JPS636750A - Nonaqueous electrolyte battery - Google Patents
Nonaqueous electrolyte batteryInfo
- Publication number
- JPS636750A JPS636750A JP61150583A JP15058386A JPS636750A JP S636750 A JPS636750 A JP S636750A JP 61150583 A JP61150583 A JP 61150583A JP 15058386 A JP15058386 A JP 15058386A JP S636750 A JPS636750 A JP S636750A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- nonaqueous electrolyte
- cupric oxide
- chalcopyrite
- 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
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 10
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 21
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052951 chalcopyrite Inorganic materials 0.000 claims abstract description 12
- NFMAZVUSKIJEIH-UHFFFAOYSA-N bis(sulfanylidene)iron Chemical compound S=[Fe]=S NFMAZVUSKIJEIH-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910000339 iron disulfide Inorganic materials 0.000 claims abstract description 11
- 229960004643 cupric oxide Drugs 0.000 claims abstract description 10
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000011149 active material Substances 0.000 claims abstract description 4
- 229910000733 Li alloy Inorganic materials 0.000 claims description 2
- 239000001989 lithium alloy Substances 0.000 claims description 2
- 208000028659 discharge Diseases 0.000 abstract description 21
- 229910052960 marcasite Inorganic materials 0.000 abstract description 5
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052683 pyrite Inorganic materials 0.000 abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- -1 and in addition Chemical compound 0.000 abstract description 2
- 239000011230 binding agent Substances 0.000 abstract description 2
- BUGICWZUDIWQRQ-UHFFFAOYSA-N copper iron sulfane Chemical compound S.[Fe].[Cu] BUGICWZUDIWQRQ-UHFFFAOYSA-N 0.000 abstract description 2
- 229910002804 graphite Inorganic materials 0.000 abstract description 2
- 239000010439 graphite Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract 1
- 239000004020 conductor Substances 0.000 abstract 1
- 239000011737 fluorine Substances 0.000 abstract 1
- 229910052731 fluorine Inorganic materials 0.000 abstract 1
- 239000013067 intermediate product Substances 0.000 abstract 1
- 239000011347 resin Substances 0.000 abstract 1
- 229920005989 resin Polymers 0.000 abstract 1
- 238000010586 diagram Methods 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
-
- 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】
イ）産業上の利用分野
本発明はリチウム又はリチウム合金を負極活物質とし、
酸化第二銅を正極活物質とする非水電解液電池に関する
ものである、
（ロ）従来の技術
この種電源は高エネルギー密度を有すると共に自己放電
が少なく、且電池電圧が約１．５Ｖであるので既存の１
．５ｖ系電池の代替として注目されているが、放電初期
に電池電圧が落ち込む、又高率放電時における作動電圧
が低いという欠点がある。[Detailed description of the invention] a) Industrial application field The present invention uses lithium or a lithium alloy as a negative electrode active material,
This relates to a non-aqueous electrolyte battery that uses cupric oxide as the positive electrode active material. (b) Conventional technology This type of power source has high energy density, little self-discharge, and a battery voltage of about 1.5V. There is an existing 1
．． Although it is attracting attention as an alternative to 5V type batteries, it has the drawbacks that the battery voltage drops at the beginning of discharge and the operating voltage is low during high rate discharge.
ところで、例えば特開昭５５−１５４０７１号公報に開
示されているように酸化第二銅に硫化鉄を添加すること
が提案されているが上記欠点を解決するには至っていな
い。By the way, it has been proposed to add iron sulfide to cupric oxide, as disclosed in, for example, Japanese Patent Application Laid-Open No. 55-154071, but this has not yet solved the above-mentioned drawbacks.
し１ 発明が解決しようとする問題点
本発明は酸化第二銅−リチウム系の非水電解液電池にお
ける放電初期の落込み及び高率放電時の作動電圧の低下
を改善しようとするものである。1 Problems to be Solved by the Invention The present invention seeks to improve the drop in the initial stage of discharge and the drop in operating voltage during high rate discharge in cupric oxide-lithium non-aqueous electrolyte batteries. .
に）問題点を解決するための手段
酸化第二銅を活物質とする正極に二硫化鉄及び黄銅鉱を
添加する。B) Means for solving the problem Adding iron disulfide and chalcopyrite to a positive electrode using cupric oxide as an active material.
尚、二硫化鉄及び黄銅鉱の合計添加量は正極に対して１
０〜３５重景％の範囲が好ましく、又個々について云え
ば二硫化鉄は５〜２０重量％、黄銅鉱は５〜１５重量％
の範囲が好ましい。In addition, the total amount of iron disulfide and chalcopyrite added is 1 for the positive electrode.
The preferable range is 0 to 35% by weight, and individually speaking, iron disulfide is 5 to 20% by weight, and chalcopyrite is 5 to 15% by weight.
A range of is preferred.
（羽咋用
正極に二硫化鉄及び黄銅鉱を添加すると、放電初期の電
池重圧の落込みが解消され、且高率放電特性が向上する
。(Adding iron disulfide and chalcopyrite to the positive electrode for Hakui eliminates the drop in battery pressure at the beginning of discharge and improves high rate discharge characteristics.
・（へ）実施例
市販特級の酸化第二銅（Ｃｕｂ）７０重量％に、市販特
級の二硫化鉄（ＦｅＳ２）１５５重量、市販特級の黄銅
鉱（ＣｕＦｅＳ２） ５項四％、導電剤としての黒鉛５
重量％及び結着剤としてのフッ素樹脂粉末５重量％を加
えて混合した後、この混合物を約２トン／ｄの圧力で加
圧成型して径１５．０ｍ＋、厚み１゜１聰の成型体を得
、この成型体を２００〜３００℃の温度で熱処理して正
極とする。・(f) Example 70% by weight of commercially available special grade cupric oxide (Cub), 155% by weight of commercially available special grade iron disulfide (FeS2), 4% of commercially available special grade chalcopyrite (CuFeS2), as a conductive agent. graphite 5
After adding and mixing 5% by weight of fluororesin powder as a binder, this mixture was pressure-molded at a pressure of about 2 tons/d to form a molded body with a diameter of 15.0 m+ and a thickness of 1° and 1.5 cm. This molded body is heat-treated at a temperature of 200 to 300°C to obtain a positive electrode.
負極は厚み約０．６關のリチウム圧延板を径１５．０１
に打抜いたものである。電解液はプロピレンカーボネー
トと１．２ジメト牛シエタンとの混合溶媒に過塩素酸リ
チウムを１モル／ｌ溶解させたものヲ用い、又セパレー
タはポリプロピレン不織布ヲ用いて直径２０．（）ｗｔ
１厚み２．５ ｔｔｒｍの本発明電池（Ａ）を作成した
。The negative electrode is a lithium rolled plate with a thickness of about 0.6 mm and a diameter of 15.01 mm.
It was punched out. The electrolyte used was a mixed solvent of propylene carbonate and 1.2 dimethoxyethane dissolved with 1 mol/l of lithium perchlorate, and the separator was made of polypropylene nonwoven fabric with a diameter of 20 mm. ()wt
A battery (A) of the present invention having a thickness of 2.5 ttrm was prepared.
ついで本発明電池の優位性を調べるために、下表に示す
如く正極活物質のみ本発明電池と異なる各種の比較電池
を作成した。Next, in order to examine the superiority of the batteries of the present invention, various comparative batteries were prepared, as shown in the table below, differing only in the positive electrode active material from the batteries of the present invention.
第１図はこれら電池を温度２５℃、負荷８００Ωの条件
下で放電した時の放電特性図であり、第１図より本発明
電池（Ａ）は比較電池（Ｂ）〜（Ｄ）に比して放電初期
の電池落込みがなく、且高率放電時における作動電圧も
高電圧を示すことがわかる。Figure 1 is a discharge characteristic diagram when these batteries were discharged at a temperature of 25°C and a load of 800Ω. Figure 1 shows that the battery of the present invention (A) is superior to the comparative batteries (B) to (D). It can be seen that there is no battery depression in the early stage of discharge, and that the operating voltage during high rate discharge is also high.
この理由は詳かではないが、本発明電池における正極の
場合、Ｃｕ０％ＦｅＳ２及びＣｕＦｅ３２が同時に放電
してＦｅＳ２とＣｕＦｅＳ２との間で反応中間生成物と
ｌｌｉみられる（：ｕｘｐｅｙ３ｚ （１） ｘ 。The reason for this is not clear, but in the case of the positive electrode in the battery of the present invention, Cu0%FeS2 and CuFe32 are discharged simultaneously and are considered to be reaction intermediate products between FeS2 and CuFeS2 (:uxpey3z (1) x).
２〉γ、４＞１）が生成し、この化合物がＣｕ。2>γ, 4>1) is produced, and this compound is Cu.
との並行放電において反応が円滑に進行することが要因
であると考えられる。This is thought to be due to the fact that the reaction progresses smoothly in parallel discharge.
又、第２図は）’ｅ３２とＣｕＦｅＳ２との正極に対す
る添加量と、電池放電容量との関係を示す図であり、第
２図より合計添加量としては正極に対して１０〜３５重
量％の範囲が好ましく、個々につイテ云えばＦｅ５２は
５〜２０重ｆｆｉ％、（ｕＦｅＳ２は。Furthermore, Figure 2 is a diagram showing the relationship between the amounts of 'e32 and CuFeS2 added to the positive electrode and the battery discharge capacity. A preferable range is 5 to 20 ffi% for Fe52, (for uFeS2).
５〜１５重級％の範囲が好ましいことがわかる。It can be seen that a range of 5 to 15% by weight is preferred.
（ト） 発明の効果
上述した如く、酸化第二銅を正極活物質とする非水電解
液電池において、正極に二硫化鉄及び黄銅鉱を添加する
ことにより、初期放電時の電圧落込みを解消でき、Ｌｉ
６率放電特性を改善することができるものであり、この
種電源の用途拡大に資するところ極めて大である。(g) Effects of the invention As mentioned above, in a non-aqueous electrolyte battery using cupric oxide as the positive electrode active material, by adding iron disulfide and chalcopyrite to the positive electrode, the voltage drop during initial discharge can be eliminated. Deki, Li
It is possible to improve the 6-rate discharge characteristics, and it greatly contributes to expanding the uses of this type of power source.
第１図は電池の高率放電特性比較図、第２図は二硫化鉄
と黄銅鉱の添加量と、電池放電各社との関係を示す図で
ある。FIG. 1 is a comparison diagram of high rate discharge characteristics of batteries, and FIG. 2 is a diagram showing the relationship between the amounts of iron disulfide and chalcopyrite added and battery discharge companies.
Claims (2)
、非水電解液と、酸化第二銅を活物質とする正極とを備
え、前記正極に二硫化鉄及び黄銅鉱を添加したことを特
徴とする非水電解液電池。(1) It is characterized by comprising a negative electrode using lithium or a lithium alloy as an active material, a nonaqueous electrolyte, and a positive electrode using cupric oxide as an active material, and iron disulfide and chalcopyrite are added to the positive electrode. Non-aqueous electrolyte battery.
１０〜３５重量％である特許請求の範囲第（１）項記載
の非水電解液電池。(2) The non-aqueous electrolyte battery according to claim (1), wherein the total amount of iron disulfide and chalcopyrite added is 10 to 35% by weight based on the positive electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61150583A JPH0677456B2 (en) | 1986-06-26 | 1986-06-26 | Non-aqueous electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61150583A JPH0677456B2 (en) | 1986-06-26 | 1986-06-26 | Non-aqueous electrolyte battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS636750A true JPS636750A (en) | 1988-01-12 |
| JPH0677456B2 JPH0677456B2 (en) | 1994-09-28 |
Family
ID=15500057
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61150583A Expired - Fee Related JPH0677456B2 (en) | 1986-06-26 | 1986-06-26 | Non-aqueous electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0677456B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012523100A (en) * | 2009-04-06 | 2012-09-27 | イーグルピッチャー テクノロジーズ，エルエルシー | Thermal battery cathode material and battery containing the same |
-
1986
- 1986-06-26 JP JP61150583A patent/JPH0677456B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012523100A (en) * | 2009-04-06 | 2012-09-27 | イーグルピッチャー テクノロジーズ，エルエルシー | Thermal battery cathode material and battery containing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0677456B2 (en) | 1994-09-28 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |