, and as a result, have found that the general formula: Fe 1-X S (0 <x <1) The sulfur compound of iron represented by can be applied to the positive electrode or the negative electrode of the lithium primary battery, by using the positive electrode or the negative electrode,
The inventors have found that a new lithium primary battery that has never existed before can be constructed, and have completed the present invention.
【０００９】[0009]
【作用】以下、本発明を具体的に説明する。The present invention will be specifically described below.
【００１０】本発明のリチウム一次電池には、一般式、
Ｆｅ1-x Ｓ（０＜ｘ＜１）で表される鉄の硫黄化合物を
用いる。The lithium primary battery of the present invention has a general formula:
An iron sulfur compound represented by Fe 1-x S (0 <x <1) is used.
【００１１】鉄の硫黄化合物としては、一般にＦｅＳ及
び不定比組成のＦｅＳ1+x と、Ｆｅ2 Ｓ3 等の硫化鉄が
知られているが、本発明のリチウム一次電池に用いる鉄
の硫黄化合物としては、一般式、Ｆｅ1-x Ｓ（０＜ｘ＜
１）の関係を満たす化合物であれば特に制限されるもの
ではなく、上記３つのタイプの硫化鉄の少なくとも１種
類以上からなる混合物または複合物であっても良い。As iron sulfur compounds, FeS and iron sulfides such as FeS 1 + x having a non-stoichiometric composition and Fe 2 S 3 are generally known. Is represented by the general formula: Fe 1-x S (0 <x <
The compound is not particularly limited as long as the compound satisfies the relation of 1), and may be a mixture or a composite of at least one of the above three types of iron sulfide.
【００１２】一般式 Ｆｅ1-x Ｓ（０＜ｘ＜１）で表さ
れる鉄の硫黄化合物を構成する成分として例示されるＦ
ｅＳ、ＦｅＳ1+x 、Ｆｅ2 Ｓ3 及びＦｅＳ2 は以下に示
される性状を示す化合物である。F is exemplified as a component constituting a sulfur compound of iron represented by the general formula Fe 1-x S (0 <x <1).
eS, FeS 1 + x , Fe 2 S 3 and FeS 2 are compounds having the following properties.
【００１３】硫化鉄（II) は、純粋なＦｅＳとＦｅＳ
1+x で表される不定比組成のいずれかの化合物である。Iron (II) sulfide is composed of pure FeS and FeS
Any compound having a non-stoichiometric composition represented by 1 + x .
【００１４】純粋なＦｅＳは、還元鉄と蒸留イオウをと
を真空密閉容器中で１０００℃で２４時間熱してつくら
れる。また、鉄（II) 塩水溶液に硫化アンモニウムを加
えても得られる。その性状は無色ないし淡褐色の結晶で
ある。Pure FeS is made by heating reduced iron and distilled sulfur in a vacuum sealed vessel at 1000 ° C. for 24 hours. It can also be obtained by adding ammonium sulfide to an aqueous iron (II) salt solution. Its properties are colorless to light brown crystals.
【００１５】不定比組成のＦｅＳ1+x は、天然には磁硫
鉄鉱として産する化合物である。また、工業的には鉄粉
とイオウとをるつぼ中で融解してつくられ、その性状は
灰黒色片または塊状である。FeS 1 + x having a non-stoichiometric composition is a compound that naturally occurs as pyrrhotite. In addition, it is industrially produced by melting iron powder and sulfur in a crucible, and its properties are gray-black flakes or lumps.
【００１６】不定比組成の化合物では、湿った状態で空
気中で酸化されてイオウを分離し、褐色の塩基性硫酸塩
となることがある。A compound having a non-stoichiometric composition may be oxidized in the air in a wet state to separate sulfur and form a brown basic sulfate.
【００１７】Ｆｅ2 Ｓ3 は、鉄（III)塩溶液に硫化アン
モニウムを十分量加えると得られる黒色粉末で、湿った
空気中ではイオウを遊離して酸化物の水和物になること
がある。Fe 2 S 3 is a black powder obtained by adding a sufficient amount of ammonium sulfide to an iron (III) salt solution, and may release sulfur in humid air to become a hydrate of an oxide. .
【００１８】ＦｅＳ2 は、鉱石としては、白鉄鉱（鉱物
名 marcasite）及び黄鉄鉱（鉱物名pyrite)として産出
するが、この内、電池として機能するのは、充填密度が
高く電子伝導性が良い、岩塩型の結晶構造を有する黄鉄
鉱である。黄鉄鉱は合成可能であるが、電池材料として
機能するのは天然に産出する鉱石から得られるもののみ
である。As ores, FeS 2 is produced as pyrite (mineral name marcasite) and pyrite (mineral name pyrite). Of these, the one that functions as a battery is that it has a high packing density and good electron conductivity. It is a pyrite having a rock salt type crystal structure. Although pyrite is synthesizable, it only functions as a battery material from naturally occurring ores.
【００１９】本発明のリチウム一次電池に用いる、一般
式、Ｆｅ1-x Ｓ（０＜ｘ＜１）で表される鉄の硫黄化合
物をリチウム一次電池の電極に用いる場合には、特に制
限されるものではないが、通常のリチウム一次電池材料
の前処理として行われる加熱処理以外にも、予め加熱処
理を行った後に一次電池材料としての通常の加熱処理を
行っても良い。When an iron sulfur compound represented by the general formula, Fe 1-x S (0 <x <1), which is used for the lithium primary battery of the present invention, is used for an electrode of the lithium primary battery, there is no particular limitation. Although not limited to the above, in addition to the heat treatment performed as a pretreatment of the normal lithium primary battery material, a normal heat treatment as the primary battery material may be performed after the heat treatment is performed in advance.
【００２０】予め加熱処理を行う方法については、材料
組成が一般式、Ｆｅ1-x Ｓ（０＜ｘ＜１) の関係を維持
できる加熱処理であれば特に制限されるものではない。The method of performing the heat treatment in advance is not particularly limited as long as the material composition can maintain the relationship represented by the general formula, Fe 1-x S (0 <x <1).
【００２１】本発明のリチウム一次電池において、一般
式、Ｆｅ1-x Ｓ（０＜ｘ＜１）で表される鉄の硫黄化合
物をリチウム一次電池の正極に用いる場合には、負極に
は、リチウム金属、リチウム合金、及び本発明の鉄の硫
黄化合物よりも酸化還元電位の低いリチウムを予め含有
したリチウムを吸蔵可能な物質のいづれか少なくとも１
種類以上を用いることが必要である。In the lithium primary battery of the present invention, when an iron sulfur compound represented by the general formula, Fe 1-x S (0 <x <1) is used for the positive electrode of the lithium primary battery, the negative electrode: At least one of lithium metal, a lithium alloy, and a lithium-storable substance containing lithium in advance, which has a lower redox potential than the sulfur compound of iron of the present invention.
It is necessary to use more than one type.
【００２２】また、本発明のリチウム一次電池におい
て、一般式、Ｆｅ1-x Ｓ（０＜ｘ＜１）で表される鉄の
硫黄化合物を負極に用いる場合には、正極には本発明の
鉄の硫黄化合物よりも酸化還元電位の高いリチウムを予
め含有したリチウムを放出可能な物質を用いることが必
要である。In the lithium primary battery of the present invention, when a sulfur compound of iron represented by the general formula Fe 1-x S (0 <x <1) is used for the negative electrode, the positive electrode of the present invention is used for the positive electrode. It is necessary to use a substance capable of releasing lithium containing lithium having a higher oxidation-reduction potential than an iron sulfur compound.
【００２３】リチウム合金としては、例えば、リチウム
／アルミニウム合金、リチウム／スズ合金、リチウム／
鉛合金等が例示される。As the lithium alloy, for example, lithium / aluminum alloy, lithium / tin alloy, lithium / tin alloy
A lead alloy or the like is exemplified.
【００２４】リチウムを予め含有したリチウムを吸蔵ま
たは放出可能な物質としては、特に制限されないが、Ｌ
ｉＭｎ2 Ｏ4 、ＬｉＭｎＯ2 、ＬｉＣｏＯ2 、ＬｉＮｉ
Ｏ2 、ＬｉＦｅＯ2 及びこれら化合物の複合体等の含リチ
ウム遷移金属酸化物等の酸化物や、グラファイト、黒鉛
等の炭素質材料、ＦｅＯ、Ｆｅ2 Ｏ3 、Ｆｅ3 Ｏ4 等の
酸化鉄、ＣｏＯ、Ｃｏ2 Ｏ3 、Ｃｏ3 Ｏ4 等の酸化コバ
ルトに予めリチウムをドープした化合物が例示される。
なお、これらのリチウムを予め含有したリチウムを吸蔵
放出可能な物質は、その酸化還元電位によって、負極ま
たは正極への適用が制限される。The substance capable of occluding or releasing lithium containing lithium in advance is not particularly limited.
iMn 2 O 4 , LiMnO 2 , LiCoO 2 , LiNi
Oxides such as lithium-containing transition metal oxides such as O 2 , LiFeO 2 and composites of these compounds; carbonaceous materials such as graphite and graphite; iron oxides such as FeO, Fe 2 O 3 and Fe 3 O 4 ; Examples include compounds in which cobalt oxide such as CoO, Co 2 O 3 , and Co 3 O 4 is doped with lithium in advance.
Note that application of these substances containing lithium in advance and capable of inserting and extracting lithium to the negative electrode or the positive electrode is restricted by the oxidation-reduction potential.
【００２５】また、本発明のリチウム一次電池の電解質
は、特に制限されないが、例えば、炭酸プロピレン、炭
酸ジエチル、炭酸ジメチル等のカーボネート類や、スル
ホラン、ジメチルスルホキシド等のスルホラン類、γ−
ブチルラクトン等のラクトン類、ジメトキシエタン等の
エーテル類の少なくとも１種類以の有機溶媒中に、過塩
素酸リチウム、四フッ化ホウ酸リチウム、六フッ化リン
酸リチウム、トリフルオロメタンスルホン酸リチウム等
のリチウム塩の少なくとも１種類以上を溶解したもの
や、無機系及び有機系のリチウムイオン導電性の固体電
解質等を用いることができる。The electrolyte of the lithium primary battery of the present invention is not particularly limited. For example, carbonates such as propylene carbonate, diethyl carbonate and dimethyl carbonate, sulfolane such as sulfolane and dimethyl sulfoxide, and γ-
Lactones such as butyl lactone, and ethers such as dimethoxyethane in at least one organic solvent, such as lithium perchlorate, lithium tetrafluoroborate, lithium hexafluorophosphate, lithium trifluoromethanesulfonate, etc. A solution in which at least one kind of lithium salt is dissolved, an inorganic or organic lithium ion conductive solid electrolyte, or the like can be used.
【００２６】本発明の鉄化合物複合体を正極または負極
に用いて、図１に示す電池を構成した。A battery shown in FIG. 1 was constructed using the iron compound composite of the present invention for a positive electrode or a negative electrode.
【００２７】図中において、１：正極用リード線、２：
正極集電用メッシュ、３：正極、４：セパレータ、５：
負極、６：負極集電用メッシュ、７：負極用リード線、
８：容器、を示す。In the figure, 1: lead wire for positive electrode, 2:
Positive electrode collecting mesh, 3: Positive electrode, 4: Separator, 5:
Negative electrode, 6: negative electrode current collector mesh, 7: negative electrode lead wire,
8: Container.
【００２８】以下に、本発明の具体例として実施例を示
すが、本発明はこれらの実施例により限定されるもので
はない。Examples are shown below as specific examples of the present invention, but the present invention is not limited to these examples.
【００２９】[0029]
実施例１ ［電池の構成］実施例１として、ＦｅＳ（試薬１級）と
導電剤のポリテトラフルオロエチレンとアセチレンブラ
ックの混合物（商品名：ＴＡＢ−２）を、重量比で２：
１の割合で混合した。混合物７５ｍｇを１ｔｏｎ／ｃｍ
2 の圧力で、２０ｍｍφのメッシュ（ＳＵＳ ３１６）
上にペレット状に成型したのちに、２００℃で５時間、
減圧乾燥処理を行った。これを、図１の３の正極に用い
て、図１の５の負極にはリチウム箔から切り取ったリチ
ウム片を用いて、電解液には六フッ化リン酸リチウムを
１ｍｏｌ／ｄｍ3 の濃度で溶解したエチレンカーボネー
トとジエチルカーボネートの体積比１：２の混合溶媒に
溶解したものを図１の４のセパレータに含浸させて、断
面積２．５ｃｍ2 の図１に示した電池を構成した。Example 1 [Structure of Battery] In Example 1, a mixture of FeS (reagent first grade), polytetrafluoroethylene as a conductive agent and acetylene black (trade name: TAB-2) was used in a weight ratio of 2:
1 was mixed. 75 mg of the mixture is 1 ton / cm
At a pressure of 2 , 20mmφ mesh (SUS 316)
After being molded into a pellet on top, at 200 ° C for 5 hours,
A vacuum drying treatment was performed. This was used for the positive electrode in FIG. 1, 3 for the negative electrode in FIG. 1, a lithium piece cut from a lithium foil for the negative electrode in FIG. 1, and lithium hexafluorophosphate at a concentration of 1 mol / dm 3 for the electrolytic solution. A solution of ethylene carbonate and diethyl carbonate dissolved in a mixed solvent having a volume ratio of 1: 2 was impregnated into the separator of FIG. 1 to form the battery shown in FIG. 1 having a cross-sectional area of 2.5 cm 2 .
【００３０】［評価］上記方法で作成した電池を、０．
４ｍＡ／ｃｍ2 の一定電流で電池電圧が１．２Ｖまで放
電を行った。平坦な放電曲線を示し、正極活物質重量当
り４００ｍＡｈの放電容量が得られた。[Evaluation] The battery prepared by the above method was used in a
The battery was discharged at a constant current of 4 mA / cm 2 until the battery voltage reached 1.2 V. A flat discharge curve was shown, and a discharge capacity of 400 mAh per weight of the positive electrode active material was obtained.
【００３１】実施例２ 実施例２として、正極に予め大気中１１０℃の温度で１
２時間熱処理したものを用いた以外は実施例１と同様に
して電池を作成し評価を行った。正極活物質重量当り４
２０ｍＡｈの放電容量が得られた。Example 2 As Example 2, the positive electrode was previously heated to 110 ° C. in air at a temperature of 110 ° C.
A battery was prepared and evaluated in the same manner as in Example 1, except that a battery heat-treated for 2 hours was used. 4 per weight of positive electrode active material
A discharge capacity of 20 mAh was obtained.
【００３２】実施例３ 実施例３として、正極に予め大気中２２０℃の温度で１
２時間熱処理したものを用いた以外は実施例１と同様に
して電池を作成し評価を行った。正極活物質重量当り４
５０ｍＡｈの放電容量が得られた。Example 3 As Example 3, a positive electrode was previously applied to the positive electrode at a temperature of 220 ° C. in air.
A battery was prepared and evaluated in the same manner as in Example 1, except that a battery heat-treated for 2 hours was used. 4 per weight of positive electrode active material
A discharge capacity of 50 mAh was obtained.
【００３３】実施例４ 実施例３として、実施例１で正極に用いたＦｅＳと導電
剤との混合物を図１の５の負極に用いて、図１の３の正
極には市販のリチウムマンガンスピネル( ＬｉＭｎ2 Ｏ
4)を導電剤のポリテトラフルオロエチレンとアセチレン
ブラックの混合物（商品名：ＴＡＢ−２）を、重量比で
２：１の割合で混合し、混合物７５ｍｇを１ｔｏｎ／ｃ
ｍ2 の圧力で、２０ｍｍφのメッシュ（ＳＵＳ ３１
６）上にペレット状に成型したのちに、２００℃で５時
間、減圧乾燥処理を行ったものを用いた以外は、実施例
１と同様な電池を構成し評価を行った。Example 4 As Example 3, a mixture of FeS and the conductive agent used for the positive electrode in Example 1 was used for the negative electrode in FIG. 1, and a commercially available lithium manganese spinel was used in the positive electrode in FIG. (LiMn2O
4) was mixed with a mixture of polytetrafluoroethylene and acetylene black (trade name: TAB-2) at a ratio of 2: 1 by weight, and 75 mg of the mixture was 1 ton / c.
At a pressure of m2, a mesh of 20 mmφ (SUS 31
6) A battery was formed and evaluated in the same manner as in Example 1 except that a pellet was formed thereon and then subjected to a vacuum drying treatment at 200 ° C. for 5 hours.
【００３４】正極活物質重量当り１１０ｍＡｈの放電容
量が得られた。A discharge capacity of 110 mAh per weight of the positive electrode active material was obtained.
【００３５】[0035]
【発明の効果】以上述べてきたとおり、一般式、Ｆｅ
1-x Ｓ（０＜ｘ＜１）で表される鉄の硫黄化合物をリチ
ウム一次電池の正極または負極に用いることで、新規な
リチウム一次電池が構成できる。新規なリチウム一次電
池を提案することは、産業上有益な知見である。As described above, the general formula, Fe
By using a sulfur compound of iron represented by 1-xS (0 <x <1) for a positive electrode or a negative electrode of a lithium primary battery, a novel lithium primary battery can be formed. Proposing a new lithium primary battery is an industrially useful finding.
【図１】実施例で構成した電池の実施態様を示す断面図
である。FIG. 1 is a cross-sectional view showing an embodiment of a battery constituted in an example.
１ 正極リード線 ２ 正極集電用メッシュ ３ 正極 ４ セパレータ ５ 負極 ６ 負極集電用メッシュ ７ 負極用リード線 ８ 容器 REFERENCE SIGNS LIST 1 positive electrode lead wire 2 positive electrode current collecting mesh 3 positive electrode 4 separator 5 negative electrode 6 negative electrode current collecting mesh 7 negative electrode lead wire 8 container
Claims (1)
れる鉄の硫黄化合物を正極又は負極に用いるリチウム一
次電池。1. A lithium primary battery in which a sulfur compound of iron represented by the general formula Fe 1-x S (0 <x <1) is used for a positive electrode or a negative electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9002895A JPH10199544A (en) | 1997-01-10 | 1997-01-10 | Lithium primary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9002895A JPH10199544A (en) | 1997-01-10 | 1997-01-10 | Lithium primary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10199544A true JPH10199544A (en) | 1998-07-31 |
Family
ID=11542101
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9002895A Pending JPH10199544A (en) | 1997-01-10 | 1997-01-10 | Lithium primary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10199544A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6821677B2 (en) * | 2001-03-29 | 2004-11-23 | Kabushiki Kaisha Toshiba | Negative electrode active material and nonaqueous electrolyte battery |
| CN112599737A (en) * | 2020-12-14 | 2021-04-02 | 南京航空航天大学 | Sodium ion battery transition metal sulfide carbon composite negative electrode material and preparation method and application thereof |
-
1997
- 1997-01-10 JP JP9002895A patent/JPH10199544A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6821677B2 (en) * | 2001-03-29 | 2004-11-23 | Kabushiki Kaisha Toshiba | Negative electrode active material and nonaqueous electrolyte battery |
| CN112599737A (en) * | 2020-12-14 | 2021-04-02 | 南京航空航天大学 | Sodium ion battery transition metal sulfide carbon composite negative electrode material and preparation method and application thereof |
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